JP2012246474A - Detergent composition for plate display device - Google Patents
Detergent composition for plate display device Download PDFInfo
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- JP2012246474A JP2012246474A JP2012030676A JP2012030676A JP2012246474A JP 2012246474 A JP2012246474 A JP 2012246474A JP 2012030676 A JP2012030676 A JP 2012030676A JP 2012030676 A JP2012030676 A JP 2012030676A JP 2012246474 A JP2012246474 A JP 2012246474A
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- flat panel
- phosphate
- panel display
- cleaning composition
- display device
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- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 239000003599 detergent Substances 0.000 title abstract description 5
- -1 quaternary ammonium salt compound Chemical class 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims description 59
- 239000000126 substance Substances 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
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 claims description 4
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 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
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 claims description 2
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 claims description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 claims description 2
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical group OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 abstract description 26
- 239000000758 substrate Substances 0.000 abstract description 26
- 239000002245 particle Substances 0.000 abstract description 17
- 239000011521 glass Substances 0.000 abstract description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 5
- 235000011187 glycerol Nutrition 0.000 abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 27
- 239000010949 copper Substances 0.000 description 27
- 229910052802 copper Inorganic materials 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 8
- 239000012459 cleaning agent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000011109 contamination Methods 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000000809 air pollutant Substances 0.000 description 4
- 231100001243 air pollutant Toxicity 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- 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
- C11D7/36—Organic compounds containing phosphorus
-
- 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
- C11D1/62—Quaternary ammonium 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
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/266—Esters or carbonates
-
- 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)
- 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)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Cleaning By Liquid Or Steam (AREA)
Abstract
Description
本発明は、平板表示装置用洗浄剤組成物に関する。 The present invention relates to a cleaning composition for flat panel display devices.
平板表示装置(flat panel display device)は、半導体デバイスのように、成膜、露光、エッチングなどの工程を経て製品が製造される。ところが、このような製造工程によって、基板の表面に、各種の有機物や無機物などの大きさが１μｍ以下の非常に小さいパーティクル(particle)により付着汚染が発生する。このようなパーティクルが付着したままで、次の工程処理を施した場合、膜のピンホールまたはピット、配線のショートまたはブリッジが発生し、製品の製造収率が低下する。 A flat panel display device, like a semiconductor device, is manufactured through processes such as film formation, exposure, and etching. However, due to such a manufacturing process, adhesion contamination occurs on the surface of the substrate due to extremely small particles having a size of 1 μm or less such as various organic substances and inorganic substances. When the next process is performed with such particles still attached, film pinholes or pits, wiring shorts or bridges are generated, and the production yield of the product is lowered.
したがって、汚染物を除去するための洗浄が各工程の間に行われており、このための洗浄剤についても多くの研究があった。特許文献１では、有機アミン、有機ホスホン酸、直鎖糖アルコール及び水からなる半導体素子用剥離剤組成物を開示している。ところが、前記特許文献１は、半導体素子に用途が限定されており、銅及び銅合金からなる配線に対する防食能力がないという欠点がある。特許文献２では、アルカノールアミン、有機溶媒、キレート化合物及び水からなる、半導体及びＴＦＴ−ＬＣＤ(Thin Film Transistor-Liquid Crystal Display)用洗浄剤組成物を開示している。ところが、前記特許文献２の公開特許は、有機汚染物及びパーティクルの除去力に劣り、ポリヒドロキシベンゼン系キレート化合物としてのカテコールまたは没食子酸などにより長期間使用の際に析出などの問題が発生しうる。特許文献３では、有機酸成分、有機アルカリ成分、界面活性剤成分および水を含む、半導体デバイス用基板の洗浄剤を開示している。ところが、特許文献３の洗浄剤は、酸性範囲の溶液なので、洗浄初期段階の基本的特性である、有機物や無機物などの大きさが１μｍ以下の非常に小さいパーティクルに対する除去性が不十分である。そして、銅配線に対する防食効果のみがあるという欠点がある。 Therefore, cleaning for removing contaminants is performed between the processes, and there has been much research on cleaning agents for this purpose. Patent Document 1 discloses a release agent composition for a semiconductor element comprising an organic amine, an organic phosphonic acid, a linear sugar alcohol, and water. However, Patent Document 1 has a drawback in that its use is limited to semiconductor elements and there is no anticorrosion ability for wiring made of copper and copper alloys. Patent Document 2 discloses a cleaning composition for a semiconductor and TFT-LCD (Thin Film Transistor-Liquid Crystal Display), which comprises an alkanolamine, an organic solvent, a chelate compound, and water. However, the published patent of Patent Document 2 has poor ability to remove organic contaminants and particles, and may cause problems such as precipitation during long-term use due to catechol or gallic acid as a polyhydroxybenzene chelate compound. . Patent Document 3 discloses a semiconductor device substrate cleaning agent containing an organic acid component, an organic alkali component, a surfactant component, and water. However, since the cleaning agent disclosed in Patent Document 3 is a solution in the acidic range, the removability with respect to very small particles having a size of 1 μm or less such as an organic substance or an inorganic substance, which is a basic characteristic in the initial stage of cleaning, is insufficient. And there exists a fault that there exists only the anticorrosion effect with respect to a copper wiring.
