WO2019156363A1 - Mask cleaning solution composition - Google Patents

Mask cleaning solution composition Download PDF

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Publication number
WO2019156363A1
WO2019156363A1 PCT/KR2019/000230 KR2019000230W WO2019156363A1 WO 2019156363 A1 WO2019156363 A1 WO 2019156363A1 KR 2019000230 W KR2019000230 W KR 2019000230W WO 2019156363 A1 WO2019156363 A1 WO 2019156363A1
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WO
WIPO (PCT)
Prior art keywords
minutes
cleaning liquid
liquid composition
mask cleaning
mask
Prior art date
Application number
PCT/KR2019/000230
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French (fr)
Korean (ko)
Inventor
김성식
고경준
김정현
방순홍
Original Assignee
동우 화인켐 주식회사
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Priority claimed from KR1020180157353A external-priority patent/KR102640138B1/en
Application filed by 동우 화인켐 주식회사 filed Critical 동우 화인켐 주식회사
Publication of WO2019156363A1 publication Critical patent/WO2019156363A1/en

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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • 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
    • C11D7/50—Solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof

Definitions

  • the present invention relates to a mask cleaning liquid composition, specifically, a mask cleaning liquid composition for removing various organic substances on a mask used in a deposition process.
  • FPDs Flat panel displays
  • OLEDs organic light emitting diodes
  • the liquid crystal display device that is most used as a display has advantages such as light weight, small volume, and low power, compared to a conventional CRT (Cathode ray tube).
  • CRT Cathode ray tube
  • the backlight should be used, and the viewing angle is limited by using liquid crystal.
  • OLED devices have advantages such as low voltage driving, high luminous efficiency, wide viewing angle, and fast response speed, and above all, they do not need back light because they are self-luminous.
  • the OLED device emits light by recombining electrons and holes supplied from a cathode and an anode using a light emitting organic material that emits light.
  • a semiconductor device or a flat panel display such as an OLED may perform deposition of an organic material using a mask to form organic material layers such as various light emitting layers, hole injection layers, hole transport layers, electron transport layers, electron injection layers, and the like during the manufacturing process.
  • organic material layers such as various light emitting layers, hole injection layers, hole transport layers, electron transport layers, electron injection layers, and the like during the manufacturing process.
  • the organic material is attached to the surface of the mask, the shape of the pattern formed by the mask may be deformed due to the organic material attached. This causes a decrease in the efficiency of the deposition process and may affect the performance of the semiconductor device or flat panel display to be manufactured, so it is necessary to remove the organic matter deposited on the mask.
  • Republic of Korea Patent Publication No. 2011-0095814 relates to a deposition material cleaning liquid composition and a cleaning method using the same, N-methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone); And 1,3-dimethyl-2-imidazolidinone (1,3-Dimethyl-2-imidazolidinone).
  • Korean Patent No. 1388283 relates to a mask cleaning apparatus, comprising: an ultrasonic cleaner for generating ultrasonic waves to clean a mask immersed in a cleaning liquid;
  • the ultrasonic cleaning unit includes a cleaning solution circulation unit for discharging and supplying the cleaning solution, and the ultrasonic wave in the ultrasonic cleaning unit has a frequency of 75 KHz or more and 90 KHz or less, the intensity is 800 W or more and 1100 W or less, and the cleaning solution is NMP (N-Methyl Pyrrolidinone).
  • N-methylpyrrolidinone N-methylpyrrolidinone
  • NMP N-methyl-2-pyrrolidone
  • the mask cleaning process should not degrade performance after long-term storage in the standby state because the operating time is determined according to the manufacturing process conditions. In particular, due to exposure to the atmosphere, there should be no degradation in water absorption.
  • Patent Document 1 Republic of Korea Patent Publication No. 2011-0095814 (2011.08.25.)
  • Patent Document 2 Republic of Korea Patent No. 1388283 (2014.04.16.)
  • An object of the present invention is to provide a cleaning liquid composition that exhibits good cleaning power without including an environmental regulatory substance.
  • the present invention provides a mask cleaning liquid composition
  • a mask cleaning liquid composition comprising a glyme-based compound represented by the following formula (1) and containing no nonpolar solvent.
  • R1 and R2 are each independently C1 to C10 straight chain or C3 to C10 branched alkyl group
  • R3 is C1 to C10 straight chain or C3 to C10 branched alkylene group
  • n is an integer of 1-4.
  • the mask cleaning liquid composition according to the present invention can exhibit a good cleaning power without including an environmental regulatory material such as NMP, there is an advantage in the easy operation of the process.
  • the mask cleaning liquid composition according to the present invention has the advantage that the performance degradation due to moisture absorption is suppressed.
  • a member when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.
  • One aspect of the present invention relates to a mask cleaning liquid composition containing a glyme-based compound represented by the following formula (1) and containing no nonpolar solvent.
  • R1 and R2 are each independently C1 to C10 straight chain or C3 to C10 branched alkyl group
  • R3 is C1 to C10 straight chain or C3 to C10 branched alkylene group
  • n is an integer of 1-4.
  • the linear or branched alkyl group is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl , n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n -Heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1-e
  • alkyl group may be applied except that the alkylene group is divalent.
  • the mask cleaning liquid composition according to the present invention may be in a neat state of the glame-based compound represented by Chemical Formula 1.
  • the mask cleaning liquid composition according to the present invention may be formed of a glymeic compound represented by Chemical Formula 1.
  • the glyme compound represented by the formula (1) is ethylene glycol dimethyl ether (DMG), diethylene glycol dimethyl ether (DMDG), triethylene glycol dimethyl ether (DMTG), diethylene glycol diethyl Ether (DEDG), diethylene glycol methyl ethyl ether (MEDG), diethylene glycol methyl butyl ether (MBDG), triethylene glycol methyl butyl ether (MBTG), propylene glycol dimethyl ether (PDM), dipropylene glycol dimethyl ether (DPDM )
  • ethylene glycol diethyl ether (DEG) may be one or more selected from, for example, the glyme-based compound may be used alone or in combination of two or more thereof.
  • the glyme-based compound represented by Formula 1 has a ⁇ P of 4.5 to 6.5 MPa 1/2 , ⁇ H
  • The may be one having a Hansen solubility constant (Hansen Solubility Parameter) value of 4.0 to 6.0 MPa 1/2.
  • the glyme-based compound represented by Formula 1 has a Hansen Parameter value that satisfies the above range, since the polar solubility parameter and the hydrogen bonding solubility parameter have low values at the same time, It is preferable to have an advantage of obtaining a mask cleaning liquid having high solubility and excellent cleaning / removing ability with respect to an organic material including a polymer material.
  • Glidden critical compound of the formula (1) is the ⁇ P is 4.5 to 6.5 MPa 1/2, ⁇ H Of 4.0 to 6.0 and MPa 1/2, ⁇ D is 15.0 to 16.0 MPa 1/2, ⁇ T is 16 to 25 MPa 1/2, specifically, ⁇ T is 16.5 to 18.0 MPa 1/2 the Hansen solubility constant It can be used, and in this case it is preferable because the above-described advantages can be maximized.
  • the ⁇ T is ( ⁇ P 2 + ⁇ H 2 + ⁇ D 2 ) Can be calculated as 1/2 .
  • the mask cleaning liquid composition according to the present invention includes the glyme-based compound represented by Chemical Formula 1, the mask cleaning liquid composition has excellent mask cleaning power, and does not cause damage to materials such as SUS and Invar forming a mask, for example, NMP. Because it can be used instead of environmentally harmful substances such as environmentally friendly and has an easy advantage in terms of process. Specifically, the mask cleaning liquid composition according to the present invention does not cause damage such as corrosion, such as a mask of Invar material used to form the organic light emitting device and a stainless steel (SUS 304, 316, 420, etc.) supporting the mask. There is this.
  • the mask cleaning liquid composition according to the present invention does not contain nonpolar solvents, and thus has an advantage of excellent cleaning power.
  • the nonpolar solvent is not limited thereto, for example, hexane, heptane, carbon tetrachloride, benzene, toluene, xylene, N-methylpyrrolidone, tetrahydrofuran, nitrobenzene, N, N-dimethylformamide, dimethyl sulfoxide (dimethylsulfoxide) diethylcarbonate, benzyl acetate, dimethyl glutarate, dimethyl acetate, ethylacetoacetate, isobutyl isobutanoate, isobutyl acetate ), Meta-cresol or a mixture of two or more thereof, but is not limited thereto.
  • the mask cleaning liquid composition according to the present invention does not contain the non-polar solvent, thereby having an advantage of preventing the problem.
  • the mask cleaning liquid composition according to the present invention is excellent in cleaning power for various organic substances adhered to the mask.
  • the organic material may be, for example, a material forming an emission layer, a hole transport layer (HTL), a hole injection layer (HIL), or the like that emits red, green, and / or blue light.
  • the emission layer may emit red, green, and / or blue, and may be formed of a phosphor or a fluorescent material.
  • the light emitting host material may be CBP ((carbazole-9-yl) biphenyl), BSBF (2- (9,9-Spirobifluoren-2-yl) -9,9-spirobifluorene), TPBi (1,3,5- Tris (1-phenyl-1Hbenzimidazol-2-yl) benzene) or mCP (1,3-bis (carbazol-9-yl) -benzene) may be used, but is not limited thereto.
  • CBP ((carbazole-9-yl) biphenyl)
  • BSBF (9,9-Spirobifluoren-2-yl) -9,9-spirobifluorene
  • TPBi 1,3,5- Tris (1-phenyl-1Hbenzimidazol-2-yl) benzene
  • mCP 1,3-bis (carbazol-9-yl) -benzene
  • Red luminescent dopants include PIQIr (acac) (bis (1-phenylisoquinoline) acetylacetonato iridium), PQIr (acac) (bis (1-phenylquinoline) acetylacetonato iridium), PQIr (tris (1-phenylquinoline) iridium), PtOEP (octaethylporphyrin platinum) Phosphors such as), fluorescent materials such as tris- (8-hydroxyquinoline) aluminum), and the like may be used.
  • a phosphor such as Ir (ppy) 3 (fac tris (2-phenylpyridine) iridium) or a fluorescent material such as Alq3 (tris- (8-hydroxyquinoline) aluminum) may be used, but is not limited thereto. no.
  • blue light emitting dopants include phosphors such as (4,6-F 2 ppy) 2 Irpic, spiro-DPVBi, spiro-6P, ditylbenzene (DSB), distriarylene (DSA), PFO-based polymers, and PPV.
  • Fluorescent materials such as polymers may be used, but are not limited thereto.
  • the hole transport layer is NPD (N, N'-Di (1-naphthyl) -N, N ''-diphenyl- (1,1'-biphenyl) -4,4'-diamine), TPD (N, N'-bis -(3-methylphenyl) -N, N'-bis- (phenyl) -benzidine), s-TAD and MTDATA (4,4 ', 4 "-Tris (N-3-methylphenyl-N-phenyl-amino)- triphenylamine), but is not limited thereto, such as triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkaine derivatives, pyrazoline derivatives and pyrazolone derivatives, for example, as a hole transport layer material.
  • Phenylenediamine derivatives Phenylenediamine derivatives, arylamine derivatives, amino substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, polysilane-based, aniline-based aerials Copolymers, conductive polymer oligomers (particularly thiophene oligomers) and the like.
  • oxadiazole derivatives triazole derivatives, phenanthroline derivatives, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), aluminum complexes and the like contained in the hole blocking layer may be used.
  • the material for the hole injection layer at least one selected from the group consisting of copper phthalocyanine (PuPc), poly (3,4) -ethylenedioxythiophene (PEDOT), polyaniline (PANI), and NPD may be used.
  • the mask cleaning liquid composition may further comprise a water-soluble polar solvent.
  • the water-soluble polar solvent may include one or more selected from the group consisting of a proton polar solvent and an aprotic polar solvent.
  • the water-soluble polar solvent according to the present invention may include a proton polar solvent and an aprotic polar solvent, and these may be used alone or in combination.
  • the proton polar solvent is, for example, ethylene glycol monomethyl ether (MG), ethylene glycol monoethyl ether (EC), ethylene glycol monoisopropyl ether (iPG), ethylene glycol monobutyl ether (BC), diethylene glycol monomethyl ether (MDG), diethylene glycol monoethyl ether (EDG), diethylene glycol monoisopropyl ether (iBDG), diethylene glycol monobutyl ether (BDG), triethylene glycol monomethyl ether (MTG), triethylene glycol monoethyl Ether (ETG), triethylene glycol monoisopropyl ether (iBTG), triethylene glycol monobutyl ether (BTG), polyethylene glycol monomethyl ether (MPG), polyethylene glycol monobutyl ether (BPG), propylene glycol monomethyl ether ( Alkylene glycol monoalkyl ethers such as MFG), dipropylene glycol monomethyl ether (MFDG), and tripropylene glyco
  • the aprotic polar solvent is, for example, N, N-dimethylpropionamide (DMPA), N, N, -dimethylacetamide (DMAC), N, N-dimethylisobutylamide (DMIB), N, N-dimethylacrylamide ( DMAR), N, N-dimethylmethacrylamide, N, N-dimethyldecanamide (DMDA), N, N-diethylformamide (DEF), N, N-diethylacetamide (DEAC), N, N -Diethylpropionamide (DEPA), N, N-diethylisobutylamide (DEIB), N, N-diethylacrylamide (DEA), N, N-diethylmethacrylamide, 3-methoxy-N Dialkylamides such as N-dimethylpropionamide (MDMP) and 3-butoxy-N, N-dimethylpropionamide, N, N-diethylformamide (DEF) and N, N-dimethylform
  • an amide compound such as a dialkylamide compound or a monoamide compound, and more preferably a dialkylamide compound is preferable in view of washability.
  • the water-soluble polar solvent serves to dissolve the organic material remaining in the mask with the glyme-based compound represented by the formula (1), and also to facilitate the removal of the cleaning solution by water in the rinse process of deionized water after cleaning Minimize the resorption / reattachment of the organic material or can play a role that can be implemented to improve the removal of the specific organic material.
  • the water-soluble polar solvent may be selected according to the performance required in the subsequent cleaning process, it is preferable that the water-soluble polar solvent does not have a low boiling point for proper cleaning power and stable operation of the process. For example, it is preferable to have a boiling point of 150-290 degreeC. When using a water-soluble polar solvent having a boiling point within the above range it may be preferable in terms of environmental and process.
  • the boiling point of the water-soluble solvent is low, it is preferable to use a water-soluble polar solvent having a boiling point within the above range because it may be volatilized in the cleaning process and the process usage may increase and adversely affect the working environment.
  • the water-soluble polar solvent may be included in an amount of 0 to 90 parts by weight, preferably 0 to 80 parts by weight, based on 100 parts by weight of the cleaning liquid composition.
  • the water-soluble polar solvent is included in the above range, it is preferable because it has an excellent cleaning power, it is possible to prepare a cleaning liquid composition that is easy to remove the cleaning liquid by water in the rinse process of deionized water after cleaning.
  • water may be included in an amount of 7 parts by weight or less based on 100 parts by weight in total.
  • the mask cleaning liquid composition may contain 5 parts by weight or less based on 100 parts by weight of the total.
  • the mask cleaning liquid composition may include 3 parts by weight or less of the water based on 100 parts by weight of the total.
  • the water may be deionized water (DIW) or ultrapure water in which impurities are reduced as much as possible, but are not limited thereto.
  • DIW deionized water
  • ultrapure water in which impurities are reduced as much as possible, but are not limited thereto.
  • the water may be included by absorbing moisture over time, it is preferable that the cleaning liquid composition according to the present invention does not contain water.
  • the cleaning liquid composition according to the present invention has excellent cleaning power including the glyme-based compound represented by Chemical Formula 1, ultrasonic cleaning and electrolytic cleaning are unnecessary.
  • the mask cleaning liquid composition may be a mask cleaning liquid composition for cleaning a mask used in an organic material vacuum deposition process.
  • the mask cleaning liquid composition according to the present invention has an advantage of excellent cleaning power without including environmental regulatory substances such as NMP, NEP, DMF, and the like.
  • the organic material was separated from the mask, made into a powder form using a mortar, and then separated into a 224 ⁇ m sieve.
  • the solubility (melting rate, measurement in minutes) was dissolved by dissolving the organic material powder in the mask cleaning liquid composition at room temperature to satisfy 0.1% by weight with respect to 100% by weight of the total mask cleaning liquid composition prepared according to the Examples and Comparative Examples using a 50 ml beaker. The evaluation is shown in Table 2 below.
  • Comparative Example 1 which includes an environmental regulatory substance, one or more masks showed 30 minutes or more, indicating that the dissolving ability was reduced.
  • the organic material was separated from the mask, and then made into a powder form using a mortar and then separated into a 224 ⁇ m sieve.
  • a glass 50 ml glass bottle was aliquoted and then room temperature. After leaving for 24 hours in the evaluation of the stability (turbidity increase and precipitate) of the mask cleaning liquid composition (chemical solution) according to Examples and Comparative Examples are shown in Table 3 below.
  • Example 1 ⁇ ⁇ ⁇ Example 2 ⁇ ⁇ ⁇ Example 3 ⁇ ⁇ ⁇ Example 4 ⁇ ⁇ ⁇ Example 5 ⁇ ⁇ ⁇ Example 6 ⁇ ⁇ ⁇ Example 7 ⁇ ⁇ ⁇ Example 8 ⁇ ⁇ ⁇ Example 9 ⁇ ⁇ ⁇ Example 10 ⁇ ⁇ ⁇ Example 11 ⁇ ⁇ ⁇ Example 12 ⁇ ⁇ ⁇ Example 13 ⁇ ⁇ ⁇ Example 14 ⁇ ⁇ ⁇ Example 15 ⁇ ⁇ ⁇ Example 16 ⁇ ⁇ ⁇ Example 17 ⁇ ⁇ ⁇ Example 18 ⁇ ⁇ ⁇ Example 19 ⁇ ⁇ ⁇ Example 20 ⁇ ⁇ ⁇ Example 21 ⁇ ⁇ ⁇ Example 22 ⁇ ⁇ ⁇ Example 23 ⁇ ⁇ ⁇ Example 24 ⁇ ⁇ ⁇ Example 25 ⁇ ⁇ ⁇ Comparative Example 1 ⁇ ⁇ ⁇ Comparative Example 2 ⁇ ⁇ ⁇ Comparative Example 3 ⁇ ⁇ ⁇ Comparative Example 4 ⁇
  • Comparative Examples except for Comparative Example 1 containing an environmental regulatory substance it may be confirmed that one or more chemical solutions are opaque and the dissolution stability is lowered.
  • the comparative example containing a nonpolar solvent it can confirm that melt

