WO2019156364A1 - Mask cleaning liquid composition - Google Patents

Mask cleaning liquid composition Download PDF

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Publication number
WO2019156364A1
WO2019156364A1 PCT/KR2019/000231 KR2019000231W WO2019156364A1 WO 2019156364 A1 WO2019156364 A1 WO 2019156364A1 KR 2019000231 W KR2019000231 W KR 2019000231W WO 2019156364 A1 WO2019156364 A1 WO 2019156364A1
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WO
WIPO (PCT)
Prior art keywords
cleaning liquid
liquid composition
mask cleaning
mask
group
Prior art date
Application number
PCT/KR2019/000231
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French (fr)
Korean (ko)
Inventor
이영재
조한혁
김정현
Original Assignee
동우 화인켐 주식회사
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Priority claimed from KR1020180157345A external-priority patent/KR102640141B1/en
Application filed by 동우 화인켐 주식회사 filed Critical 동우 화인켐 주식회사
Publication of WO2019156364A1 publication Critical patent/WO2019156364A1/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
    • C11D7/02—Inorganic 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
    • 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
    • C11D7/32—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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 mask cleaning liquid compositions, and in particular mask cleaning liquid compositions which facilitate the removal of various organics, in particular organic particles, on the mask used in the 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 waves in the ultrasonic cleaning unit have 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.
  • organic particles to improve the performance when forming the organic layer, such as the light emitting layer, hole injection layer, hole transport layer, electron transport layer, electron injection layer, etc. described above, these organic particles are mostly insoluble The problem arises that it is not easy to clean because of the bet.
  • 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.)
  • the present invention is an amide compound represented by the formula (1); And it provides a mask cleaning liquid composition comprising an alkaline compound.
  • R1 and R2 are each independently hydrogen, a methyl group or an ethyl group
  • R3 is hydrogen; Or a C1 to C4 saturated or C2 to C4 unsaturated hydrocarbon group unsubstituted or substituted with a C1 to C4 alkoxy group,
  • R 3 is a C 2 to C 4 saturated or unsaturated hydrocarbon group unsubstituted or substituted with a C 1 to C 4 alkoxy group.
  • the mask cleaning liquid composition according to the present invention can exhibit good cleaning power, in particular, good cleaning power with respect to organic particles, without including an environmental regulation material such as NMP, and thus has an advantage of easy process operation.
  • 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.
  • the amide compound represented by the formula (1) represented by the formula (1); And a mask cleaning liquid composition containing an alkaline compound.
  • R1 and R2 are each independently hydrogen, a methyl group or an ethyl group
  • R3 is hydrogen; Or a C1 to C4 saturated or C2 to C4 unsaturated hydrocarbon group unsubstituted or substituted with a C1 to C4 alkoxy group,
  • R 3 is a C 2 to C 4 saturated or unsaturated hydrocarbon group unsubstituted or substituted with a C 1 to C 4 alkoxy group.
  • the alkoxy group may be linear, branched or cyclic. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C4. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy and the like, but is not limited thereto.
  • the saturated hydrocarbon group may be any of linear or branched chain and cyclic group that satisfy the carbon number.
  • linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group; Branched alkyl groups, such as an isopropyl group and an isobutyl group, etc. are mentioned.
  • the saturated hydrocarbon group is preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms. However, when both R1 and R2 are methyl groups, the saturated hydrocarbon group has 2 to 4 carbon atoms.
  • Cyclopropyl group, cyclobutyl group, etc. are mentioned as said cyclic saturated hydrocarbon group.
  • the unsaturated hydrocarbon group has an unsaturated group at the terminal, and may be a C 2 to C 4 linear aliphatic unsaturated hydrocarbon group or a branched aliphatic hydrocarbon group.
  • linear aliphatic unsaturated hydrocarbon group examples include vinyl group, propenyl group (allyl group) and butynyl group.
  • branched aliphatic unsaturated hydrocarbon group examples include 1-methylpropenyl group and 2-methylpropenyl group. However, it is not limited thereto.
  • the amide compound represented by Formula 1 is N, N-dimethylpropionamide, N, N-dimethylisobutylamide, N, N-dimethylacrylamide, N, N-dimethylmetha Krillamide, N-ethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-diethylpropionamide, N, N-diethylisobutylamide, N, N- It may be at least one selected from the group consisting of diethylacrylamide, N, N-diethyl methacrylamide, 3-methoxy-N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide. .
