CN101000468B - 薄膜晶体管液晶显示器用彩色抗蚀剂剥离液组合物 - Google Patents
薄膜晶体管液晶显示器用彩色抗蚀剂剥离液组合物 Download PDFInfo
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- CN101000468B CN101000468B CN2007100012672A CN200710001267A CN101000468B CN 101000468 B CN101000468 B CN 101000468B CN 2007100012672 A CN2007100012672 A CN 2007100012672A CN 200710001267 A CN200710001267 A CN 200710001267A CN 101000468 B CN101000468 B CN 101000468B
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- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 239000007788 liquid Substances 0.000 title claims abstract description 16
- 239000010409 thin film Substances 0.000 title abstract description 5
- 239000004973 liquid crystal related substance Substances 0.000 title abstract description 4
- -1 inorganic base hydroxides Chemical class 0.000 claims abstract description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000005210 alkyl ammonium group Chemical group 0.000 claims abstract description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000007529 inorganic bases Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
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- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 3
- BQCCJWMQESHLIT-UHFFFAOYSA-N 1-propylsulfinylpropane Chemical compound CCCS(=O)CCC BQCCJWMQESHLIT-UHFFFAOYSA-N 0.000 claims description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 3
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 3
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 3
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 claims description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 14
- 239000000758 substrate Substances 0.000 abstract description 11
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
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- 239000010953 base metal Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
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- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229940087646 methanolamine Drugs 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
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- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