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Abstract

A mask cleaning solution composition according to the present invention comprises a glyme-based compound represented by chemical formula 1 but does not contain a nonpolar solvent. The mask cleaning solution composition according to the present invention exhibits good cleaning power even without comprising environmentally regulated materials.

Description

마스크 세정액 조성물Mask Cleaning Liquid Composition
본 발명은 마스크 세정액 조성물, 구체적으로 증착 공정에서 사용되는 마스크 상의 각종 유기물을 제거하는 마스크 세정액 조성물에 관한 것이다.The present invention relates to a mask cleaning liquid composition, specifically, a mask cleaning liquid composition for removing various organic substances on a mask used in a deposition process.
평판 디스플레이(flat panel display, FPD)는 표시장치로서 주목받고 있으며, 그 중에서도 액정표시장치와 OLED(Organic Light Emitting Diode)가 관심의 대상이 되고 있다.Flat panel displays (FPDs) are attracting attention as display devices, and among them, liquid crystal displays and organic light emitting diodes (OLEDs) are of interest.
현재 디스플레이로서 가장 많이 사용되고 있는 액정표시장치는, 기존의 CRT (Cathode ray tube; 음극선관)에 비해 가볍고 부피가 작으며 저전력 등의 장점을 가지고 있다. 그러나 자체발광이 아니기 때문에 후면광(Backlight)을 사용하여야 하며, 액정을 사용하여 시야각이 제한을 받는 단점이 있다.Currently, the liquid crystal display device that is most used as a display has advantages such as light weight, small volume, and low power, compared to a conventional CRT (Cathode ray tube). However, since it is not self-luminous, the backlight should be used, and the viewing angle is limited by using liquid crystal.
이에 비해 OLED 소자는 저전압구동, 높은 발광 효율, 넓은 시야각, 빠른 응답속도 등의 장점이 있으며, 무엇보다도 자체발광형이기 때문에 후면광 등이 필요하지 않은 장점이 있다. 이러한 OLED 소자는 자체발광을 하는 발광 유기물을 사용하여 음극과 양극으로부터 공급된 전자와 정공이 재결합되면서 발광이 일어나게 된다.On the other hand, OLED devices have advantages such as low voltage driving, high luminous efficiency, wide viewing angle, and fast response speed, and above all, they do not need back light because they are self-luminous. The OLED device emits light by recombining electrons and holes supplied from a cathode and an anode using a light emitting organic material that emits light.
이런 OLED와 같은 반도체 디바이스 또는 평판 디스플레이는 제조 공정 중 각종 발광층, 정공 주입층, 정공 수송층, 전자 수송층, 전자 주입층 등과 같은 유기물층을 형성하기 위하여 마스크를 이용하여 유기물의 증착을 수행하게 된다. 이때, 마스크의 표면에도 유기물이 부착되게 되며, 이렇게 부착된 유기물로 인하여 마스크로 형성된 패턴의 형상이 변형될 수 있다. 이는, 증착공정의 효율 저하를 야기하며, 제조되는 반도체 디바이스 또는 평판 디스플레이의 성능에도 영향을 미칠 수 있으므로, 마스크에 증착된 유기물을 제거해야 할 필요가 있다.A semiconductor device or a flat panel display such as an OLED may perform deposition of an organic material using a mask to form organic material layers such as various light emitting layers, hole injection layers, hole transport layers, electron transport layers, electron injection layers, and the like during the manufacturing process. At this time, the organic material is attached to the surface of the mask, the shape of the pattern formed by the mask may be deformed due to the organic material attached. This causes a decrease in the efficiency of the deposition process and may affect the performance of the semiconductor device or flat panel display to be manufactured, so it is necessary to remove the organic matter deposited on the mask.
대한민국 공개특허 제2011-0095814호는 증착 재료 세정액 조성물 및 이를 이용한 세정 방법에 관한 것으로서, N-메틸-2-피롤리돈(N-Methyl-2-pyrrolidone); 및 1,3-디메틸-2-이미다졸리디논(1,3-Dimethyl-2-imidazolidinone)을 포함하는 증착 재료 세정액 조성물에 관한 내용을 개시하고 있다.Republic of Korea Patent Publication No. 2011-0095814 relates to a deposition material cleaning liquid composition and a cleaning method using the same, N-methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone); And 1,3-dimethyl-2-imidazolidinone (1,3-Dimethyl-2-imidazolidinone).
대한민국 등록특허 제1388283호는 마스크 세정장치에 관한 것으로서, 초음파를 발생시켜 세정액에 잠겨있는 마스크를 세정하는 초음파 세정부; 상기 초음파 세정부의 세정액 배출과 공급을 위한 세정액 순환부를 포함하고, 상기 초음파 세정부에서의 초음파는 주파수가 75KHz이상 90KHz이하이며, 세기가 800W이상 1100W이하이고, 상기 세정액은 NMP(N-Methyl Pyrrolidinone; N-메틸피롤리딘온) 혼합물인 것을 특징으로 하는 마스크 세정장치에 관한 내용을 개시하고 있다.Korean Patent No. 1388283 relates to a mask cleaning apparatus, comprising: an ultrasonic cleaner for generating ultrasonic waves to clean a mask immersed in a cleaning liquid; The ultrasonic cleaning unit includes a cleaning solution circulation unit for discharging and supplying the cleaning solution, and the ultrasonic wave in the ultrasonic cleaning unit has a frequency of 75 KHz or more and 90 KHz or less, the intensity is 800 W or more and 1100 W or less, and the cleaning solution is NMP (N-Methyl Pyrrolidinone). N-methylpyrrolidinone) is disclosed as a mask cleaning device characterized in that the mixture.
그러나, 종래 마스크 세정액에 사용되던 N-메틸-2-피롤리돈(NMP)은 유독물질로서, 구체적으로 국립환경과학원 제2014-25호에 따르면 0.3 중량% 이상 함유시 유독물로 분류되는 물질이다. NMP가 포함된 마스크 세정액을 사용할 경우 인체에 유해할 뿐만 아니라 환경적인 측면에서도 좋지 않다.However, N-methyl-2-pyrrolidone (NMP), which is used in mask cleaning liquids in the related art, is a toxic substance. Specifically, according to the National Institute of Environmental Research, 2014-25, it is a substance classified as a toxic substance when 0.3 wt% or more is contained. The use of a mask cleaning liquid containing NMP is not only harmful to the human body but also bad for the environment.
또한, 마스크 세정 공정은 제조 공정 상황에 따라 가동 시간이 결정 되는 관계로 대기 상태에서 장기 보관 후 성능 저하가 발생 하지 않아야 한다. 특히 대기 중에 노출 되는 관계로 수분 흡수에 대하여 성능 저하가 발생 하지 않아야 한다. In addition, the mask cleaning process should not degrade performance after long-term storage in the standby state because the operating time is determined according to the manufacturing process conditions. In particular, due to exposure to the atmosphere, there should be no degradation in water absorption.
그러므로, NMP와 같은 환경규제물질을 포함하지 않으면서도, 세정력이 우수하고 수분 흡수에 따른 성능 저하가 발생하지 않으며, 공정 운전에 용이한 마스크 세정액의 개발이 요구되고 있다.Therefore, it is required to develop a mask cleaning liquid that is excellent in cleaning power, does not cause performance deterioration due to moisture absorption, and does not contain environmental regulatory substances such as NMP.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
(특허문헌 1) 대한민국 공개특허 제2011-0095814호 (2011.08.25.)(Patent Document 1) Republic of Korea Patent Publication No. 2011-0095814 (2011.08.25.)
(특허문헌 2) 대한민국 등록특허 제1388283호 (2014.04.16.)(Patent Document 2) Republic of Korea Patent No. 1388283 (2014.04.16.)
본 발명의 목적은 환경규제물질을 포함하지 않고도 양호한 세정력을 나타내는 세정액 조성물을 제공하는 데 있다.SUMMARY OF THE INVENTION An object of the present invention is to provide a cleaning liquid composition that exhibits good cleaning power without including an environmental regulatory substance.
또한, 본 발명의 목적은 초음파 및 전해 세정이 불필요하며 안정성이 우수하여 공정 운전에 용이한 세정액 조성물을 제공하는 데 있다.In addition, it is an object of the present invention to provide a cleaning liquid composition which is easy to process operation due to excellent stability and ultrasonic and electrolytic cleaning is unnecessary.
본 발명은 하기 화학식 1로 표시되는 글라임계 화합물을 포함하고, 무극성 용매를 함유하지 않는 마스크 세정액 조성물을 제공한다.The present invention provides a mask cleaning liquid composition comprising a glyme-based compound represented by the following formula (1) and containing no nonpolar solvent.
[화학식 1][Formula 1]
Figure PCTKR2019000230-appb-I000001
Figure PCTKR2019000230-appb-I000001
상기 화학식 1에서,In Chemical Formula 1,
R1 및 R2는 각각 독립적으로 C1 내지 C10의 직쇄 또는 C3 내지 C10의 분지쇄 알킬기이고,R1 and R2 are each independently C1 to C10 straight chain or C3 to C10 branched alkyl group,
R3는 C1 내지 C10의 직쇄 또는 C3 내지 C10의 분지쇄 알킬렌기이며,R3 is C1 to C10 straight chain or C3 to C10 branched alkylene group,
n은 1 내지 4의 정수이다.n is an integer of 1-4.
본 발명에 따른 마스크 세정액 조성물은 NMP와 같은 환경규제물질을 포함하지 않고도 양호한 세정력을 나타낼 수 있어 공정 운전에 용이한 이점이 있다.The mask cleaning liquid composition according to the present invention can exhibit a good cleaning power without including an environmental regulatory material such as NMP, there is an advantage in the easy operation of the process.
또한, 본 발명에 따른 마스크 세정액 조성물은 수분 흡수에 따른 성능 저하가 억제되는 이점이 있다.In addition, the mask cleaning liquid composition according to the present invention has the advantage that the performance degradation due to moisture absorption is suppressed.
또한, 본 발명에 따른 마스크 세정액 조성물을 이용하여 마스크를 세정할 경우 초음파 및 전해 세정이 불필요한 이점이 있다.In addition, when the mask is cleaned using the mask cleaning liquid composition according to the present invention, ultrasonic and electrolytic cleaning are unnecessary.
이하, 본 발명에 대하여 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명에서 어떤 부재가 다른 부재 "상에" 위치하고 있다고 할 때, 이는 어떤 부재가 다른 부재에 접해 있는 경우뿐 아니라 두 부재 사이에 또 다른 부재가 존재하는 경우도 포함한다.In the present invention, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.
본 발명에서 어떤 부분이 어떤 구성요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있는 것을 의미한다.In the present invention, when a part "includes" a certain component, this means that it may further include other components, without excluding the other components unless otherwise stated.
본 발명의 한 양태는, 하기 화학식 1로 표시되는 글라임계 화합물을 포함하고, 무극성 용매를 함유하지 않는 마스크 세정액 조성물에 관한 것이다.One aspect of the present invention relates to a mask cleaning liquid composition containing a glyme-based compound represented by the following formula (1) and containing no nonpolar solvent.
[화학식 1][Formula 1]
Figure PCTKR2019000230-appb-I000002
Figure PCTKR2019000230-appb-I000002
상기 화학식 1에서,In Chemical Formula 1,
R1 및 R2는 각각 독립적으로 C1 내지 C10의 직쇄 또는 C3 내지 C10의 분지쇄 알킬기이고,R1 and R2 are each independently C1 to C10 straight chain or C3 to C10 branched alkyl group,
R3는 C1 내지 C10의 직쇄 또는 C3 내지 C10의 분지쇄 알킬렌기이며,R3 is C1 to C10 straight chain or C3 to C10 branched alkylene group,
n은 1 내지 4의 정수이다.n is an integer of 1-4.