  • the mask cleaning liquid composition according to the present invention includes the amide-based compound represented by Chemical Formula 1, the mask cleaning liquid composition is excellent in 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 amide compound represented by Chemical Formula 1 may be included in an amount of 50 to 99.9 parts by weight, preferably 60 to 98 parts by weight, and more preferably 75 to 95 parts by weight, based on 100 parts by weight of the mask cleaning liquid composition. There is an advantage that the solvent and cleaning ability to the organic light emitting material is excellent.
  • 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), biphenyl-3,3'-diyl ) bis (diphenylphosphine oxide) (BiPh-m-BiDPO), or mCP (1,3-bis (carbazol-9-yl)) may be used, but is not limited thereto.
  • CBP ((carbazole-9-yl) biphenyl)
  • BSBF (9,9-Spirobifluoren-2-yl) -9,9-spirobifluorene
  • mCP 1,3-bis (carbazol-9-yl)
  • Red luminescent dopants include PIQIr (acac) (bis (1-phenylisoquinoline) acetylacetonate iridium), PQIr (acac) (bis (1-phenylquinoline) acetylacetonate 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)
  • CuPc copper phthalocyanine
  • PEDOT poly (3,4) -ethylenedioxythiophene
  • At least one selected from the group consisting of PANI (polyaniline) and NPD, Bis [2- (2-pyridinyl-N) phenyl-C] (2,4-pentanedionato-O2 as a material of a capping layer (CPL) , O4) iridium (III) and the like can be used.
  • the mask cleaning liquid composition according to the present invention comprises an alkaline compound, and since the mask cleaning liquid composition according to the present invention includes the above-mentioned amide compound and an alkaline compound, various organic substances attached to the mask, in particular, in the form of organic particles, are fired. There is an advantage that the cleaning of the soluble organic material is easy.
  • the alkaline compound is insoluble in the form of a metal complex due to the action of raising the pH in the solution to lift off the adsorbed organic material.
  • Organic materials such as Bis [2- (2-pyridinyl-N) phenyl-C] (2,4-pentanedionato-O2, O4) iridium (III), Poly (9,9-dioctylfluorene-alt-N- (4- It is easy to clean insoluble organic materials such as sec-butylphenyl) -diphenylamine).
  • the alkaline compound may include at least one selected from the group consisting of an inorganic base and an organic base.
  • the inorganic base may include, for example, ammonium hydroxide, sodium hydroxide, potassium hydroxide, and the like, but is not limited thereto, and inorganic bases commonly used in the art may be used without limitation as long as the object of the present invention is not impaired.
  • the organic base may be, for example, primary amines such as methyl amine, ethylamine, isopropyl amine, monoisopropylamine and the like; Secondary amines such as diethyl amine, diisopropyl amine and dibutylamine; Tertiary amines such as trimethylamine, triethylamine, triisopropylamine and tributylamine; Quaternary amines such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide; Choline, monoethanolamine, diethanol amine, 2-amino ethanol, 2- (ethyl amino) ethanol, 2- (methyl amino) ethanol, N-methyl diethanol amine, dimethylaminoethanol, diethylaminoethanol, nitrilotriethanol , Alkanolamines such as 2- (2
  • the organic base may include an amine compound.
  • an amine compound having a hydroxyl group in order to prevent resorption phenomenon after the cleaning is completed.
  • the alkaline compound may be included in an amount of 0.05 to 10 parts by weight, preferably 1 to 7 parts by weight, based on 100 parts by weight of the mask cleaning liquid composition.
  • the alkaline compound may be included in an amount of 0.05 to 10 parts by weight, preferably 1 to 7 parts by weight, based on 100 parts by weight of the mask cleaning liquid composition.
  • 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, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Isopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monobutyl Alkylene glycol monoalkyl ethers such as ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether; And tetrahydrofurfuryl alcohol; And 4-hydroxymethyl-1,3-dioxolane, 4-hydroxymethyl-2,2-dimethyl-1,3-
  • 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.