本発明の目的は、ガラス基板、電極または配線上に存在する有無機汚染物またはパーティクルを除去することが可能な平板表示装置用洗浄剤組成物を提供することにある。 An object of the present invention is to provide a cleaning composition for a flat panel display capable of removing presence / absence contaminants or particles present on a glass substrate, electrode or wiring.
本発明の他の目的は、平板表示装置に用いられる銅を含む金属からなる電極または配線などを腐食させることなく、洗浄効果を発揮する平板表示装置用洗浄剤組成物を提供することにある。 Another object of the present invention is to provide a cleaning composition for a flat panel display device that exhibits a cleaning effect without corroding an electrode or wiring made of a metal containing copper used in the flat display device.
本発明の別の目的は、リンス問題が発生せず、経済的かつ環境調和的な平板表示装置用洗浄剤組成物を提供することにある。 Another object of the present invention is to provide a cleaning composition for a flat panel display device that does not cause a rinse problem and is economical and environmentally friendly.
上記目的を達成するために、本発明は、組成物の総重量に対して、第４級アンモニウム塩化合物０．０１〜１０重量％、グリコールエーテル化合物０．０１〜１０重量％、リン酸エステル化合物０．０１〜１０重量％、グリセリン化合物０．０１〜５重量％及び接触角低下剤０．０１〜１重量％を含有し、残部が水からなることを特徴とする、平板表示装置用洗浄剤組成物を提供する。 In order to achieve the above object, the present invention provides a quaternary ammonium salt compound of 0.01 to 10% by weight, a glycol ether compound of 0.01 to 10% by weight, and a phosphate ester compound, based on the total weight of the composition. A cleaning agent for flat panel displays, comprising 0.01 to 10% by weight, 0.01 to 5% by weight of a glycerin compound and 0.01 to 1% by weight of a contact angle reducing agent, the balance being water. A composition is provided.
本発明の平板表示装置用洗浄剤組成物は、ガラス基板、電極または配線上に存在する有無機汚染物またはパーティクルを除去することができる。本発明の平板表示装置用洗浄剤組成物は、平板表示装置に用いられる銅を含む金属からなる電極または配線などを腐食させることなく、洗浄効果を発揮することができる。本発明の平板表示装置用洗浄剤組成物は、多量の水を使用することにより、リンス問題が発生する可能性を低める。そして、本発明の平板表示装置用洗浄剤組成物は経済的かつ環境調和的である。 The cleaning composition for a flat panel display device of the present invention can remove the presence / absence contaminants or particles present on the glass substrate, electrode or wiring. The cleaning composition for a flat panel display device of the present invention can exert a cleaning effect without corroding an electrode or wiring made of a metal containing copper used in the flat panel display device. The cleaning composition for a flat panel display device of the present invention reduces the possibility of causing a rinse problem by using a large amount of water. The flat panel display cleaner composition of the present invention is economical and environmentally friendly.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の平板表示装置用洗浄剤組成物は、第４級アンモニウム塩化合物、グリコールエーテル化合物、リン酸エステル化合物、グリセリン化合物、接触角低下剤及び水を含んでなる。 The flat panel display cleaner composition of the present invention comprises a quaternary ammonium salt compound, a glycol ether compound, a phosphate ester compound, a glycerin compound, a contact angle reducing agent and water.