본 발명에서 상기 직쇄 또는 분지쇄의 알킬기는 예컨대, 메틸, 에틸, n-프로필, 이소프로필, n-부틸, 이소부틸, tert-부틸, sec-부틸, 1-메틸-부틸, 1-에틸-부틸, n-펜틸, 이소펜틸, 네오펜틸, tert-펜틸, n-헥실, 1-메틸펜틸, 2-메틸펜틸, 4-메틸-2-펜틸, 3,3-디메틸부틸, 2-에틸부틸, n-헵틸, 1-메틸헥실, n-옥틸, tert-옥틸, 1-메틸헵틸, 2-에틸헥실, 2-프로필펜틸, n-노닐, 2,2-디메틸헵틸, 1-에틸-프로필, 1,1-디메틸-프로필, 이소헥실, 2-메틸펜틸, 4-메틸헥실, 5-메틸헥실 등일 수 있으나, 이들에 한정되지 않는다.In the present invention, the linear or branched alkyl group is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl , n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n -Heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1, 1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.
상기 알킬렌기는 2가인 것을 제외하고는 전술한 알킬기의 설명을 적용할 수 있다.The above description of the alkyl group may be applied except that the alkylene group is divalent.
본 발명에 따른 마스크 세정액 조성물은 상기 화학식 1로 표시되는 글라임계 화합물 단독(neat) 상태일 수 있다. 요컨대, 본 발명에 따른 마스크 세정액 조성물은 상기 화학식 1로 표시되는 글라임계 화합물로 이루어질 수 있다.The mask cleaning liquid composition according to the present invention may be in a neat state of the glame-based compound represented by Chemical Formula 1. In short, the mask cleaning liquid composition according to the present invention may be formed of a glymeic compound represented by Chemical Formula 1.
본 발명의 일 실시형태에 있어서, 상기 화학식 1로 표시되는 글라임계 화합물은 에틸렌 글리콜 디메틸 에테르(DMG), 디에틸렌 글리콜 디메틸 에테르(DMDG), 트리에틸렌 글리콜 디메틸 에테르(DMTG), 디에틸렌 글리콜 디에틸 에테르(DEDG), 디에틸렌 글리콜 메틸 에틸 에테르(MEDG), 디에틸렌 글리콜 메틸 부틸 에테르(MBDG), 트리에틸렌 글리콜 메틸 부틸 에테르(MBTG), 프로필렌 글리콜 디메틸 에테르(PDM), 디프로필렌 글리콜 디메틸 에테르(DPDM) 및 에틸렌 글리콜 디에틸 에테르(DEG)로 이루어진 군으로부터 선택되는 1 이상일 수 있으며, 예컨대, 상기 글라임계 화합물을 단독으로 또는 2종 이상 혼합하여 사용할 수 있다.In one embodiment of the present invention, the glyme compound represented by the formula (1) is ethylene glycol dimethyl ether (DMG), diethylene glycol dimethyl ether (DMDG), triethylene glycol dimethyl ether (DMTG), diethylene glycol diethyl Ether (DEDG), diethylene glycol methyl ethyl ether (MEDG), diethylene glycol methyl butyl ether (MBDG), triethylene glycol methyl butyl ether (MBTG), propylene glycol dimethyl ether (PDM), dipropylene glycol dimethyl ether (DPDM ) And ethylene glycol diethyl ether (DEG) may be one or more selected from, for example, the glyme-based compound may be used alone or in combination of two or more thereof.
본 발명의 또 다른 실시형태에 있어서, 상기 화학식 1로 표시되는 글라임계 화합물은 δP가 4.5 내지 6.5 MPa1/2이고, δH 가 4.0 내지 6.0 MPa1/ 2 의 한센 용해도 상수(Hansen Solubility Parameter) 값을 갖는 것일 수 있다.In another embodiment of the present invention, the glyme-based compound represented by Formula 1 has a δ P of 4.5 to 6.5 MPa 1/2 , δ H The may be one having a Hansen solubility constant (Hansen Solubility Parameter) value of 4.0 to 6.0 MPa 1/2.
상기 화학식 1로 표시되는 글라임계 화합물이 상기 범위를 만족하는 Hansen Parameter 값을 갖는 경우, 극성 용해도 파라미터(polar solubility parameter)와 수소결합 용해도 파라미터(hydrogen bonding solubility parameter) 값이 동시에 낮은 값을 가지기 때문에, 고분자 물질을 포함하는 유기소재에 대하여 높은 용해도를 가지고, 우수한 세정/제거 능력을 가지는 마스크 세정액을 얻을 수 있는 이점이 있어 바람직하다.When the glyme-based compound represented by Formula 1 has a Hansen Parameter value that satisfies the above range, since the polar solubility parameter and the hydrogen bonding solubility parameter have low values at the same time, It is preferable to have an advantage of obtaining a mask cleaning liquid having high solubility and excellent cleaning / removing ability with respect to an organic material including a polymer material.
바람직하게는, 상기 화학식 1로 표시되는 글라임계 화합물은 δP가 4.5 내지 6.5 MPa1 /2이고, δH 가 4.0 내지 6.0 MPa1/ 2 이며, δD가 15.0 내지 16.0 MPa1 /2, δT가 16 내지 25 MPa1 /2 , 구체적으로 δT가 16.5 내지 18.0 MPa1 /2인 한센 용해도 상수 값을 가지는 것을 사용할 수 있으며, 이 경우 전술한 이점이 극대화될 수 있어 바람직하다.Preferably, Glidden critical compound of the formula (1) is the δ P is 4.5 to 6.5 MPa 1/2, δ H Of 4.0 to 6.0 and MPa 1/2, δ D is 15.0 to 16.0 MPa 1/2, δ T is 16 to 25 MPa 1/2, specifically, δ T is 16.5 to 18.0 MPa 1/2 the Hansen solubility constant It can be used, and in this case it is preferable because the above-described advantages can be maximized.
본 발명에서, 상기 δT는 (δP 2 + δH 2 + δD 2 )1/2로 계산될 수 있다.In the present invention, the δ T is (δ P 2 + δ H 2 + δ D 2 ) Can be calculated as 1/2 .
본 발명에 따른 마스크 세정액 조성물은 상기 화학식 1로 표시되는 글라임계 화합물을 포함하기 때문에 마스크 세정력이 우수하고, 마스크, 예컨대 마스크를 이루고 있는 SUS, Invar 등의 물질에는 데미지를 입히지 않는 이점이 있으며, NMP와 같은 환경유해물질 대신 이용될 수 있기 때문에 환경적인 측면에서도 우수하고 공정적인 측면에서도 용이한 이점이 있다. 구체적으로, 본 발명에 따른 마스크 세정액 조성물은 유기발광소자의 패턴 형성에 사용되는 Invar 재질의 마스크 및 상기 마스크를 지지하는 스테인레스(SUS 304, 316, 420 등) 기재 등에 부식 등과 같은 데미지를 주지 않는 이점이 있다.Since the mask cleaning liquid composition according to the present invention includes the glyme-based compound represented by Chemical Formula 1, the mask cleaning liquid composition has excellent mask cleaning power, and does not cause damage to materials such as SUS and Invar forming a mask, for example, NMP. Because it can be used instead of environmentally harmful substances such as environmentally friendly and has an easy advantage in terms of process. Specifically, the mask cleaning liquid composition according to the present invention does not cause damage such as corrosion, such as a mask of Invar material used to form the organic light emitting device and a stainless steel (SUS 304, 316, 420, etc.) supporting the mask. There is this.
또한, 본 발명에 따른 마스크 세정액 조성물은 무극성 용매(nonpolar solvents)류를 함유하지 않아, 세정력이 우수한 이점이 있다.In addition, the mask cleaning liquid composition according to the present invention does not contain nonpolar solvents, and thus has an advantage of excellent cleaning power.
상기 무극성 용매는 이에 제한되는 것은 아니나, 예컨대, 헥산, 헵탄, 사염화탄소, 벤젠, 톨루엔, 자일렌, N-메틸피롤리돈, 테트라하이드로퓨란, 니트로벤젠, N,N-디메틸포름아미드, 디메틸설폭사이드(dimethylsulfoxide) 디에틸카보네이트(diethylcarbonate), 벤질 아세테이트(benzyl acetate), 디메틸 글루타레이트(dimethyl glutarate), 에틸아세토아세테이트(ehtylacetoacetate), 이소부틸 이소부타노에이트(isobutyl isobutanoate), 이소부틸 아세테이트(isobutyl acetate), 메타-크레졸(meta-cresol) 또는 이들의 2종 이상의 혼합물일 수 있으나 이에 한정되지는 않는다.The nonpolar solvent is not limited thereto, for example, hexane, heptane, carbon tetrachloride, benzene, toluene, xylene, N-methylpyrrolidone, tetrahydrofuran, nitrobenzene, N, N-dimethylformamide, dimethyl sulfoxide (dimethylsulfoxide) diethylcarbonate, benzyl acetate, dimethyl glutarate, dimethyl acetate, ethylacetoacetate, isobutyl isobutanoate, isobutyl acetate ), Meta-cresol or a mixture of two or more thereof, but is not limited thereto.
상기 무극성 용매가 함유되는 경우, 세정 후 무극성 용매가 잔류되는 문제가 발생할 수 있으나, 본 발명에 따른 마스크 세정액 조성물은 상기 무극성 용매를 함유하지 않음으로써, 상기 문제를 방지할 수 있는 이점이 있다.When the non-polar solvent is contained, the problem that the non-polar solvent remains after cleaning may occur, but the mask cleaning liquid composition according to the present invention does not contain the non-polar solvent, thereby having an advantage of preventing the problem.
요컨대, 본 발명에 따른 마스크 세정액 조성물은 상기 마스크에 부착되어 있는 각종 유기 물질에 대한 세정력이 우수하다.In short, the mask cleaning liquid composition according to the present invention is excellent in cleaning power for various organic substances adhered to the mask.
상기 유기 물질은 예컨대, 적색, 녹색 및/또는 청색을 발광하는 발광층, 정공수송층(HTL), 정공주입층(HIL) 등을 이루는 물질일 수 있다. 상기 발광층은 적색, 녹색 및/또는 청색을 발광할 수 있으며 인광 물질 또는 형광 물질로 이루어질 수 있다. 이때 상기 발광 호스트 재료로는 CBP((carbazole-9-yl)biphenyl), BSBF(2-(9,9-Spirobifluoren-2-yl)-9,9-spirobifluorene), TPBi(1,3,5-Tris(1-phenyl-1Hbenzimidazol-2-yl)benzene)또는 mCP(1,3-bis(carbazol-9-yl)-benzene)이 사용될 수 있으나, 이에만 한정된 것은 아니다.The organic material may be, for example, a material forming an emission layer, a hole transport layer (HTL), a hole injection layer (HIL), or the like that emits red, green, and / or blue light. The emission layer may emit red, green, and / or blue, and may be formed of a phosphor or a fluorescent material. The light emitting host material may be CBP ((carbazole-9-yl) biphenyl), BSBF (2- (9,9-Spirobifluoren-2-yl) -9,9-spirobifluorene), TPBi (1,3,5- Tris (1-phenyl-1Hbenzimidazol-2-yl) benzene) or mCP (1,3-bis (carbazol-9-yl) -benzene) may be used, but is not limited thereto.
적색 발광 도펀트로는 PIQIr(acac)(bis(1-phenylisoquinoline)acetylacetonato iridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonato iridium), PQIr(tris(1-phenylquinoline)iridium), PtOEP(octaethylporphyrin platinum)와 같은 인광 물질이나, Alq3(tris-(8-hydroxyquinoline)aluminum)와 같은 형광 물질 등이 사용될 수 있다.Red luminescent dopants include PIQIr (acac) (bis (1-phenylisoquinoline) acetylacetonato iridium), PQIr (acac) (bis (1-phenylquinoline) acetylacetonato iridium), PQIr (tris (1-phenylquinoline) iridium), PtOEP (octaethylporphyrin platinum) Phosphors such as), fluorescent materials such as tris- (8-hydroxyquinoline) aluminum), and the like may be used.
녹색 발광 도펀트로는 Ir(ppy)3(fac tris(2-phenylpyridine)iridium)와 같은 인광 물질이나, Alq3(tris-(8-hydroxyquinoline)aluminum)와 같은 형광 물질이 사용될 수 있으나, 이에만 한정된 것은 아니다. As the green light emitting dopant, a phosphor such as Ir (ppy) 3 (fac tris (2-phenylpyridine) iridium) or a fluorescent material such as Alq3 (tris- (8-hydroxyquinoline) aluminum) may be used, but is not limited thereto. no.
청색 발광 도펀트로는 (4,6-F2ppy)2Irpic와 같은 인광 물질이나, spiro-DPVBi, spiro-6P, 디스틸벤젠(DSB), 디스트릴아릴렌(DSA), PFO계 고분자, PPV계 고분자와 같은 형광 물질이 사용될 수 있으나, 이에만 한정된 것은 아니다.Examples of blue light emitting dopants include phosphors such as (4,6-F 2 ppy) 2 Irpic, spiro-DPVBi, spiro-6P, ditylbenzene (DSB), distriarylene (DSA), PFO-based polymers, and PPV. Fluorescent materials such as polymers may be used, but are not limited thereto.