  • the aprotic polar solvents include, for example, N, N-dimethylpropionamide (DMPA), N, N-dimethylisobutylamide (DMIB), N, N-dimethylacrylamide (DMAR), N, N-dimethylmethacrylamide, N, N-diethylformamide, N, N-diethylacetamide (DEAC), N, N-diethylpropionamide, N, N-diethylisobutylamide, N, N-diethylacrylamide, N , N-diethylmethacrylamide, 3-methoxy-N, N-dimethylpropionamide (MDMP) and 3-butoxy-N, N-dimethylpropionamide, N, N-diethylformamide (DEF), Dialkylamide compounds such as N, N-dimethylformamide (DMF); Mono such as N-methylformamide (NMF), N-methylpropionamide (NMPA), N-methylacetamide (NMA), N-eth
  • 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 plays a role of dissolving the organic material remaining in the mask together with the amide compound and the alkaline compound represented by the formula (1), and also facilitates the removal of the cleaning solution by water in the rinse process of deionized water after washing. By minimizing the resorption / reattachment of the removed organic material or may play a role in improving the removal power of a 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.
  • a water-soluble polar solvent having a boiling point within the above range it may be preferable in terms of environmental and process. Specifically, it is preferable because it is volatilized in the washing step, the amount of the process used increases, and the phenomenon which adversely affects the working environment can be suppressed.
  • the water-soluble polar solvent may be included in 5 to 35 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 20 parts by weight based on 100 parts by weight of the total cleaning liquid composition. have.
  • the water-soluble polar solvent is included in the above range, it is preferable because there is an advantage in that the cleaning liquid composition can be prepared excellent in cleaning power and easy to remove the cleaning liquid by water in the rinsing process of deionized water after washing.
  • the mask cleaning liquid composition may contain 5 parts by weight or less based on 100 parts by weight of the total.
  • the water may be included in an amount of preferably 3 parts by weight or less based on 100 parts by weight of the mask cleaning solution composition.
  • 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 amide compound and the alkaline 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, DMF, DMAC, and NMF.
  • 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 ⁇ ⁇ ⁇ ⁇ Comparative

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Abstract

A mask cleaning liquid composition according to the present invention is characterized by comprising: an amide-based compound represented by chemical formula 1; and an alkaline compound. The mask cleaning liquid composition according to the present invention has an advantage of exhibiting favorable cleaning power even without comprising an environmentally controlled substance, such as NMP.

Description

마스크 세정액 조성물Mask Cleaning Liquid Composition
본 발명은 마스크 세정액 조성물, 구체적으로 증착 공정에서 사용되는 마스크 상의 각종 유기물, 특히 유기 파티클의 제거가 용이한 마스크 세정액 조성물에 관한 것이다.The present invention relates to mask cleaning liquid compositions, and in particular mask cleaning liquid compositions which facilitate the removal of various organics, in particular organic particles, on the mask used in the 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 75KHz 이상 90KHz 이하이며, 세기가 800W 이상 1100W 이하이고, 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 waves in the ultrasonic cleaning unit have 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.
한편, 전술한 발광층, 정공 주입층, 정공 수송층, 전자 수송층, 전자 주입층 등과 같은 유기물층을 형성할 때 그 성능을 개선하기 위하여 유기 파티클의 사용이 증가되고 있으나, 이러한 유기 파티클은 대부분 불용해성을 나타내기 때문에 세정이 용이하지 않은 문제가 발생하고 있다.On the other hand, the use of organic particles to improve the performance when forming the organic layer, such as the light emitting layer, hole injection layer, hole transport layer, electron transport layer, electron injection layer, etc. described above, these organic particles are mostly insoluble The problem arises that it is not easy to clean because of the bet.
그러므로, NMP와 같은 환경규제물질을 포함하지 않으면서도, 세정력이 우수, 특히 유기 파티클에 대한 세정력이 우수하고 수분 흡수에 따른 성능 저하가 발생하지 않으며, 공정 운전에 용이한 마스크 세정액의 개발이 요구되고 있다.Therefore, it does not contain environmental regulatory substances such as NMP, but also has excellent cleaning power, in particular, excellent cleaning power for organic particles, no performance degradation due to moisture absorption, and development of a mask cleaning liquid that is easy to process operation is required. have.