本発明の平板表示装置用洗浄剤組成物に含まれる第４級アンモニウム塩化合物は、有無機汚染物及びパーティクルに対して優れた洗浄能力を提供し、銅を含む金属からなる電極または配線に対する優れた防食能力を提供する。 The quaternary ammonium salt compound contained in the cleaning composition for a flat panel display device of the present invention provides an excellent cleaning ability for presence / absence of contaminants and particles, and is excellent for an electrode or wiring made of a metal containing copper. Provide anti-corrosion ability.
前記第４級アンモニウム塩化合物は、組成物の総重量に対して、０．０１〜１０重量％、好ましくは０．０５〜５重量％で含まれる。上述した範囲を満足すると、有無機汚染物およびパーティクルに対して洗浄能力が優秀になり、銅を含む金属からなる電極または配線に対する防食能力が優秀になる。 The quaternary ammonium salt compound is contained in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total weight of the composition. When the above-mentioned range is satisfied, the cleaning ability is excellent with respect to the presence / absence of contaminants and particles, and the anticorrosion ability with respect to the electrode or wiring made of a metal containing copper is excellent.
前記第４級アンモニウム塩化合物は、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）、テトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）、テトラプロピルアンモニウムヒドロキシド（ＴＰＡＨ）及びテトラブチルアンモニウムヒドロキシド（ＴＢＡＨ）よりなる群から選ばれる１種または２種以上であることが好ましい。 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). It is preferable that it is a seed | species or 2 or more types.
本発明の平板表示装置用洗浄剤組成物に含まれるグリコールエーテル化合物は、有無機汚染物とパーティクルに対する溶解力を増加させ、経済的かつ環境的に利点を提供する。 The glycol ether compound contained in the cleaning composition for a flat panel display device of the present invention increases the dissolving power with respect to presence / absence of contaminants and particles, and provides an economical and environmental advantage.
前記グリコールエーテル化合物は、組成物の総重量に対して、０．０１〜１０重量％、好ましくは０．０５〜５重量％で含まれる。上述した範囲を満足すると、有無機汚染物とパーティクルに対する溶解力が増加し、洗浄工程が仕上がった後に洗浄剤の残留問題が起こらず、経済的かつ環境的に利点を提供することができる。 The glycol ether compound is contained in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total weight of the composition. If the above-mentioned range is satisfied, the dissolving power with respect to the presence / absence machine contaminants and particles is increased, and there is no problem of remaining of the cleaning agent after the cleaning process is completed, thereby providing an economical and environmental advantage.
前記グリコールエーテル化合物は、エチレングリコールモノブチルエーテル（ＢＧ）、ジエチレングリコールモノメチルエーテル（ＭＤＧ）、ジエチレングリコールモノエチルエテル（カルビトール）、ジエチレングリコールモノブチルエーテル（ＢＤＧ）、ジプロピレングリコールモノメチルエーテル（ＤＰＭ）、ジプロピレングリコールモノエチルエーテル（ＭＦＤＧ）、トリエチレングリコールモノブチルエーテル（ＢＴＧ）、トリエチレングリコールモノエチルエーテル（ＭＴＧ）及びプロピレングリコールモノメチルエーテル（ＭＦＧ）よりなる群から選ばれる１種または２種以上であることが好ましい。 The glycol ether compound includes ethylene glycol monobutyl ether (BG), diethylene glycol monomethyl ether (MDG), diethylene glycol monoethyl ether (carbitol), diethylene glycol monobutyl ether (BDG), dipropylene glycol monomethyl ether (DPM), dipropylene glycol mono One or more selected from the group consisting of ethyl ether (MFDG), triethylene glycol monobutyl ether (BTG), triethylene glycol monoethyl ether (MTG) and propylene glycol monomethyl ether (MFG) are preferred.
本発明の平板表示装置用洗浄剤組成物に含まれるリン酸エステル化合物は、量子性、非量子性溶媒の共溶媒の役目として作用し、基板上に位置する有機汚染物および有機起因性斑に対する優れた洗浄効果を提供する。そして、少量でも優れた有機汚染物除去能力を持つ。 The phosphate ester compound contained in the cleaning composition for flat panel display of the present invention acts as a co-solvent of quantum and non-quantum solvents, and prevents organic contaminants and organic-caused spots located on the substrate. Provides an excellent cleaning effect. And even with a small amount, it has excellent organic contaminant removal ability.