정공수송층은 NPD(N,N'-Di(1-naphthyl)-N,N′'-diphenyl-(1,1'-biphenyl)-4,4'-diamine), TPD(N,N'-bis-(3-methylphenyl)-N,N'-bis-(phenyl)-benzidine), s-TAD 및 MTDATA(4,4',4"- Tris(N-3-methylphenyl-N-phenyl-amino)-triphenylamine)로 이루어진 군에서 선택된 어느 하나 이상으로 이루어질 수 있으나 이에 한정되지 않는다. 예컨대 정공수송층 재료로서 트라이아졸 유도체, 옥사다이아졸 유도체, 이미다졸 유도체, 폴리아릴알케인 유도체, 피라졸린 유도체 및 피라졸론 유도체, 페닐렌다이아민 유도체, 아릴아민 유도체, 아미노 치환 칼콘 유도체, 옥사졸 유도체, 스타이릴안트라센 유도체, 플루오렌온 유도체, 하이드라존 유도체, 스틸벤 유도체, 실라제인 유도체, 폴리실레인계, 아닐린계 공중합체, 도전성 고분자 올리고머(특히 싸이오펜 올리고머) 등을 들 수 있다.The hole transport layer is NPD (N, N'-Di (1-naphthyl) -N, N ''-diphenyl- (1,1'-biphenyl) -4,4'-diamine), TPD (N, N'-bis -(3-methylphenyl) -N, N'-bis- (phenyl) -benzidine), s-TAD and MTDATA (4,4 ', 4 "-Tris (N-3-methylphenyl-N-phenyl-amino)- triphenylamine), but is not limited thereto, such as triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkaine derivatives, pyrazoline derivatives and pyrazolone derivatives, for example, as a hole transport layer material. , Phenylenediamine derivatives, arylamine derivatives, amino substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, polysilane-based, aniline-based aerials Copolymers, conductive polymer oligomers (particularly thiophene oligomers) and the like.
또한, 그 외에도 정공저지층에 포함되는 옥사디졸 유도체나 트리아졸 유도체, 페난트롤린 유도체, BCP(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), 알루미늄 착물 등을 사용할 수 있으며, 정공 주입층에 재료로서 CuPc(copper phthalocyanine), PEDOT(poly(3,4)-ethylenedioxythiophene), PANI(polyaniline) 및 NPD로 이루어진 군에서 선택되는 1 이상이 사용될 수 있다.In addition, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), aluminum complexes and the like contained in the hole blocking layer may be used. As the material for the hole injection layer, at least one selected from the group consisting of copper phthalocyanine (PuPc), poly (3,4) -ethylenedioxythiophene (PEDOT), polyaniline (PANI), and NPD may be used.
본 발명의 또 다른 실시형태에 있어서, 상기 마스크 세정액 조성물은 수용성 극성용매를 더 포함할 수 있다.In another embodiment of the present invention, the mask cleaning liquid composition may further comprise a water-soluble polar solvent.
본 발명의 또 다른 실시형태에 있어서, 상기 수용성 극성용매는 양자성 극성용매 및 비양자성 극성용매로 이루어진 군에서 선택되는 1 이상을 포함할 수 있다.In still another embodiment of the present invention, the water-soluble polar solvent may include one or more selected from the group consisting of a proton polar solvent and an aprotic polar solvent.
구체적으로, 본 발명에 따른 수용성 극성용매는 양자성 극성용매와 비양자성 극성용매를 들 수 있으며, 이들을 각각 단독으로 또는 혼합하여 사용할 수 있다.Specifically, the water-soluble polar solvent according to the present invention may include a proton polar solvent and an aprotic polar solvent, and these may be used alone or in combination.
상기 양자성 극성용매는 예컨대 에틸렌글리콜 모노메틸 에테르(MG), 에틸렌글리콜 모노에틸 에테르(EC), 에틸렌글리콜 모노이소프로필 에테르(iPG), 에틸렌글리콜 모노부틸 에테르(BC), 디에틸렌글리콜 모노메틸 에테르(MDG), 디에틸렌글리콜 모노에틸 에테르(EDG), 디에틸렌글리콜 모노이소프로필 에테르(iBDG), 디에틸렌글리콜 모노부틸 에테르(BDG), 트리에틸렌글리콜 모노메틸 에테르(MTG), 트리에틸렌글리콜 모노에틸 에테르(ETG), 트리에틸렌글리콜 모노이소프로필 에테르(iBTG), 트리에틸렌글리콜 모노부틸 에테르(BTG), 폴리에틸렌글리콜 모노메틸 에테르(MPG), 폴리에틸렌글리콜 모노부틸 에테르(BPG), 프로필렌글리콜 모노메틸 에테르(MFG), 디프로필렌글리콜 모노메틸 에테르(MFDG), 트리프로필렌글리콜 모노메틸 에테르(MFTG) 등의 알킬렌글리콜 모노알킬 에테르 화합물; 4-하이드록시메틸-1,3-디옥솔란(HMD), 4-하이드록시메틸-2,2-디메틸-1,3-디옥솔란(HMDMDO), 4-하이드록시에틸-2,2-디메틸-1,3-디옥솔란, 4-하이드록시프로필-2,2-디메틸-1,3-디옥솔란, 4-하이드록시부틸-2,2-디메틸-1,3-디옥솔란, 4-하이드록시메틸-2,2-디에틸-1,3-디옥솔란, 4-하이드록시메틸-2-메틸-2-에틸-1,3-디옥솔란 등의 하이드록시 디옥솔란계 화합물;을 들 수 있으며 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있으나, 이에 한정되지는 않으며, 본 발명의 목적을 저해하지 않는 양자성 극성용매를 사용할 수 있다.The proton polar solvent is, for example, ethylene glycol monomethyl ether (MG), ethylene glycol monoethyl ether (EC), ethylene glycol monoisopropyl ether (iPG), ethylene glycol monobutyl ether (BC), diethylene glycol monomethyl ether (MDG), diethylene glycol monoethyl ether (EDG), diethylene glycol monoisopropyl ether (iBDG), diethylene glycol monobutyl ether (BDG), triethylene glycol monomethyl ether (MTG), triethylene glycol monoethyl Ether (ETG), triethylene glycol monoisopropyl ether (iBTG), triethylene glycol monobutyl ether (BTG), polyethylene glycol monomethyl ether (MPG), polyethylene glycol monobutyl ether (BPG), propylene glycol monomethyl ether ( Alkylene glycol monoalkyl ethers such as MFG), dipropylene glycol monomethyl ether (MFDG), and tripropylene glycol monomethyl ether (MFTG) Compound; 4-hydroxymethyl-1,3-dioxolane (HMD), 4-hydroxymethyl-2,2-dimethyl-1,3-dioxolane (HMDMDO), 4-hydroxyethyl-2,2-dimethyl- 1,3-dioxolane, 4-hydroxypropyl-2,2-dimethyl-1,3-dioxolane, 4-hydroxybutyl-2,2-dimethyl-1,3-dioxolane, 4-hydroxymethyl Hydroxydioxolane compounds such as -2,2-diethyl-1,3-dioxolane and 4-hydroxymethyl-2-methyl-2-ethyl-1,3-dioxolane; One or two or more species may be used together, but is not limited thereto, and a quantum polar solvent may be used that does not impair the object of the present invention.
상기 비양자성 극성용매는 예컨대 N,N-디메틸프로피온아미드(DMPA),N,N,-디메틸아세트아미드(DMAC), N,N-디메틸이소부틸아미드(DMIB), N,N-디메틸아크릴아미드(DMAR), N,N-디메틸메타크릴아미드, N,N-디메틸데칸아미드(DMDA), N,N-디에틸포름아미드(DEF), N,N-디에틸아세트아미드(DEAC), N,N-디에틸프로피온아미드(DEPA), N,N-디에틸이소부틸아미드(DEIB), N,N-디에틸아크릴아미드(DEA), N,N-디에틸메타크릴아미드, 3-메톡시-N,N-디메틸프로피온아미드(MDMP) 및 3-부톡시-N,N-디메틸프로피온아미드, N,N-디에틸포름아미드(DEF), N,N-디메틸포름아미드(DMF) 등의 디알킬아미드계 화합물; N-메틸포름아미드(NMF), N-에틸포름아미드(NEF), N-메틸프로피온아미드(NMPA), N-메틸아세트아미드(NMA), N-에틸아세트아미드(NEA), N-(2-히드록시에틸)아세트아미드 등의 모노아미드계 화합물; γ―부티로락톤 등의 락톤 화합물; 디메틸술폭사이드(DMSO), 술폴란 등의 설폭사이드 화합물; 트리에틸포스페이트(TEP), 트리부틸포스페이트(TBP) 등의 포스페이트 화합물; 디메틸카보네이트(DMC), 에틸렌카보네이트(EC), 프로필렌카보네이트(PC) 등의 카보네이트 화합물; 1,3-디메틸-2-이미다조리디논 (DMI) 등의 이미다졸 화합물 등을 들 수 있으며, 이들은 단독으로 또는 2종 이상을 혼합하여 사용할 수 있으나, 역시 이에 한정되지 않는다.The aprotic polar solvent is, for example, N, N-dimethylpropionamide (DMPA), N, N, -dimethylacetamide (DMAC), N, N-dimethylisobutylamide (DMIB), N, N-dimethylacrylamide ( DMAR), N, N-dimethylmethacrylamide, N, N-dimethyldecanamide (DMDA), N, N-diethylformamide (DEF), N, N-diethylacetamide (DEAC), N, N -Diethylpropionamide (DEPA), N, N-diethylisobutylamide (DEIB), N, N-diethylacrylamide (DEA), N, N-diethylmethacrylamide, 3-methoxy-N Dialkylamides such as N-dimethylpropionamide (MDMP) and 3-butoxy-N, N-dimethylpropionamide, N, N-diethylformamide (DEF) and N, N-dimethylformamide (DMF) System compounds; N-methylformamide (NMF), N-ethylformamide (NEF), N-methylpropionamide (NMPA), N-methylacetamide (NMA), N-ethylacetamide (NEA), N- (2- Monoamide compounds such as hydroxyethyl) acetamide; lactone compounds such as γ-butyrolactone; Sulfoxide compounds such as dimethyl sulfoxide (DMSO) and sulfolane; Phosphate compounds such as triethyl phosphate (TEP) and tributyl phosphate (TBP); Carbonate compounds such as dimethyl carbonate (DMC), ethylene carbonate (EC), and propylene carbonate (PC); And imidazole compounds such as 1,3-dimethyl-2-imidazoridinone (DMI), and the like, and these may be used alone or in combination of two or more, but are not limited thereto.
바람직하게는, 디알킬아미드계 화합물, 모노아미드계 화합물과 같은 아미드계 화합물, 더욱 바람직하게는 디알킬아미드계 화합물을 사용하는 것이, 세정성 측면에서 좋다.Preferably, an amide compound such as a dialkylamide compound or a monoamide compound, and more preferably a dialkylamide compound is preferable in view of washability.
상기 수용성 극성용매는 상기 화학식 1로 표시되는 글라임계 화합물과 함께 마스크에 잔류하는 유기소재를 용해 시키는 역할을 수행하며, 또한 세정 후 탈이온수의 린스 과정에서 물에 의한 세정액 제거를 수월하게 하여 제거된 유기소재의 재흡착/재부착을 최소화하거나 특정 유기소재의 제거력 향상에 구현할 수 있는 역할을 수행할 수 있다.The water-soluble polar solvent serves to dissolve the organic material remaining in the mask with the glyme-based compound represented by the formula (1), and also to facilitate the removal of the cleaning solution by water in the rinse process of deionized water after cleaning Minimize the resorption / reattachment of the organic material or can play a role that can be implemented to improve the removal of the specific organic material.
상기 수용성 극성용매는 추후 세정 공정에서 요구되는 성능에 따라 선택될 수 있으며, 상기 수용성 극성용매는 적당한 세정력 및 공정의 안정적 운영을 위해 비점이 낮지 않은 것이 바람직하다. 예컨대 150 내지 290 ℃의 비점을 가지는 것이 바람직하다. 상기 범위 내의 비점을 가지는 수용성 극성 용매를 사용하는 경우 환경적, 공정적인 측면에서 바람직할 수 있다. The water-soluble polar solvent may be selected according to the performance required in the subsequent cleaning process, it is preferable that the water-soluble polar solvent does not have a low boiling point for proper cleaning power and stable operation of the process. For example, it is preferable to have a boiling point of 150-290 degreeC. When using a water-soluble polar solvent having a boiling point within the above range it may be preferable in terms of environmental and process.
상기 수용성 용매의 비점이 낮은 경우 세정 공정에서 휘발되어 공정 사용량이 많아 지고 작업 환경에 악영향을 미칠 수 있으므로 상기 범위 내의 비점을 가지는 수용성 극성 용매를 사용하는 것이 바람직하다.When the boiling point of the water-soluble solvent is low, it is preferable to use a water-soluble polar solvent having a boiling point within the above range because it may be volatilized in the cleaning process and the process usage may increase and adversely affect the working environment.
상기 수용성 극성용매는 상기 세정액 조성물 전체 100 중량부에 대하여 0 내지 90 중량부, 바람직하게는 0 내지 80 중량부로 포함될 수 있다. 상기 수용성 극성용매가 상기 범위 내로 포함되는 경우, 세정력이 우수하면서도, 세정 후 탈이온수의 린스 과정에서 물에 의한 세정액 제거가 용이한 세정액 조성물을 제조할 수 있는 이점이 있으므로 바람직하다.The water-soluble polar solvent may be included in an amount of 0 to 90 parts by weight, preferably 0 to 80 parts by weight, based on 100 parts by weight of the cleaning liquid composition. When the water-soluble polar solvent is included in the above range, it is preferable because it has an excellent cleaning power, it is possible to prepare a cleaning liquid composition that is easy to remove the cleaning liquid by water in the rinse process of deionized water after cleaning.
본 발명의 또 다른 실시형태에 있어서, 물을 전체 100 중량부에 대하여 7 중량부 이하로 포함할 수 있다.In still another embodiment of the present invention, water may be included in an amount of 7 parts by weight or less based on 100 parts by weight in total.
본 발명의 또 다른 실시형태에 있어서, 상기 마스크 세정액 조성물은, 물을 전체 100 중량부에 대하여 5 중량부 이하로 포함할 수 있다.In still another embodiment of the present invention, the mask cleaning liquid composition may contain 5 parts by weight or less based on 100 parts by weight of the total.