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- 239000005977 Ethylene Substances 0.000 description 1
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- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
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- 229910018503 SF6 Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DPRMFUAMSRXGDE-UHFFFAOYSA-N ac1o530g Chemical compound NCCN.NCCN DPRMFUAMSRXGDE-UHFFFAOYSA-N 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
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- 150000003961 organosilicon compounds Chemical class 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
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- YTWOHSWDLJUCRK-UHFFFAOYSA-N thiolane 1,1-dioxide Chemical compound O=S1(=O)CCCC1.O=S1(=O)CCCC1 YTWOHSWDLJUCRK-UHFFFAOYSA-N 0.000 description 1
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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
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/40—Monoamines or polyamines; Salts thereof
-
- 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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- 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
- G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
-
- 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
-
- 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
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Optical Filters (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
本发明涉及一种，为了再利用TFT-LCD彩色滤光片的制造过程中产生的不良基板，去除彩色抗蚀剂及涂层的薄膜晶体管液晶显示器用彩色抗蚀剂剥离液组合物，具体涉及一种包括：(a)1-50w％的选自无机碱氢氧化物、烷基氢氧化铵及苯基烷基氢氧化铵的氢氧化物，所述烷基氢氧化铵包含C1-C4的烷基；(b)5-30w％的极性硫化物；(c)5-35w％的烷撑二醇醚，所述烷撑二醇醚包含C1-C4的烷基；(d)2-30w％的烷撑二醇二烷基醚，所述烷撑二醇二烷基醚包含C1-C4的烷基；(e)2-30w％的水溶性胺化合物；(f)残余量水的彩色抗蚀剂用剥离液组合物。
Description
技术领域
本发明涉及一种薄膜晶体管液晶显示器(以下简称“TFT-LCD”)用彩色抗蚀剂的剥离液组合物，尤其涉及一种用于去除在彩色滤光片制程中所产生的不良基板上的彩色抗蚀剂和含彩色抗蚀剂的覆膜(over coat)，使之能够作为黑膜(Black Mask)或玻璃基板回收使用的TFT-LCD彩色抗蚀剂剥离液组合物。
背景技术
彩色滤光基板由红绿蓝色图案、黑色矩阵、保护膜(即覆膜)及公用电极所构成。其中，黑色矩阵用于防止各像素之间的漏光，提高对比度，公用电极用于对液晶单元施加电压。
彩色滤光片的制造工序如下。首先，根据用途在玻璃基板上涂覆作为黑色矩阵材料的铬/氧化铬(Cr/CrOx)或有机材料，以形成图案。形成黑膜图案之后，为了显现色彩，通过照相平板印刷术形成彩色抗蚀剂图案。将彩色抗蚀剂涂敷在玻璃基板上并进行曝光，从而通过光聚合反应硬化彩色抗蚀剂。曝光工序之后，通过显影工序去除彩色抗蚀剂中未经曝光的部分，之后进行烧成工序。