前記リン酸エステル化合物は、組成物の総重量に対して、０．０１〜１０重量％、好ましくは０．０５〜５重量％で含まれる。上述した範囲を満足すると、基板上に位置する有機汚染物及び有機起因性斑に対する優れた洗浄効果を提供することができる。 The phosphoric acid ester compound is contained in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total weight of the composition. When the above-mentioned range is satisfied, an excellent cleaning effect for organic contaminants and organic-caused spots located on the substrate can be provided.
前記リン酸エステル化合物は、下記化学式１で表されることが好ましい。 The phosphate ester compound is preferably represented by the following chemical formula 1.
式中、Ｒ1〜Ｒ３はそれぞれ独立に水素原子、Ｃ1〜Ｃ１０の直鎖または分岐鎖のアルキル基である。前記アルキル基は、メチル基、エチル基、プロピル基またはブチル基であることが好ましい。 In the formula, R1 to R3 each independently represent a hydrogen atom or a C1 to C10 linear or branched alkyl group. The alkyl group is preferably a methyl group, an ethyl group, a propyl group or a butyl group.
前記化学式１で表されるリン酸エステル化合物の例としては、メチルホスフェート、ジメチルホスフェート、トリメチルホスフェート、エチルホスフェート、ジエチルホスフェート、トリエチルホスフェート、トリプロピルホスフェート及びトリブチルホスフェートなどを挙げることができる。 Examples of the phosphate ester compound represented by Formula 1 include methyl phosphate, dimethyl phosphate, trimethyl phosphate, ethyl phosphate, diethyl phosphate, triethyl phosphate, tripropyl phosphate, and tributyl phosphate.
前記リン酸エステル化合物は、単独でまたは２種以上を混合して用いることができる。
本発明の平板表示装置用洗浄剤組成物に含まれるグリセリン化合物は、銅を含む金属からなる電極又は配線の腐食を防止し、有機洗浄力を向上させる。
The phosphoric acid ester compounds can be used alone or in admixture of two or more.
The glycerin compound contained in the cleaning composition for a flat panel display device of the present invention prevents corrosion of an electrode or wiring made of a metal containing copper and improves organic cleaning power.
前記グリセリン化合物は、組成物の総重量に対して、０．０１〜５重量％、好ましくは０．０５〜２重量％で含まれる。上述した範囲を満足すると、有機汚染物に対する洗浄力が低下することなく、銅を含む金属からなる電極又は配線に対する防食特性が優秀になる。 The glycerin compound is contained in an amount of 0.01 to 5% by weight, preferably 0.05 to 2% by weight, based on the total weight of the composition. When the above-described range is satisfied, the anticorrosion property for the electrode or wiring made of a metal containing copper is excellent without deteriorating the detergency against organic contaminants.
本発明の平板表示装置用洗浄剤組成物に含まれる接触角低下剤は、洗浄工程後の基板の親水性を確保するために含まれるもので、銅を含む金属の腐食を防止する。 The contact angle reducing agent contained in the cleaning composition for a flat panel display device of the present invention is included to ensure the hydrophilicity of the substrate after the cleaning step, and prevents corrosion of metals including copper.
前記接触角低下剤は、組成物の総重量に対して、０．０１〜１重量％、好ましくは０．０１〜０．５重量％で含まれる。上述した範囲を満足すると、洗浄工程後の基板の親水性確保がより容易であり、銅を含む金属からなる電極または配線に対する防食特性を向上させることができる。前記接触角低下剤はチオグリセリンであることが好ましい。 The contact angle reducing agent is included in an amount of 0.01 to 1% by weight, preferably 0.01 to 0.5% by weight, based on the total weight of the composition. When the above-described range is satisfied, it is easier to ensure the hydrophilicity of the substrate after the cleaning step, and the anticorrosion property for the electrode or wiring made of a metal containing copper can be improved. The contact angle reducing agent is preferably thioglycerin.