본 발명의 또 다른 실시형태에 있어서, 상기 마스크 세정액 조성물은, 상기 물을 전체 100 중량부에 대하여 3 중량부 이하로 포함할 수 있다.In another embodiment of the present invention, the mask cleaning liquid composition may include 3 parts by weight or less of the water based on 100 parts by weight of the total.
상기 물이 상기 범위 이하로 포함되는 경우 유기 EL(Organic Electro Luminescence)의 용해성 저하를 야기하지 않아 바람직하다.When the water is included below the above range it is preferable not to cause a decrease in the solubility of organic EL (Organic Electro Luminescence).
상기 물은 불순물을 최대한 저감시킨 탈이온수(deionized water, DIW) 또는 초순수(ultrapure water)일 수 있으나, 이에 한정되지 않는다.The water may be deionized water (DIW) or ultrapure water in which impurities are reduced as much as possible, but are not limited thereto.
또한, 상기 물은 시간이 지남에 따라 수분을 흡수함으로써 포함될 수도 있지만, 본 발명에 따른 세정액 조성물은 물을 함유하지 않는 것이 바람직하다.In addition, the water may be included by absorbing moisture over time, it is preferable that the cleaning liquid composition according to the present invention does not contain water.
본 발명에 따른 세정액 조성물은 상기 화학식 1로 표시되는 글라임계 화합물을 포함하여 우수한 세정력을 가지기 때문에 초음파 및 전해 세정 등이 불필요한 이점이 있다.Since the cleaning liquid composition according to the present invention has excellent cleaning power including the glyme-based compound represented by Chemical Formula 1, ultrasonic cleaning and electrolytic cleaning are unnecessary.
본 발명의 또 다른 실시형태에 있어서, 상기 마스크 세정액 조성물은 유기 소재 진공 증착 공정에 사용되는 마스크를 세정하는 마스크 세정액 조성물일 수 있다.In still another embodiment of the present invention, the mask cleaning liquid composition may be a mask cleaning liquid composition for cleaning a mask used in an organic material vacuum deposition process.
본 발명에 따른 마스크 세정액 조성물은, NMP, NEP, DMF 등과 같은 환경규제물질을 포함하지 않으면서도 세정력이 우수한 이점이 있다.The mask cleaning liquid composition according to the present invention has an advantage of excellent cleaning power without including environmental regulatory substances such as NMP, NEP, DMF, and the like.
이하, 본 명세서를 구체적으로 설명하기 위해 실시예를 들어 상세히 설명한다. 그러나, 본 명세서에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 명세서의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되지는 않는다. 본 명세서의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 명세서를 보다 완전하게 설명하기 위해 제공되는 것이다. 또한, 이하에서 함유량을 나타내는 "%" 및 "부"는 특별히 언급하지 않는 한 중량 기준이다.Hereinafter, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present disclosure may be modified in various other forms, and the scope of the present specification is not to be interpreted as being limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art. In addition, "%" and "part" which show content below are a basis of weight unless there is particular notice.
실시예Example 및  And 비교예Comparative example : 세정액 조성물의 제조: Preparation of Cleaning Liquid Composition
하기 표 1의 구성 및 조성에 따라 실시예 및 비교예에 따른 세정액 조성물을 제조하였다.To prepare a cleaning solution composition according to the Example and Comparative Example according to the configuration and composition of Table 1.
구분division 글라임계 화합물Glymeic Compound [중량%][weight%] 수용성 극성용매Water soluble polar solvent 기타Etc [중량%][weight%]
비양자성 극성용매Aprotic Polar Solvent [중량%][weight%] 양자성 극성용매Quantum polar solvent [중량%][weight%]
실시예 1Example 1 DEDGDEDG 100100 -- -- -- -- -- --
실시예 2Example 2 DMDGDMDG 100100 -- -- -- -- -- --
실시예 3Example 3 DMTGDMTG 100100 -- -- -- -- -- --
실시예 4Example 4 MEDGMEDG 100100 -- -- -- -- -- --
실시예 5Example 5 PDMPDM 100100 -- -- -- -- -- --
실시예 6Example 6 DPDMDPDM 100100 -- -- -- -- -- --
실시예 7Example 7 DEDGDEDG 7070 -- -- -- -- -- --
DMDGDMDG 3030 -- -- -- -- -- --
실시예 8Example 8 PDMPDM 8080 -- -- -- -- -- --
DPDMDPDM 2020 -- -- -- -- -- --
실시예 9Example 9 DEDGDEDG 8080 DMPADMPA 2020 -- -- -- --
실시예 10Example 10 MEDGMEDG 6565 DMACDMAC 3535 -- -- -- --
실시예 11Example 11 DEDGDEDG 7070 DEFDEF 3030 -- -- -- --
실시예 12Example 12 MEDGMEDG 1010 DEACDEAC 9090 -- -- -- --
실시예 13Example 13 MBDGMBDG 2020 NEFNEF 8080 -- -- -- --
실시예 14Example 14 MBTGMBTG 5050 NMPANMPA 5050 -- -- -- --
실시예 15Example 15 MEDGMEDG 6565 DMPADMPA 2525 EDGEDG 1010 -- --
실시예 16Example 16 DEDGDEDG 5050 DMACDMAC 3535 HMDMDOHMDMDO 1515 -- --
실시예 17Example 17 DMDGDMDG 8080 -- -- HMDHMD 2020 -- --
실시예 18Example 18 DMTGDMTG 8080 -- -- MDGMDG 2020 -- --
실시예 19Example 19 PDMPDM 3030 DEFDEF 7070 -- -- -- --
실시예 20Example 20 DEDGDEDG 99.599.5 -- -- -- -- DIWDIW 0.50.5
실시예 21Example 21 DMDGDMDG 9999 -- -- -- -- DIWDIW 1One
실시예 22Example 22 DEDGDEDG 9898 -- -- -- -- DIWDIW 22
실시예 23Example 23 DMDGDMDG 9797 -- -- -- -- DIWDIW 33
실시예 24Example 24 DEDGDEDG 9595 -- -- -- -- DIWDIW 55
실시예 25Example 25 DMDGDMDG 9090 -- -- -- -- DIWDIW 1010
비교예 1Comparative Example 1 -- -- NMPNMP 100100 -- -- -- --
비교예 2Comparative Example 2 -- -- DMFDMF 100100 -- -- -- --
비교예 3Comparative Example 3 -- -- DMSODMSO 100100 -- -- -- --
비교예 4Comparative Example 4 -- -- PCPC 100100 -- -- -- --
비교예 5Comparative Example 5 -- -- DEFDEF 100100 -- -- -- --
비교예 6Comparative Example 6 -- -- DMACDMAC 100100 -- -- -- --
비교예 7Comparative Example 7 -- -- NEFNEF 100100 -- -- -- --
비교예 8Comparative Example 8 -- -- NMPANMPA 100100 -- -- -- --
비교예 9Comparative Example 9 -- -- NMFNMF 100100 -- -- -- --
비교예 10Comparative Example 10 -- -- -- -- EDGEDG 100100 -- --
비교예 11Comparative Example 11 -- -- -- -- MDGMDG 100100 -- --
비교예 12Comparative Example 12 -- -- -- -- MTGMTG 100100 -- --
비교예 13Comparative Example 13 -- -- -- -- MFDGMFDG 100100 -- --
비교예 14Comparative Example 14 -- -- -- -- MFTGMFTG 100100 -- --
비교예 15Comparative Example 15 -- -- DEFDEF 5050 MFDGMFDG 5050 -- --
비교예 16Comparative Example 16 -- -- DMACDMAC 5050 MFTGMFTG 5050 -- --
비교예 17Comparative Example 17 -- -- -- -- MDGMDG 5050 -- --
-- -- -- -- MFGMFG 5050 -- --
비교예 18Comparative Example 18 -- -- -- -- -- -- HexaneHexane 100100
비교예19Comparative Example 19 -- -- -- -- -- -- Cyclo pentaneCyclo pentane 100100
비교예 20Comparative Example 20 MEDGMEDG 5050 -- -- -- -- Cyclo pentaneCyclo pentane 5050
비교 예21Comparative Example 21 MEDGMEDG 8080 -- -- -- -- Cyclo pentaneCyclo pentane 2020
DEDG : 디에틸렌 글리콜 디에틸 에테르, DMDG : 디에틸렌 글리콜 디메틸 에테르, DMTG : 트리에틸렌 글리콜 디메틸 에테르, MEDG : 디에틸렌 글리콜 메틸 에틸 에테르, PDM : 프로필렌 글리콜 디메틸 에테르, DPDM : 디프로필렌 글리콜 디메틸 에테르, DMPA : N,N-디메틸프로피온아미드, DMAC : N,N-디메틸아세트아미드, DEF : N,N-디에틸포름아미드, DEAC : N,N-디에틸아세트아미드, NEF : N-에틸포름아미드, NMPA : N-메틸프로피온아미드, EDG : 디에틸렌글리콜 모노에틸 에테르, HMDMDO : 4-하이드록시메틸-2,2-디메틸-1,3-디옥솔란, HMD : 4-하이드록시메틸-1,3-디옥솔란, MDG : 디에틸렌글리콜 모노메틸 에테르, NMP : N-메틸-2-피롤리돈, DMF : N,N-디메틸포름아미드, DMSO : 디메틸술폭사이드, PC : 프로필렌카보네이트, NMF : N-메틸포름아미드, MTG : 트리에틸렌글리콜 모노메틸 에테르, MFDG : 디프로필렌글리콜 모노메틸 에테르, MFTG : 트리프로필렌글리콜 모노메틸 에테르, MFG : 프로필렌글리콜 모노메틸 에테르DEDG: diethylene glycol diethyl ether, DMDG: diethylene glycol dimethyl ether, DMTG: triethylene glycol dimethyl ether, MEDG: diethylene glycol methyl ethyl ether, PDM: propylene glycol dimethyl ether, DPDM: dipropylene glycol dimethyl ether, DMPA : N, N-dimethylpropionamide, DMAC: N, N-dimethylacetamide, DEF: N, N-diethylformamide, DEAC: N, N-diethylacetamide, NEF: N-ethylformamide, NMPA : N-methylpropionamide, EDG: diethylene glycol monoethyl ether, HMDMDO: 4-hydroxymethyl-2,2-dimethyl-1,3-dioxolane, HMD: 4-hydroxymethyl-1,3-diox Solan, MDG: diethylene glycol monomethyl ether, NMP: N-methyl-2-pyrrolidone, DMF: N, N-dimethylformamide, DMSO: dimethyl sulfoxide, PC: propylene carbonate, NMF: N-methylform Amide, MTG: triethylene glycol monomethyl ether, MFDG: dipropyl Glycol monomethyl ether, MFTG: tripropylene glycol monomethyl ether, MFG: Propylene glycol monomethyl ether
실험예Experimental Example 1: 유기발광 소자 용해성 평가 1: Solubility evaluation of organic light emitting device
실시예 및 비교예에 따른 마스크 세정액 조성물의 세정 효과를 확인하기 위하여 통상적인 증착 공정에 따라 유기발광소자에 포함되는 발광층 및 전자/정공 수송층으로 사용되는 유기 소재가 각각 별도로 흡착된 3종의 마스크(재질: Invar)에 대한 용해성 평가를 실시하였다.In order to confirm the cleaning effect of the mask cleaning liquid compositions according to the Examples and Comparative Examples, three kinds of masks in which an organic material used as an emission layer and an electron / hole transport layer included in an organic light emitting device are separately adsorbed according to a conventional deposition process ( Material: Invar) was evaluated for solubility.
증착 공정 후 마스크로부터 유기 소재를 분리한 후, 막자 사발을 이용하여 파우더 형태로 만든 후 224㎛ 체로 분리하였다. 50ml 비커를 사용하여 실시예 및 비교예에 따라 제조한 마스크 세정액 조성물 전체 100 중량%에 대하여 0.1 중량%를 만족하도록 상온에서 마스크 세정액 조성물에 유기소재 파우더를 녹여 용해성(녹는 속도, 분 단위 측정)을 평가하여 하기 표 2에 나타내었다.After the deposition process, the organic material was separated from the mask, made into a powder form using a mortar, and then separated into a 224 μm sieve. The solubility (melting rate, measurement in minutes) was dissolved by dissolving the organic material powder in the mask cleaning liquid composition at room temperature to satisfy 0.1% by weight with respect to 100% by weight of the total mask cleaning liquid composition prepared according to the Examples and Comparative Examples using a 50 ml beaker. The evaluation is shown in Table 2 below.
구분division 용해성 평가Solubility Assessment
Mask 1분리 유기소재Mask 1 separated organic material Mask 2분리 유기소재Mask 2 separated organic material Mask 3분리 유기소재Mask 3 separated organic material
실시예 1Example 1 5분5 minutes 6분6 minutes 15분15 minutes
실시예 2Example 2 6분6 minutes 6분6 minutes 15분15 minutes
실시예 3Example 3 7분7 minutes 7분7 minutes 15분15 minutes
실시예 4Example 4 6분6 minutes 5분5 minutes 15분15 minutes
실시예 5Example 5 7분7 minutes 8분8 minutes 17분17 minutes
실시예 6Example 6 8분8 minutes 7분7 minutes 17분17 minutes
실시예 7Example 7 7분7 minutes 7분7 minutes 15분15 minutes
실시예 8Example 8 8분8 minutes 8분8 minutes 15분15 minutes
실시예 9Example 9 5분5 minutes 5분5 minutes 12분12 minutes
실시예 10Example 10 5분5 minutes 4분4 minutes 13분13 minutes
실시예 11Example 11 5분5 minutes 4분4 minutes 12분12 minutes