彩色抗蚀剂可通过颜料分散法、染色法、电着法(ElectrodepesitionMethod)等方法制造，而常用的方法是颜料分散法。其中，通常在光致抗蚀剂等感光组合物即光聚合引发剂、单体、粘合剂中分散有用于实现色彩的有机颜料。光聚合引发剂是在受光后产生自由基的高感光性化合物，而单体则通过自由基引发聚合反应后，结合成高分子形态，从而成为不溶解于显影溶剂的形态。粘合剂，在常温条件下保护液体状单体使之不易于溶解于显影液，并决定颜料分散的稳定性及红绿蓝图案的耐热性、耐光性、耐化学性等可靠性。
目前，在彩色滤光片制造过程中所产生的不良彩色滤光片基板，其彩色抗蚀剂一经硬化几乎不可能去除，因而无法修正图案中的错误部分，而且目前几乎没有可去除彩色抗蚀剂的溶剂，所以大部分不良彩色滤光片都不经过修正等再处理过程，就直接作出废弃处理。
上述彩色抗蚀剂具有负性抗蚀剂的特性，通常，负性抗蚀剂与正性抗蚀剂相比，更难以进行剥离，因此负性抗蚀剂要求强劲的剥离性能。
因此，以往采用了使用无机类剥离液和等离子体的活性离子蚀刻方法(RIE，reactive ion etching)。但是，当使用上述无机类剥离液时，如果将硫酸、硝酸、发烟硫酸、硝酸及过氧化氢的混合液加热到120℃以上，不仅对操作者的安全造成威胁，而且因加热而增加发生火灾的危险性，所以在使用时必须多加小心。例如，日本专利公开公报昭51-72503号公开了烷基苯磺酸和沸点为150℃以上的非卤化芳香烃溶剂的混合液；美国专利第4165294号公开了烷基芳基磺酸盐和水溶性芳族磺酸、非卤化芳香烃溶剂的混合液；欧洲专利第0119337号公开了有机磺酸和1，2-二羟基苯中加入极性或非极性有机溶剂的剥离剂。
另外，美国专利第5756239号公开了一种利用等离子体的活性离子蚀刻(reactive ion etching，RIE)方法，该方法通过连续使用氧-活性离子蚀刻(O2-RIE)、六氟化硫-活性离子蚀刻(SF6-RIE)，去除以常用的湿式蚀刻无法去除的硬化的彩色抗蚀剂；而美国专利第5059500号公开了一种利用等离子体的活性离子蚀刻(RIE)方法，该方法对于用聚酯、聚酰胺、酚醛清漆树脂形成吸收层，用聚硅烷、聚硅氧烷、有机硅化合物、氧化硅、氮化硅混合物形成障壁层的已硬化的彩色抗蚀剂，由使用氧气的等离子体去除吸收层，并由使用六氟化硫或三氯化氮去除障壁层。但是，上述利用等离子体的彩色滤光片蚀刻方法，需要有高真空环境及高能量，难以控制工艺条件，难以用于大面积彩色滤光片上，且其设备昂贵。
如上所述，以往的彩色抗蚀剂剥离方法，存在难以稳定地去除大量彩色抗蚀剂，且威胁操作者的安全，以及降低生产效率或产量等问题。
因此，目前需要有一种方法能够通过安全的方式来去除大量的彩色抗蚀剂。
发明内容
本发明鉴于上述问题而作，其目的在于提供一种剥离液组合物，该组合物能够通过安全的方式来大量去除TFT-LCD彩色滤光片的制程中所使用的彩色抗蚀剂及涂层。
为实现上述目的，本发明提供一种彩色抗蚀剂剥离液组合物，其特征在于，包括：
a)1-50w％的选自无机碱氢氧化物(alkali Hydroxide)、烷基氢氧化铵(alkyl ammonium hydroxide)及苯基烷基氢氧化铵(alkyl phenyl ammoniumhydroxide)的氢氧化物，所述烷基氢氧化铵包含C1-C4的烷基；
b)5-30w％的极性硫化物；
c)5-35w％的烷撑二醇醚(alkylene glycol ether)，所述烷撑二醇醚包含C1-C4的烷基；
d)2-30w％的烷撑二醇二烷基醚(alkylene glycol dialkyl ether)，所述烷撑二醇二烷基醚包含C1-C4的烷基；
e)230w％的水溶性胺化合物；
f)残余量水。
本发明的彩色抗蚀剂剥离液组合物，可在短时间内轻易除去彩色抗蚀剂，且在后续的冲洗工序中，无需使用异丙醇、二甲亚砜等有机溶剂，只需使用纯水就可以冲洗。
具体实施方式
下面，详细说明本发明。
为了研发对彩色抗蚀剂及涂层更为有效的剥离方法，使以往基本上都被废弃的彩色滤光片基板能够得到回收使用而进行重复研究的结果，发现使用具有特定组分的剥离液组合物，就可易于去除彩色抗蚀剂及涂层，从而完成了本发明。
用于本发明剥离液组合物的a)氢氧化物，优选选自无机碱氢氧化物、烷基氢氧化铵及苯基烷基氢氧化铵中，其中，所述烷基氢氧化铵包含C1-C4的烷基。彩色滤光片的制程中，由于残留金属不会受太大的影响，因此也可使用无机碱氢氧化物。基于上述组合物的总量，上述氢氧化物优选可包含1-50w％，如果其含量低于1w％，就会使其对构成彩色抗蚀剂的高分子成分的渗透力下降，从而难以完全地去除彩色抗蚀剂；而如果其含量超过50w％，就会加深溶胀现象，并析出无机碱来改变剥离液组分，进而在特定组分下发生分层现象而对剥离性能产生负面影响。另外，由于烷基氢氧化铵及烷基烯丙基氢氧化铵(Alkyl allyl ammonium hydroxide)的性质不稳定，所以最好是将其溶于水后使用。
上述a)无机碱氢氧化物，优选选自氢氧化锂(lithium hydroxide)、氢氧化钠(Sodium hydroxide)、氢氧化钾(potassium hydroxide)及其混合物。上述包含C1-C4的烷基的烷基氢氧化铵，优选选自四乙基氢氧化铵(Tetraethylammonium hydroxide)、四甲基氢氧化铵(tetramethylammonium hydroxide)、四丁基氢氧化铵(tetrabutylammonium hydroxide)及其混合物。另外，上述苯基烷基氢氧化铵优选使用三甲基苄基氢氧化铵(Benzyltrimethylammoniumhydroxide)。