[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 세정력, 특히 유기 파티클에 대하여 양호한 세정력을 나타내는 마스크 세정액 조성물을 제공하는 데 있다.It is an object of the present invention to provide a mask cleaning liquid composition which exhibits good cleaning power, in particular, good cleaning power with respect to organic particles, without including environmental regulatory substances.
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 아미드계 화합물; 및 알칼리성 화합물을 포함하는 마스크 세정액 조성물을 제공한다.The present invention is an amide compound represented by the formula (1); And it provides a mask cleaning liquid composition comprising an alkaline compound.
[화학식 1][Formula 1]
Figure PCTKR2019000231-appb-I000001
Figure PCTKR2019000231-appb-I000001
상기 화학식 1에서,In Chemical Formula 1,
R1 및 R2는 각각 독립적으로 수소, 메틸기 또는 에틸기이고,R1 and R2 are each independently hydrogen, a methyl group or an ethyl group,
R3는 수소; 또는 C1 내지 C4의 알콕시기로 치환 또는 비치환된 C1 내지 C4의 포화 또는 C2 내지 C4의 불포화 탄화수소기이며,R3 is hydrogen; Or a C1 to C4 saturated or C2 to C4 unsaturated hydrocarbon group unsubstituted or substituted with a C1 to C4 alkoxy group,
단, R1 및 R2가 메틸기인 경우,Provided that when R1 and R2 are methyl groups,
R3는 C1 내지 C4의 알콕시기로 치환 또는 비치환된 C2 내지 C4의 포화 또는 불포화 탄화수소기이다.R 3 is a C 2 to C 4 saturated or unsaturated hydrocarbon group unsubstituted or substituted with a C 1 to C 4 alkoxy group.
본 발명에 따른 마스크 세정액 조성물은 NMP와 같은 환경규제물질을 포함하지 않고도 양호한 세정력, 특히 유기 파티클에 대하여 양호한 세정력을 나타낼 수 있어 공정 운전에 용이한 이점이 있다.The mask cleaning liquid composition according to the present invention can exhibit good cleaning power, in particular, good cleaning power with respect to organic particles, without including an environmental regulation material such as NMP, and thus has an advantage of easy process operation.
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 아미드계 화합물; 및 알칼리성 화합물을 포함하는 마스크 세정액 조성물에 관한 것이다.One embodiment of the present invention, the amide compound represented by the formula (1); And a mask cleaning liquid composition containing an alkaline compound.
[화학식 1][Formula 1]
Figure PCTKR2019000231-appb-I000002
Figure PCTKR2019000231-appb-I000002
상기 화학식 1에서,In Chemical Formula 1,
R1 및 R2는 각각 독립적으로 수소, 메틸기 또는 에틸기이고,R1 and R2 are each independently hydrogen, a methyl group or an ethyl group,
R3는 수소; 또는 C1 내지 C4의 알콕시기로 치환 또는 비치환된 C1 내지 C4의 포화 또는 C2 내지 C4의 불포화 탄화수소기이며,R3 is hydrogen; Or a C1 to C4 saturated or C2 to C4 unsaturated hydrocarbon group unsubstituted or substituted with a C1 to C4 alkoxy group,
단, R1 및 R2가 메틸기인 경우,Provided that when R1 and R2 are methyl groups,
R3는 C1 내지 C4의 알콕시기로 치환 또는 비치환된 C2 내지 C4의 포화 또는 불포화 탄화수소기이다.R 3 is a C 2 to C 4 saturated or unsaturated hydrocarbon group unsubstituted or substituted with a C 1 to C 4 alkoxy group.
본 발명에서 알콕시기는 직쇄, 분지쇄 또는 고리쇄일 수 있다. 알콕시기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 4인 것이 바람직하다. 구체적으로, 메톡시, 에톡시, n-프로폭시, 이소프로폭시, n-부톡시, 이소부톡시, tert-부톡시, sec-부톡시 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present invention, the alkoxy group may be linear, branched or cyclic. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C4. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy and the like, but is not limited thereto.
본 발명에서 포화 탄화수소기는 상기 탄소수를 만족하는 직쇄 또는 분지쇄 및 환상의 어느 것일 수 있다. In the present invention, the saturated hydrocarbon group may be any of linear or branched chain and cyclic group that satisfy the carbon number.