실시예 12Example 12 10분10 minutes 8분8 minutes 12분12 minutes
실시예 13Example 13 10분10 minutes 6분6 minutes 25분25 minutes
실시예 14Example 14 8분8 minutes 5분5 minutes 25분25 minutes
실시예 15Example 15 4분4 minutes 16분16 minutes 12분12 minutes
실시예 16Example 16 5분5 minutes 14분14 minutes 13분13 minutes
실시예 17Example 17 4분4 minutes 15분15 minutes 20분20 minutes
실시예 18Example 18 5분5 minutes 14분14 minutes 20분20 minutes
실시예 19Example 19 6분6 minutes 6분6 minutes 12분12 minutes
실시예 20Example 20 5분5 minutes 6분6 minutes 15분15 minutes
실시예 21Example 21 6분6 minutes 6분6 minutes 15분15 minutes
실시예 22Example 22 6분6 minutes 6분6 minutes 15분15 minutes
실시예 23Example 23 6분6 minutes 6분6 minutes 15분15 minutes
실시예 24Example 24 8분8 minutes 7분7 minutes 17분17 minutes
실시예 25Example 25 10분10 minutes 14분14 minutes 30분30 minutes
비교예 1Comparative Example 1 5분5 minutes 5분5 minutes 12분12 minutes
비교예 2Comparative Example 2 10분10 minutes 30분30 minutes 30분30 minutes
비교예 3Comparative Example 3 10분10 minutes 40분40 minutes 30분30 minutes
비교예 4Comparative Example 4 40분40 minutes 40분40 minutes 60분60 minutes
비교예 5Comparative Example 5 10분10 minutes 30분30 minutes 20분20 minutes
비교예 6Comparative Example 6 10분10 minutes 40분40 minutes 20분20 minutes
비교예 7Comparative Example 7 11분11 minutes 45분45 minutes 30분30 minutes
비교예 8Comparative Example 8 12분12 minutes 55분 55 minutes 30분30 minutes
비교예 9Comparative Example 9 11분11 minutes 50분50 minutes 35분35 minutes
비교예 10Comparative Example 10 30분30 minutes 30분30 minutes 60분60 minutes
비교예 11Comparative Example 11 30분30 minutes 30분30 minutes 60분60 minutes
비교예 12Comparative Example 12 30분30 minutes 30분30 minutes 60분60 minutes
비교예 13Comparative Example 13 30분30 minutes 30분30 minutes 60분60 minutes
비교예 14Comparative Example 14 30분30 minutes 30분30 minutes 60분60 minutes
비교예 15Comparative Example 15 40분40 minutes 40분40 minutes 30분30 minutes
비교예 16Comparative Example 16 35분35 minutes 45분45 minutes 30분30 minutes
비교예 17Comparative Example 17 40분40 minutes 40분40 minutes 60분60 minutes
비교예 18Comparative Example 18 60분 이상More than 60 minutes 60분 이상More than 60 minutes 60분 이상More than 60 minutes
비교예 19Comparative Example 19 60분 이상More than 60 minutes 60분 이상More than 60 minutes 60분 이상More than 60 minutes
비교예 20Comparative Example 20 40분40 minutes 45분45 minutes 60분60 minutes
비교예 21Comparative Example 21 30분30 minutes 35분35 minutes 40분40 minutes
Mask 1 흡착 물질: 1,3-bis(carbazol-9-yl)-benzene (mCP), Mask 2 흡착 물질: 2-(9,9-Spirobifluoren-2-yl)-9,9-spirobifluorene(BSBF), Mask 3 흡착 물질: 1,3,5-Tris(1-phenyl-1Hbenzimidazol- 2-yl)benzene(TPBi)Mask 1 adsorbent: 1,3-bis (carbazol-9-yl) -benzene (mCP), Mask 2 adsorbent: 2- (9,9-Spirobifluoren-2-yl) -9,9-spirobifluorene (BSBF) , Mask 3 Adsorbent: 1,3,5-Tris (1-phenyl-1Hbenzimidazol-2-yl) benzene (TPBi)
표 2를 살펴 보면 화학식 1로 표시되는 글라임계 화합물, 화학식 1로 표시되는 글라임계 화합물 및 수용성 극성 용매를 혼합한 실시예는 용해력이 우수한 것을 알 수 있다.Looking at Table 2, it can be seen that the examples in which the glyme-based compound represented by the formula (1), the glyme-based compound represented by the formula (1) and the water-soluble polar solvent are mixed have excellent dissolving power.
환경 규제 물질을 포함하는 비교예 1을 제외하고는 한 개 이상의 Mask에서 30분 이상을 보여 용해력이 저하된 것을 확인 할 수 있다.Except for Comparative Example 1, which includes an environmental regulatory substance, one or more masks showed 30 minutes or more, indicating that the dissolving ability was reduced.
화학식 1로 표시되는 글라임계 물질을 사용하지 않고, 수용성 극성용매 중 비양자성 극성용매와 양자성극성용매를 단독 또는 혼합한 비교예에서는 Mask 1~3의 용해력이 저하되는 것을 확인 할 수 있다. In the comparative example in which the aprotic polar solvent and the quantum polar solvent are used alone or in a mixed solution without using the glyme-based material represented by the formula (1), it can be seen that the dissolving power of the masks 1 to 3 decreases.
무극성 용매를 포함하는 비교예의 경우 Mask 1~3의 용해력이 저하되는 것을 확인할 수 있었으며, 특히, 무극성 용매만을 이용한 비교예의 경우 Mask 1~3의 용해력이 크게 저하되는 것을 확인 할 수 있다.In the case of the comparative example containing a non-polar solvent it was confirmed that the dissolving power of Mask 1 to 3 is reduced, in particular, in the case of the comparative example using only a non-polar solvent it can be confirmed that the dissolving power of Mask 1 to 3 greatly reduced.
실험예Experimental Example 2: 유기발광소자 용해 안정성 평가 2: Evaluation of dissolution stability of organic light emitting device
실시예 및 비교예에 따른 마스크 세정액 조성물의 세정 효과를 확인하기 위하여 통상적인 증착 공정에 따라 유기발광소자에 포함되는 발광층 및 전자/정공 수송층으로 사용되는 유기 소재가 각각 별도로 흡착된 3종의 마스크(재질: Invar)에 대한 용해 안정성 평가를 실시하였다.In order to confirm the cleaning effect of the mask cleaning liquid compositions according to the Examples and Comparative Examples, three kinds of masks in which an organic material used as an emission layer and an electron / hole transport layer included in an organic light emitting device are separately adsorbed according to a conventional deposition process ( Material: Invar) was evaluated for dissolution stability.
증착 공정 후 마스크로부터 유기소재를 분리한 후, 막자 사발을 이용하여 파우더 형태를 만든 후, 224㎛ 체로 분리하였다. 실시예 및 비교예에 따라 제조한 마스크 세정액 조성물 전체 100 중량%에 대하여 0.1 중량%를 만족하도록 마스크 세정액 조성물에 유기소재 파우더를 60℃에서 1시간 용해 후 유리재질의 투명 50ml 유리병으로 분취 후 상온에서 24시간 방치 후 실시예 및 비교예에 따른 마스크 세정액 조성물(약액)의 안정성(탁도 증가 및 침전물)을 평가 하여 하기 표 3에 나타내었다. After the deposition process, the organic material was separated from the mask, and then made into a powder form using a mortar and then separated into a 224㎛ sieve. After dissolving the organic material powder in the mask cleaning liquid composition at 60 ° C. for 1 hour to satisfy 0.1% by weight with respect to 100% by weight of the total mask cleaning liquid composition prepared according to the Examples and Comparative Examples, a glass 50 ml glass bottle was aliquoted and then room temperature. After leaving for 24 hours in the evaluation of the stability (turbidity increase and precipitate) of the mask cleaning liquid composition (chemical solution) according to Examples and Comparative Examples are shown in Table 3 below.
평가 기준은 하기와 같다.Evaluation criteria are as follows.
육안으로 평가 시 약액의 투명도 변화 없음: ◎No change in the transparency of the chemical when evaluated visually: ◎
육안으로 평가 시 탁도 약간 증가(투명): ○Slightly increased turbidity when evaluated visually (transparent): ○
육안으로 평가 시 탁도 증가(불투명): △Increased turbidity (opacity) when visually assessed: △
육안으로 평가 시 침전물 발생: ×Sediment Generated By Visual Evaluation: ×
구분division 용해 안정성Melt stability
Mask 1분리 유기소재Mask 1 separated organic material Mask 2분리 유기소재Mask 2 separated organic material Mask 3분리 유기소재Mask 3 separated organic material
실시예 1Example 1 ◎◎ ◎◎ ◎◎
실시예 2Example 2 ◎◎ ◎◎ ◎◎
실시예 3Example 3 ◎◎ ◎◎ ◎◎
실시예 4Example 4 ◎◎ ◎◎ ◎◎
실시예 5Example 5 ◎◎ ○○ ○○
실시예 6Example 6 ◎◎ ◎◎ ○○
실시예 7Example 7 ◎◎ ◎◎ ◎◎
실시예 8Example 8 ◎◎ ○○ ◎◎
실시예 9Example 9 ◎◎ ◎◎ ◎◎
실시예 10Example 10 ◎◎ ◎◎ ◎◎
실시예 11Example 11 ◎◎ ◎◎ ◎◎
실시예 12Example 12 ○○ ○○ ◎◎
실시예 13Example 13 ○○ ◎◎ ○○
실시예 14Example 14 ◎◎ ◎◎ ○○
실시예 15Example 15 ◎◎ ○○ ◎◎
실시예 16Example 16 ◎◎ ○○ ◎◎
실시예 17Example 17 ◎◎ ○○ ○○
실시예 18Example 18 ◎◎ ○○ ○○
실시예 19Example 19 ◎◎ ◎◎ ◎◎
실시예 20Example 20 ◎◎ ◎◎ ◎◎
실시예 21Example 21 ◎◎ ◎◎ ◎◎
실시예 22Example 22 ◎◎ ◎◎ ◎◎
실시예 23Example 23 ◎◎ ◎◎ ◎◎
실시예 24Example 24 ◎◎ ◎◎ ○○
실시예 25Example 25 ○○ ○○ △△
비교예 1Comparative Example 1 ◎◎ ◎◎ ◎◎
비교예 2Comparative Example 2 ○○ ○○ △△
비교예 3Comparative Example 3 △△ △△ △△
비교예 4Comparative Example 4 △△ △△ ××
비교예 5Comparative Example 5 ○○ △△ ○○
비교예 6Comparative Example 6 ○○ △△ ○○
비교예 7Comparative Example 7 ○○ △△ △△
비교예 8Comparative Example 8 ○○ xx △△
비교예 9Comparative Example 9 ○○ △△ △△
비교예 10Comparative Example 10 ○○ △△ × ×
비교예 11Comparative Example 11 △△ △△ ××
비교예 12Comparative Example 12 △△ △△ ××
비교예 13Comparative Example 13 △△ △△ ××
비교예 14Comparative Example 14 △△ △△ ××
비교예 15Comparative Example 15 ○○ △△ △△
비교예 16Comparative Example 16 ○○ △△ △△
비교예 17Comparative Example 17 △△ △△ ××
비교예 18Comparative Example 18 ×× ×× ××
비교예 19Comparative Example 19 ×× ×× ××
비교예 20Comparative Example 20 △△ △△ ××
비교예 21Comparative Example 21 △△ △△ △△
Mask 1 흡착 물질: 1,3-bis(carbazol-9-yl)-benzene (mCP), Mask 2 흡착 물질: 2-(9,9-Spirobifluoren-2-yl)-9,9-spirobifluorene(BSBF), Mask 3 흡착 물질: 1,3,5-Tris(1-phenyl-1Hbenzimidazol- 2-yl)benzene(TPBi)Mask 1 adsorbent: 1,3-bis (carbazol-9-yl) -benzene (mCP), Mask 2 adsorbent: 2- (9,9-Spirobifluoren-2-yl) -9,9-spirobifluorene (BSBF) , Mask 3 Adsorbent: 1,3,5-Tris (1-phenyl-1Hbenzimidazol-2-yl) benzene (TPBi)
표 3을 살펴 보면 화학식 1로 표시되는 글라임계 화합물, 화학식 1로 표시되는 글라임계 화합물 및 수용성 극성 용매를 혼합한 실시예에서는 Mask 1~3 모두 전체적으로 용해 안정성이 우수함을 확인 할 수 있다.Looking at Table 3, in the examples in which the glyme-based compound represented by the formula (1), the glyme-based compound represented by the formula (1), and the water-soluble polar solvent are mixed, it can be confirmed that the mask 1 to 3 have excellent dissolution stability as a whole.
하지만 환경 규제 물질을 포함하는 비교예 1을 제외한 비교예 에서는 한 개 이상의 약액에서 불투명 하며 용해 안정성이 저하된 것을 확인 할 수 있다. 무극성 용매를 포함하는 비교예 에서는 용해 안정성이 저하되고 불투명 하여 상용성이 떨어지는 것을 확인 할 수 있다.However, in Comparative Examples except for Comparative Example 1 containing an environmental regulatory substance, it may be confirmed that one or more chemical solutions are opaque and the dissolution stability is lowered. In the comparative example containing a nonpolar solvent, it can confirm that melt | fusion stability falls, it is opaque and it is incompatible.
화학식 1로 표시되는 글라임계 물질을 사용하지 않고, 수용성 극성용매 중 비양자성 극성용매 와 양자성극성용매를 단독 또는 혼합한 비교예에서는 용해안정성이 저하되는 것을 확인 할 수 있다.In the comparative example in which the aprotic polar solvent and the quantum polar solvent are used alone or in a mixed solution without using the glyme-based material represented by the formula (1), it can be confirmed that the dissolution stability is lowered.