另外，本发明中上述b)极性硫化物对彩色抗蚀剂的渗透力和溶解力极佳，因此可渗透到彩色抗蚀剂的高分子之间，引发溶胀现象。基于组合物总量，优选使用5-30w％的极性硫化物。此时，如果其含量低于5w％，就难以去除全部彩色抗蚀剂；而如果其含量高于30w％，就会降低其与无机碱氢氧化物的融合，从而难以期待有剥离性能的提高。本发明的极性硫化物优选选自二甲亚砜(Dimethylsulfoxide)、二乙亚砜(ethylsulfoxide)、二丙基亚砜(dipropylsulfoxide)、环丁砜(Sulfolane)及其混合物。
上述c)包含C1-C4烷基的烷撑二醇醚对彩色抗蚀剂具有优秀的溶解力，并具有优秀的表面张力降低能力，其可降低悬浮状彩色抗蚀剂和玻璃基板表面之间的张力，使彩色抗蚀剂易于剥离，并溶解上述被剥离的彩色抗蚀剂中粘合剂或聚合物等成分。基于组合物总量，优选使用5-35w％的上述烷撑二醇醚，此时，如果其含量低于5w％，就难以完全去除彩色抗蚀剂；而如果其含量高于35w％，就会阻碍无机碱金属离子的活性，从而难以期待有剥离性能的提高。本发明所使用的烷撑二醇醚，优选选自乙二醇丁醚(ethylene glycolMonobutyl Ether)、二乙二醇一丁醚(diethylene glycol Monobutyl Ether)、三乙二醇一丁醚(triethylene glycol Monobutyl Ether)、乙二醇一甲醚(ethylene glycol Monomethyl Ether)、二乙二醇一甲醚(diethylene glycolMonomethyl Ether)、三乙二醇一甲醚(triethylene glycol MonomethylEther)、乙二醇乙醚(ethylene glycol Monoethylether)及其混合物。
上述d)包含C1-C4烷基的烷撑二醇二烷基醚(alkylene glycol dialkylether)对彩色抗蚀剂具有优秀的溶解力，因此可渗透于彩色抗蚀剂的高分子链中，起到断链和解链的作用，从而使彩色抗蚀剂易于剥离，并溶解上述被剥离的彩色抗蚀剂中粘合剂或聚合体等成分。基于组合物总量，优选使用2-30w％的上述烷撑二醇二烷基醚，最好使用5-30w％。此时，如果其含量低于2w％，就难以完全去除彩色抗蚀剂，而如果其含量超过30w％，就会阻碍无机碱金属离子的活性，从而难以期待有剥离性能的提高。本发明中的烷撑二醇二烷基醚，优选选自乙二醇二甲醚(ethylene glyco ldimethyl ether)、二甘醇二甲醚(diethylene glycol dimethyl ether)、三甘醇二甲醚(triethyleneglycol dimethyl ether)、二乙二醇二乙醚(diethylene glycol diethylether)、二丙二醇二甲醚(dipropylene glycol dimethyl ether)、二乙二醇甲乙醚(diethylene glycol methyl ethyl ether)及其混合物。
上述e)水溶性胺化合物可渗透于构成彩色抗蚀剂的高分子中，并将彩色抗蚀剂从玻璃基板上剥离。基于组合物总量，优选使用2-30w％的上述水溶性胺化合物，最好是使用5-30w％。此时，如果水溶性胺化合物的含量低于2w％，就会降低其对彩色抗蚀剂的渗透力，从而难以完全去除彩色抗蚀剂，进而在无机碱氢氧化物之间产生分层现象；而如果其含量超过30w％，就会阻碍无机碱金属离子的活性，从而难以期待有剥离性能的提高。上述水溶性胺化合物优选选自n-甲基甲醇胺(n-methyl methanol amine)、单甲醇胺(mono methanolamine)、乙二胺(ethylene diamine)及羟基胺(Hydroxylamine)。
另外，本发明中的f)水，优选使用通过离子交换树脂进行过滤的纯水，最好使用比电阻等于或高于18MΩ的超纯水。在本发明组合物中，可包含残余量的上述纯水，而基于组合物总量，优选使用4-49w％的纯水。此时，如果纯水含量低于4w％，在工艺温度下，会使组合物的成分发生变化，从而会析出无机碱离子，进而降低上述彩色滤光片用剥离液组合物的活化期稳定性(potstability)；而如果其含量超过49w％，在工程温度条件下，由于水的蒸发而将增加剥离液组合物的损失。
本发明的上述剥离液组合物和以往技术相比，可易于去除彩色抗蚀剂及涂层，而且在彩色抗蚀剂剥离工序中，可把对下层金属布线的腐蚀最小化。
下面，参照实施例进一步详细说明本发明。但下述实施例仅仅是用于说明本发明的示例，下述实施例也理所应当不能限定本发明的保护范围。
在下述实施例中，若没有其他说明，百分比及混合比均以重量为基准。
实施例1-12及比较例1-22
按照下表1及表2中所示比例，混合a至f成分，以制备如实施例1-12及比较例1-22的彩色抗蚀剂剥离液组合物。
(表1)
(表2)
注：上述表1及表2中，
EG：乙二醇