상기 직쇄 또는 분지쇄의 포화 탄화수소기로는, 메틸기, 에틸기, 프로필기, 부틸기 등의 직쇄상 알킬기; 이소프로필기, 이소부틸기 등의 분지쇄상 알킬기 등을 들 수 있다. 상기 포화 탄화수소기는 바람직하게는 탄소수 1 내지 4이며, 더욱 바람직하게는 탄소수 1 내지 3이다. 단, R1 및 R2가 모두 메틸기인 경우, 상기 포화 탄화수소기의 탄소수는 2 내지 4이다.As said linear or branched saturated hydrocarbon group, linear alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group; Branched alkyl groups, such as an isopropyl group and an isobutyl group, etc. are mentioned. The saturated hydrocarbon group is preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms. However, when both R1 and R2 are methyl groups, the saturated hydrocarbon group has 2 to 4 carbon atoms.
상기 환상의 포화 탄화수소기로는 시클로프로필기, 시클로부틸기 등을 들 수 있다.Cyclopropyl group, cyclobutyl group, etc. are mentioned as said cyclic saturated hydrocarbon group.
본 발명에서 불포화 탄화수소기는 말단에 불포화기를 갖는 것으로, 탄소수 2 내지 4의 직쇄형 지방족 불포화 탄화수소기, 분지쇄형 지방족 탄화수소기일 수 있다. 상기 직쇄형 지방족 불포화 탄화수소기는 예컨대 비닐기, 프로페닐기(알릴기), 부티닐기 등을 들 수 있으며, 상기 분지쇄형 불포화 탄화수소기로는 예컨대, 1-메틸프로페닐기, 2-메틸프로페닐기 등을 들 수 있으나 이에 한정되지는 않는다.In the present invention, the unsaturated hydrocarbon group has an unsaturated group at the terminal, and may be a C 2 to C 4 linear aliphatic unsaturated hydrocarbon group or a branched aliphatic hydrocarbon group. Examples of the linear aliphatic unsaturated hydrocarbon group include vinyl group, propenyl group (allyl group) and butynyl group. Examples of the branched aliphatic unsaturated hydrocarbon group include 1-methylpropenyl group and 2-methylpropenyl group. However, it is not limited thereto.
본 발명의 일 실시형태에 있어서, 상기 화학식 1로 표시되는 아미드계 화합물은 N,N-디메틸프로피온아미드, N,N-디메틸이소부틸아미드, N,N-디메틸아크릴아미드, N,N-디메틸메타크릴아미드, N-에틸포름아미드, N,N-디에틸포름아미드, N,N-디에틸아세트아미드, N,N-디에틸프로피온아미드, N,N-디에틸이소부틸아미드, N,N-디에틸아크릴아미드, N,N-디에틸메타크릴아미드, 3-메톡시-N,N-디메틸프로피온아미드 및 3-부톡시-N,N-디메틸프로피온아미드로 이루어진 군에서 선택되는 1 이상일 수 있다.In one embodiment of the present invention, the amide compound represented by Formula 1 is N, N-dimethylpropionamide, N, N-dimethylisobutylamide, N, N-dimethylacrylamide, N, N-dimethylmetha Krillamide, N-ethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-diethylpropionamide, N, N-diethylisobutylamide, N, N- It may be at least one selected from the group consisting of diethylacrylamide, N, N-diethyl methacrylamide, 3-methoxy-N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide. .
본 발명에 따른 마스크 세정액 조성물은 상기 화학식 1로 표시되는 아미드계 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 amide-based compound represented by Chemical Formula 1, the mask cleaning liquid composition is excellent in 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.
상기 화학식 1로 표시되는 아미드계 화합물은 상기 마스크 세정액 조성물 전체 100 중량부에 대하여 50 내지 99.9 중량부, 바람직하게는 60 내지 98 중량부, 더욱 바람직하게는 75 내지 95 중량부로 포함될 수 있으며, 이 경우 유기 발광물질에 대한 용해력 및 세정성이 우수한 이점이 있다.The amide compound represented by Chemical Formula 1 may be included in an amount of 50 to 99.9 parts by weight, preferably 60 to 98 parts by weight, and more preferably 75 to 95 parts by weight, based on 100 parts by weight of the mask cleaning liquid composition. There is an advantage that the solvent and cleaning ability to the organic light emitting material is excellent.