Claims (10)

  1. 하기 화학식 1로 표시되는 글라임계 화합물을 포함하고,To include a glyme compound represented by the formula (1),
    무극성 용매를 함유하지 않는, 마스크 세정액 조성물:Mask cleaning liquid composition, containing no nonpolar solvent:
    [화학식 1][Formula 1]
    Figure PCTKR2019000230-appb-I000003
    Figure PCTKR2019000230-appb-I000003
    상기 화학식 1에서,In Chemical Formula 1,
    R1 및 R2는 각각 독립적으로 C1 내지 C10의 직쇄 또는 C3 내지 C10의 분지쇄 알킬기이고,R1 and R2 are each independently C1 to C10 straight chain or C3 to C10 branched alkyl group,
    R3는 C1 내지 C10의 직쇄 또는 C3 내지 C10의 분지쇄 알킬렌기이며,R3 is C1 to C10 straight chain or C3 to C10 branched alkylene group,
    n은 1 내지 4의 정수이다.n is an integer of 1-4.
  2. 제1항에 있어서,The method of claim 1,
    상기 화학식 1로 표시되는 글라임계 화합물은 에틸렌 글리콜 디메틸 에테르(DMG), 디에틸렌 글리콜 디메틸 에테르(DMDG), 트리에틸렌 글리콜 디메틸 에테르(DMTG), 디에틸렌 글리콜 디에틸 에테르(DEDG), 디에틸렌 글리콜 메틸 에틸 에테르(MEDG), 디에틸렌 글리콜 메틸 부틸 에테르(MBDG), 트리에틸렌 글리콜 메틸 부틸 에테르(MBTG), 프로필렌 글리콜 디메틸 에테르(PDM), 디프로필렌 글리콜 디메틸 에테르(DPDM) 및 에틸렌 글리콜 디에틸 에테르(DEG)로 이루어진 군으로부터 선택되는 1 이상인 것인 마스크 세정액 조성물.Glyme-based compound represented by the formula (1) is ethylene glycol dimethyl ether (DMG), diethylene glycol dimethyl ether (DMDG), triethylene glycol dimethyl ether (DMTG), diethylene glycol diethyl ether (DEDG), diethylene glycol methyl Ethyl ether (MEDG), diethylene glycol methyl butyl ether (MBDG), triethylene glycol methyl butyl ether (MBTG), propylene glycol dimethyl ether (PDM), dipropylene glycol dimethyl ether (DPDM) and ethylene glycol diethyl ether (DEG Mask cleaning liquid composition is one or more selected from the group consisting of
  3. 제1항에 있어서,The method of claim 1,
    상기 화학식 1로 표시되는 글라임계 화합물은 δP가 4.5 내지 6.5 MPa1/2이고, δH 가 4.0 내지 6.0 MPa1/ 2 의 한센 용해도 상수(Hansen solubility Parameter) 값을 갖는 것인 마스크 세정액 조성물.Glyme-based compound represented by Formula 1 is δ P is 4.5 to 6.5 MPa 1/2 , δ H It is 4.0 to 6.0 MPa 1/2 Hansen solubility constant (Hansen solubility Parameter) a mask cleaning liquid composition having a value of.
  4. 제1항에 있어서,The method of claim 1,
    수용성 극성용매를 더 포함하는 것인 마스크 세정액 조성물.Mask cleaning liquid composition further comprising a water-soluble polar solvent.
  5. 제4항에 있어서,The method of claim 4, wherein
    상기 수용성 극성용매는 양자성 극성용매 및 비양자성 극성용매로 이루어진 군에서 선택되는 1 이상을 포함하는 것인 마스크 세정액 조성물.The water-soluble polar solvent is a mask cleaning liquid composition comprising at least one selected from the group consisting of a protic polar solvent and an aprotic polar solvent.
  6. 제4항에 있어서,The method of claim 4, wherein
    상기 수용성 극성용매는 상기 마스크 세정액 조성물 전체 100 중량부에 대하여 0 내지 90 중량부로 포함되는 것인 마스크 세정액 조성물.The water-soluble polar solvent is a mask cleaning liquid composition comprising 0 to 90 parts by weight based on 100 parts by weight of the total mask cleaning liquid composition.
  7. 제1항에 있어서,The method of claim 1,
    물을 전체 100 중량부에 대하여 7 중량부 이하로 포함하는 것인 마스크 세정액 조성물.The mask cleaning liquid composition comprising less than 7 parts by weight of water based on 100 parts by weight of the total.
  8. 제7항에 있어서,The method of claim 7, wherein
    상기 물을 전체 100 중량부에 대하여 5 중량부 이하로 포함하는 것인 마스크 세정액 조성물.The mask cleaning liquid composition comprising 5 parts by weight or less based on 100 parts by weight of the total water.
  9. 제8항에 있어서,The method of claim 8,
    상기 물을 전체 100 중량부에 대하여 3 중량부 이하로 포함하는 것인 마스크 세정액 조성물.The mask cleaning liquid composition comprising the water in 3 parts by weight or less based on 100 parts by weight of the total.
  10. 제1항에 있어서,The method of claim 1,
    상기 마스크 세정액 조성물은 유기 소재 진공 증착 공정에 사용되는 마스크를 세정하는 것인 마스크 세정액 조성물.The mask cleaning liquid composition is to clean the mask used in the organic material vacuum deposition process.
PCT/KR2019/000230 2018-02-06 2019-01-08 Mask cleaning solution composition WO2019156363A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20180014367 2018-02-06
KR10-2018-0014367 2018-02-06
KR1020180157353A KR102640138B1 (en) 2018-02-06 2018-12-07 Cleaning solution composition
KR10-2018-0157353 2018-12-07