本発明の平板表示装置用洗浄剤組成物に含まれる水は、組成物の総重量が１００重量％となるように残量を含む。前記水は、半導体工程用を使用し、好ましくは１８ＭΩ・ｃｍ以上の脱イオン水を使用する。 The water contained in the cleaning composition for a flat panel display of the present invention contains the remaining amount so that the total weight of the composition is 100% by weight. The water is used for a semiconductor process, preferably deionized water of 18 MΩ · cm or more.
本発明の平板表示装置用洗浄剤組成物は、トリアゾール系化合物を用いることなく、銅を含む金属からなる電極または配線に防食能力を与えることができる。前記トリアゾール系化合物を用いると、防食能力には優れるが、銅の表面に前記トリアゾール系化合物が吸着して残される問題があるので、利用を控えることが好ましい。 The cleaning composition for a flat panel display device of the present invention can provide an anticorrosive ability to an electrode or wiring made of a metal containing copper without using a triazole compound. When the triazole compound is used, the anticorrosion ability is excellent, but there is a problem that the triazole compound is adsorbed and left on the surface of copper.
本発明は、前記平板表示装置用洗浄剤組成物から製造された平板表示装置を提供する。前記平板表示装置の例としては有機電界発光素子、液晶ディスプレイなどを挙げることができる。 The present invention provides a flat panel display manufactured from the cleaning composition for a flat panel display. Examples of the flat panel display include organic electroluminescent elements and liquid crystal displays.
本発明の平板表示装置用洗浄剤組成物は、ガラス基板、電極または配線上に存在する有無機汚染物またはパーティクルを除去することができる。本発明の平板表示装置用洗浄剤組成物は、平板表示装置に用いられる銅を含む金属からなる電極または配線などを腐食させることなく、洗浄効果を発揮することができる。本発明の平板表示装置用洗浄剤組成物は、多量の水を使用することにより、リンス問題が発生する可能性を低める。そして、本発明の平板表示装置用洗浄剤組成物は経済的かつ環境調和的である。 The cleaning composition for a flat panel display device of the present invention can remove the presence / absence contaminants or particles present on the glass substrate, electrode or wiring. The cleaning composition for a flat panel display device of the present invention can exert a cleaning effect without corroding an electrode or wiring made of a metal containing copper used in the flat panel display device. The cleaning composition for a flat panel display device of the present invention reduces the possibility of causing a rinse problem by using a large amount of water. The flat panel display cleaner composition of the present invention is economical and environmentally friendly.
以下、実施例及び試験例によって本発明をさらに詳細に説明する。ところが、本発明の範囲はこれらの実施例及び試験例によって限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Test Examples. However, the scope of the present invention is not limited by these examples and test examples.
−実施例１〜実施例１２、比較例１〜比較例５：洗浄剤組成物の製造−
攪拌器が設置されている混合槽に、下記表１に記載の成分を表１に記載の組成比に基づいて混合し、常温で１時間５００ｒｐｍの速度で攪拌して洗浄剤組成物を製造した。
-Examples 1 to 12, Comparative Examples 1 to 5: Production of detergent composition-
Ingredients shown in Table 1 below were mixed in a mixing tank in which a stirrer was installed based on the composition ratios shown in Table 1 and stirred at a speed of 500 rpm for 1 hour at room temperature to produce a cleaning composition. .
−試験例：洗浄剤組成物の特性評価−
１）銅エッチング速度の評価
まず、銅が２５００Å（＝２５０ｎｍ）の厚さに形成されたガラス基板を、実施例１〜実施例１２および比較例１〜比較例５の洗浄剤組成物に３０分間浸漬させる。この際、洗浄剤の温度は、２５℃であり、銅膜の厚さを浸漬させる前及び後に測定する。また、銅膜の溶解速度を銅膜の厚さ変化から計算して測定する。結果を表２に示す。
-Test example: Characteristic evaluation of cleaning composition-
1) Evaluation of Copper Etching Rate First, a glass substrate having a copper thickness of 2500 mm (= 250 nm) was applied to the cleaning compositions of Examples 1 to 12 and Comparative Examples 1 to 5 for 30 minutes. Soak. At this time, the temperature of the cleaning agent is 25 ° C., and is measured before and after immersing the thickness of the copper film. The dissolution rate of the copper film is calculated from the change in thickness of the copper film and measured. The results are shown in Table 2.