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), biphenyl-3,3'-diyl)bis(diphenylphosphine oxide) (BiPh-m-BiDPO), 또는 mCP(1,3-bis(carbazol-9-yl)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), biphenyl-3,3'-diyl ) bis (diphenylphosphine oxide) (BiPh-m-BiDPO), or mCP (1,3-bis (carbazol-9-yl)) may be used, but is not limited thereto.
적색 발광 도펀트로는 PIQIr(acac)(bis(1-phenylisoquinoline)acetylacetonate iridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonate 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) acetylacetonate iridium), PQIr (acac) (bis (1-phenylquinoline) acetylacetonate 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), 3-(6-diphenylphosphinylnaphth-2-yl)-1,10-phenanthroline (Phen-m-PhDPO), 알루미늄 착물 등을 사용할 수 있으며, 정공 주입층의 재료로서 CuPc(copper phthalocyanine), PEDOT(poly(3,4)-ethylenedioxythiophene), PANI(polyaniline) 및 NPD로 이루어진 군에서 선택되는 1 이상, 보호층(capping layer, CPL)의 재료로서 Bis[2-(2-pyridinyl-N)phenyl-C](2,4-pentanedionato-O2,O4)iridium(III) 등이 사용될 수 있다.In addition, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) and 3- (6-diphenylphosphinylnaphth included in the hole blocking layer -2-yl) -1,10-phenanthroline (Phen-m-PhDPO), aluminum complex, etc. can be used, and CuPc (copper phthalocyanine), PEDOT (poly (3,4) -ethylenedioxythiophene) as the material of the hole injection layer , At least one selected from the group consisting of PANI (polyaniline) and NPD, Bis [2- (2-pyridinyl-N) phenyl-C] (2,4-pentanedionato-O2 as a material of a capping layer (CPL) , O4) iridium (III) and the like can be used.
본 발명에 따른 마스크 세정액 조성물은 알칼리성 화합물을 포함하며, 본 발명에 따른 마스크 세정액 조성물은 전술한 아미드계 화합물과 알칼리성 화합물을 함께 포함하기 때문에 마스크에 부착되어 있는 각종 유기물질, 특히 유기 파티클 형태의 불용해성 유기물질의 세정이 용이한 이점이 있다.The mask cleaning liquid composition according to the present invention comprises an alkaline compound, and since the mask cleaning liquid composition according to the present invention includes the above-mentioned amide compound and an alkaline compound, various organic substances attached to the mask, in particular, in the form of organic particles, are fired. There is an advantage that the cleaning of the soluble organic material is easy.
이론에 제한되는 것을 바라지는 않으나, 상기 알칼리성 화합물은 용액 내에서 pH를 상승시켜 흡착되어 있는 유기 물질을 리프트 오프(Lift off)하는 작용을 수행하기 때문에 메탈 컴플렉스(complex) 형태를 띠는 불용해성의 유기 물질, 예컨대 Bis[2-(2-pyridinyl-N)phenyl-C](2,4-pentanedionato-O2,O4)iridium(III), Poly(9,9-dioctylfluorene-alt-N-(4-sec-butylphenyl)-diphenylamine)과 같은 불용해성 유기 물질의 세정이 용이해진다. Although not wishing to be bound by theory, the alkaline compound is insoluble in the form of a metal complex due to the action of raising the pH in the solution to lift off the adsorbed organic material. Organic materials such as Bis [2- (2-pyridinyl-N) phenyl-C] (2,4-pentanedionato-O2, O4) iridium (III), Poly (9,9-dioctylfluorene-alt-N- (4- It is easy to clean insoluble organic materials such as sec-butylphenyl) -diphenylamine).
본 발명의 또 다른 실시형태에 있어서, 상기 알칼리성 화합물은 무기 염기 및 유기 염기로 이루어진 군에서 선택되는 1 이상을 포함할 수 있다.In another embodiment of the present invention, the alkaline compound may include at least one selected from the group consisting of an inorganic base and an organic base.
상기 무기 염기는 예컨대, 수산화암모늄, 수산화나트륨, 수산화 칼륨 등을 들 수 있으나 이에 한정되지는 않으며, 본 발명의 목적을 저해하지 않는다면 당업계에서 통상적으로 사용하는 무기 염기를 제한 없이 사용할 수 있다.The inorganic base may include, for example, ammonium hydroxide, sodium hydroxide, potassium hydroxide, and the like, but is not limited thereto, and inorganic bases commonly used in the art may be used without limitation as long as the object of the present invention is not impaired.