nMEA：n-甲基甲醇胺
DMSO：二甲亚砜
MEA：单乙醇胺
DESO：二乙亚砜
HDA：羟基胺
实验例
下面，使用如以下工序制得的彩色滤光片基板，对由上述实施例1-12及比较例1-22所制得的彩色抗蚀剂剥离液组合物进行性能评价。
对彩色抗蚀剂的剥离实验
制造试片
在底部镀有铬或氧化铬的康宁玻璃基板(corning glass)上形成彩色滤光片图案，并按照红、绿、蓝顺序，通过照相平板印刷工序涂覆彩色抗蚀剂，即通过旋涂法涂覆常用的彩色抗蚀剂组合物(东进世美肯株式会社制造，产品名称：DCR-725S)，并使其最终膜厚达到1.7μm。之后，将所述抗蚀膜置于热板上，并在90℃的温度下，进行120秒的预烘干。然后，进行曝光，并在常温下，以1％的氢氧化钾(KOH)显影液进行60秒的显影后，在温度为220℃的烤炉中，对上述形成图案的试片进行20分钟的硬烤。
彩色抗蚀剂剥离实验
在50℃的温度下，将上述所制得的试片分别于彩色抗蚀剂剥离液组合物中浸渍2分钟、5分钟、10分钟。接着，从彩色抗蚀剂剥离液组合物中取出上述试片，并用超纯水进行水洗之后，再利用氮气干燥，之后，用扫描电子显微镜(SEM，日立公司，产品名称：S-4100)检测图案中彩色抗蚀剂的残留情况后，按照以下基准，评价彩色抗蚀剂的去除性能，并将其结果显示在表3中。
◎：全被去除。
○：去除70％。
△：去除30％。
×：全没有去除。
(表3)
从上述表3中可知，实施例1-12即使在浸渍初期，红绿蓝颜色图案的去除率也很优秀，而经过5分钟后则完全去除红绿蓝图案，与此相反，比较例122在浸渍初期，红绿蓝图案完全没有被去除，而经过5分钟后也仍然残留部分图案，再经过更长时间之后，才能完全去除所有的图案。
Claims (4)
1.一种彩色抗蚀剂剥离液组合物，其特征在于，包括：
a)1-50w％的选自无机碱氢氧化物、烷基氢氧化铵及苯基烷基氢氧化铵的氢氧化物，所述烷基氢氧化铵包含C1-C4的烷基；
b)5-30w％的极性硫化物，其选自二甲亚砜、二乙亚砜、二丙基亚砜、环丁砜及其混合物；
c)5-35w％的烷撑二醇醚，所述烷撑二醇醚选自乙二醇一丁醚、二乙二醇一丁醚、三乙二醇一丁醚、乙二醇一甲醚、二乙二醇一甲醚、三乙二醇一甲醚、乙二醇乙醚或其混合物；
d)2-30w％的烷撑二醇二烷基醚，所述烷撑二醇二烷基醚包含C1-C4的烷基；
e)2-30w％的水溶性胺化合物，其选自n-甲基甲醇胺、单甲醇胺、乙二胺及羟基胺；以及
f)残余量水。
2.根据权利要求1所述的彩色抗蚀剂剥离液组合物，其特征在于：
上述包含C1-C4的烷基的烷撑二醇二烷基醚选自：乙二醇二甲醚，二甘醇二甲醚，三甘醇二甲醚，二乙二醇二乙醚，二丙二醇二甲醚，二乙二醇甲基乙醚及其混合物。
3.根据权利要求1所述的彩色抗蚀剂剥离液组合物，其特征在于：
上述无机碱氢氧化物选自氢氧化锂、氢氧化钠、氢氧化钾及其混合物。
4.根据权利要求1所述的彩色抗蚀剂剥离液组合物，其特征在于：
上述包含C1-C4的烷基的烷基氢氧化铵选自四乙基氢氧化铵、四甲基氢氧化铵、四丁基氢氧化铵、三甲基苄基氢氧化铵、氢氧化铵及其混合物。
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| KR100779037B1 (ko) * | 2001-09-26 | 2007-11-27 | 주식회사 동진쎄미켐 | 티에프티 엘시디용 칼라 레지스트 박리액 조성물 |
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- 2007-01-04 KR KR1020070000865A patent/KR101328097B1/ko active IP Right Grant
- 2007-01-11 TW TW096101161A patent/TWI408517B/zh active
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| EP1178359A2 (en) * | 2000-08-03 | 2002-02-06 | Shipley Co. L.L.C. | Stripping composition |
| CN1439932A (zh) * | 2002-02-19 | 2003-09-03 | 株式会社德成 | 用于剥离光刻胶的组合物 |
| CN1577112A (zh) * | 2003-07-10 | 2005-02-09 | 东进瑟弥侃株式会社 | 去除tft－lcd制造工艺中彩色抗蚀剂的剥离组合物 |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW200727093A (en) | 2007-07-16 |
| CN101000468A (zh) | 2007-07-18 |
| KR20070075277A (ko) | 2007-07-18 |
| TWI408517B (zh) | 2013-09-11 |
| KR101328097B1 (ko) | 2013-11-13 |
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