２）汚染物除去力の評価−１
有機汚染物の除去力評価のために２ｃｍ×２ｃｍのサイズに形成されたガラス基板及び銅基板上を有機成分サインペン及び指紋で汚染させ、汚染した基板をスプレー式基板洗浄装置を用いて１分間２５℃で実施例１〜実施例１２及び比較例１〜比較例５の洗浄剤組成物で洗浄した。洗浄の後、超純水で３０秒間洗浄した後、窒素で乾燥させた。
2) Evaluation of contaminant removal ability-1
In order to evaluate the removal ability of organic contaminants, the glass substrate and copper substrate formed in a size of 2 cm × 2 cm are contaminated with an organic component sign pen and fingerprint, and the contaminated substrate is used for 25 minutes for 1 minute using a spray type substrate cleaning device. Washing was performed with the detergent compositions of Examples 1 to 12 and Comparative Examples 1 to 5 at ° C. After washing, it was washed with ultrapure water for 30 seconds and then dried with nitrogen.
ここで、有機サインペンの除去有無の評価基準として、有機成分サインペンによる汚染の後、２４時間大気乾燥したものを用いて評価を行った。
○：除去された場合、×：除去されていない場合
ここで、銅基板に対する指紋の除去有無の評価基準は以下の通り。
Here, as an evaluation standard for the presence or absence of removal of the organic sign pen, evaluation was performed using an object that was air-dried for 24 hours after contamination with the organic component sign pen.
○: When removed, ×: When not removed Here, the evaluation criteria for the presence or absence of the removal of the fingerprint on the copper substrate are as follows.
１０：完全に除去された場合、０：除去されていない場合
３）汚染物除去力の評価−２
また、銅基板を大気中に２４時間放置して大気中の各種有機物、無機物、パーティクルなどに汚染させた後、スプレー式銅基板洗浄装置を用いて１分間２５℃で実施例１〜実施例１２および比較例１〜比較例５の洗浄剤組成物で洗浄した。洗浄の後、超純水で３０秒間洗浄した後、窒素で乾燥させた。前記ガラス基板上に０．５μＬの超純水の液滴を滴下させて洗浄後の接触角を測定した。結果を表２に示す。
10: When completely removed, 0: When not removed 3) Evaluation of contaminant removal power-2
Moreover, after leaving a copper substrate in air | atmosphere for 24 hours and contaminating with various organic substance, inorganic substance, particles, etc. in air | atmosphere, Example 1-Example 12 at 25 degreeC for 1 minute using a spray type copper substrate washing | cleaning apparatus. And it wash | cleaned with the cleaning composition of Comparative Examples 1-5. After washing, it was washed with ultrapure water for 30 seconds and then dried with nitrogen. A 0.5 μL ultrapure water droplet was dropped on the glass substrate, and the contact angle after cleaning was measured. The results are shown in Table 2.
４）パーティクル除去力の評価
実施例１〜実施例１２及び比較例１〜比較例５の洗浄剤組成物によって、無機パーティクルソリューションで汚染させたガラス基板に対する洗浄を行った。より詳細に説明すると、ガラス基板を平均粒径０．８μｍの有機パーティクルソリューションで汚染させ、１分間３０００ｒｐｍでスピンドライした後、スプレー式ガラス基板洗浄装置を用いて１分間２５℃でそれぞれの洗浄剤で洗浄した。洗浄の後、超純水で３０秒間洗浄した後、窒素で乾燥させた。洗浄前後のパーティクル数は表面粒子測定器（Ｔｏｐｃｏｎ ＷＭ−１５００）で０．１μｍ以上のパーティクル数を測定した。結果を表２に示す。
4) Evaluation of particle removal power The glass substrates contaminated with the inorganic particle solution were cleaned with the cleaning compositions of Examples 1 to 12 and Comparative Examples 1 to 5. More specifically, a glass substrate is contaminated with an organic particle solution having an average particle diameter of 0.8 μm, spin-dried at 3000 rpm for 1 minute, and then each cleaning agent is used at 25 ° C. for 1 minute using a spray glass substrate cleaning apparatus. Washed with. After washing, it was washed with ultrapure water for 30 seconds and then dried with nitrogen. The number of particles before and after cleaning was measured by a surface particle measuring device (Topcon WM-1500). The results are shown in Table 2.