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WO2019156363A1 true WO2019156363A1 (en) 2019-08-15

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003129089A (en) * 2001-10-24 2003-05-08 Daikin Ind Ltd Detergent composition
KR20050037511A (en) * 2002-06-06 2005-04-22 이케이씨 테크놀로지, 인코포레이티드 Semiconductor process residue removal composition and process
KR20080016930A (en) * 2005-07-19 2008-02-22 쇼와 덴코 가부시키가이샤 Removing solution for photosensitive composition
KR20080099413A (en) * 2007-05-09 2008-11-13 동우 화인켐 주식회사 Thinner composition for removing photosensitive resin
KR20120039255A (en) * 2010-10-15 2012-04-25 동우 화인켐 주식회사 Cleaning composition for removing photosensitive resin

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003129089A (en) * 2001-10-24 2003-05-08 Daikin Ind Ltd Detergent composition
KR20050037511A (en) * 2002-06-06 2005-04-22 이케이씨 테크놀로지, 인코포레이티드 Semiconductor process residue removal composition and process
KR20080016930A (en) * 2005-07-19 2008-02-22 쇼와 덴코 가부시키가이샤 Removing solution for photosensitive composition
KR20080099413A (en) * 2007-05-09 2008-11-13 동우 화인켐 주식회사 Thinner composition for removing photosensitive resin
KR20120039255A (en) * 2010-10-15 2012-04-25 동우 화인켐 주식회사 Cleaning composition for removing photosensitive resin

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