表２を参照すると、本発明に係る実施例１〜実施例１２の洗浄剤組成物は、銅に対する防食性能に優れるうえ、有機サインペン、大気汚染物に対する除去力にも優れることが分かる。 Referring to Table 2, it can be seen that the cleaning compositions of Examples 1 to 12 according to the present invention are excellent in anticorrosion performance against copper and excellent in removing power against organic sign pens and air pollutants.
一方、図１は有機汚染物のうち有機サインペンの跡で汚染されたガラス基板を示す写真である。図２は本発明の実施例４に係る洗浄剤組成物を用いて有機汚染物のうち有機サインペンの跡が除去される結果を示す写真である。図３は有機汚染物のうち指紋で汚染された銅基板を示す写真である。図４は本発明の実施例４に係る洗浄剤組成物を用いて有機汚染物のうち指紋汚染成分が除去される結果を示す写真である。 On the other hand, FIG. 1 is a photograph showing a glass substrate contaminated with traces of organic signature pens among organic contaminants. FIG. 2 is a photograph showing a result of removing traces of an organic sign pen from organic contaminants using the cleaning composition according to Example 4 of the present invention. FIG. 3 is a photograph showing a copper substrate contaminated with fingerprints among organic contaminants. FIG. 4 is a photograph showing a result of removing fingerprint contamination components among organic contaminants using the cleaning composition according to Example 4 of the present invention.
図１〜図４を参照すると、実施例４の洗浄剤組成物を用いると、有機汚染物に対する洗浄能力に優れることが分かる。 1 to 4, it can be seen that when the cleaning composition of Example 4 is used, the cleaning ability against organic contaminants is excellent.
一方、比較例１、比較例２および比較例３の場合は、有機サインペンや指紋汚染、大気汚染物などに対する洗浄力に優れないことが分かる。比較例４の場合は、銅に対する防食性能および大気汚染物に対する洗浄力に優れないことが分かる。そして、比較例５の場合は、銅に対する防食性能に優れず、大気汚染物に対する除去力にも優れなかった。 On the other hand, in the case of Comparative Example 1, Comparative Example 2 and Comparative Example 3, it can be seen that the cleaning power against organic sign pens, fingerprint contamination, air pollutants and the like is not excellent. In the case of the comparative example 4, it turns out that it is not excellent in the anti-corrosion performance with respect to copper, and the cleaning power with respect to an air pollutant. And in the case of the comparative example 5, it was not excellent in the anti-corrosion performance with respect to copper, and was not excellent also in the removal power with respect to an air pollutant.
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| KR20190030609A (en) * | 2017-09-14 | 2019-03-22 | 세메스 주식회사 | Anhydrous substrate cleaning compositions, substrate cleaning method and substrate treating apparatus |
| US11004675B2 (en) | 2017-09-14 | 2021-05-11 | Semes Co., Ltd. | Substrate cleaning composition, substrate treating method, and substrate treating apparatus |
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| KR102028484B1 (en) * | 2014-02-14 | 2019-10-04 | 동우 화인켐 주식회사 | A composition for removing reactive mesogen-organic alignment layer |
| CN106753855A (en) * | 2016-11-29 | 2017-05-31 | 枞阳县铭瑞电子科技有限公司 | A kind of good glass cleaner of corrosion-free clean effect |
| CN109266463A (en) * | 2018-09-27 | 2019-01-25 | 镇江奥视达光学有限公司 | A kind of cleaning agent of concave lens and preparation method thereof |
| KR102195007B1 (en) | 2018-10-11 | 2020-12-29 | 세메스 주식회사 | Substrate cleaning compositions, substrate cleaning method and substrate treating apparatus |
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| KR20190030609A (en) * | 2017-09-14 | 2019-03-22 | 세메스 주식회사 | Anhydrous substrate cleaning compositions, substrate cleaning method and substrate treating apparatus |
| KR102152911B1 (en) * | 2017-09-14 | 2020-09-08 | 세메스 주식회사 | Anhydrous substrate cleaning compositions, substrate cleaning method and substrate treating apparatus |
| US11004675B2 (en) | 2017-09-14 | 2021-05-11 | Semes Co., Ltd. | Substrate cleaning composition, substrate treating method, and substrate treating apparatus |
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