상기 유기 염기는 예컨대, 메틸 아민, 에틸아민, 이소프로필 아민, 모노이소프로필아민 등의 1급 아민; 디에틸 아민, 디이소프로필 아민, 디부틸아민 등의 2급 아민; 트리메틸아민, 트리에틸아민, 트리이소프로필아민, 트리부틸아민 등의 3급 아민; 테트라메틸암모늄 히드록시드, 테트라에틸암모늄 히드록시드, 테트라프로필암모늄 히드록시드, 테트라부틸암모늄 히드록시드 등의 4급 아민; 콜린, 모노에탄올아민, 디에탄올 아민, ２-아미노 에탄올, ２-(에틸 아미노) 에탄올, ２-(메틸 아미노) 에탄올, Ｎ-메틸 디에탄올 아민, 디메틸아미노에탄올, 디에틸아미노에탄올, 니트릴로트리에탄올, ２-(２-아미노 에톡시) 에탄올, １-아미노-２-프로판올, 트리에탄올아민, 모노프로판올아민, 디부탄올아민등의 알칸올아민 등이 있으며, 이들을 단독으로 또는 2개 이상 혼합하여 사용할 수 있다.The organic base may be, for example, primary amines such as methyl amine, ethylamine, isopropyl amine, monoisopropylamine and the like; Secondary amines such as diethyl amine, diisopropyl amine and dibutylamine; Tertiary amines such as trimethylamine, triethylamine, triisopropylamine and tributylamine; Quaternary amines such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide; Choline, monoethanolamine, diethanol amine, 2-amino ethanol, 2- (ethyl amino) ethanol, 2- (methyl amino) ethanol, N-methyl diethanol amine, dimethylaminoethanol, diethylaminoethanol, nitrilotriethanol , Alkanolamines such as 2- (2-aminoethoxy) ethanol, 1-amino-2-propanol, triethanolamine, monopropanolamine, dibutanolamine, and the like, and these may be used alone or in combination of two or more thereof. have.
본 발명의 또 다른 실시형태에 있어서, 상기 유기 염기는 아민계 화합물을 포함할 수 있다. 구체적으로, 유기물과 무기물을 포함하는 불용해성 발광 파티클을 세정하는 경우, 세정을 완료한 이후의 재흡착 현상을 방지하기 위하여 하이드록시기를 가지는 아민계 화합물을 사용하는 것이 바람직하다.In another embodiment of the present invention, the organic base may include an amine compound. Specifically, in the case of washing insoluble light emitting particles including organic and inorganic substances, it is preferable to use an amine compound having a hydroxyl group in order to prevent resorption phenomenon after the cleaning is completed.
본 발명의 또 다른 실시형태에 있어서, 상기 알칼리성 화합물은 상기 마스크 세정액 조성물 전체 100 중량부에 대하여 0.05 내지 10 중량부, 바람직하게는 1 내지 7 중량부로 포함될 수 있다. 이 경우, 불용해성 유기 파티클의 제거성이 극대화되는 이점이 있어 바람직하며, 상대적으로 아미드계 화합물의 함량이 감소함으로써 유기 발광물질에 대한 용해력과 세정력이 저하되는 현상을 억제할 수 있다.In still another embodiment of the present invention, the alkaline compound may be included in an amount of 0.05 to 10 parts by weight, preferably 1 to 7 parts by weight, based on 100 parts by weight of the mask cleaning liquid composition. In this case, there is an advantage of maximizing the removal of the insoluble organic particles, it is possible to suppress the phenomenon that the dissolving power and detergency for the organic light emitting material is reduced by reducing the content of the amide compound relatively.
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, 에틸렌글리콜 모노에틸 에테르, 에틸렌글리콜 모노이소프로필 에테르, 에틸렌글리콜 모노부틸 에테르, 디에틸렌글리콜 모노메틸 에테르, 디에틸렌글리콜 모노에틸 에테르, 디에틸렌글리콜 모노이소프로필 에테르, 디에틸렌글리콜 모노부틸 에테르, 트리에틸렌글리콜 모노메틸 에테르, 트리에틸렌글리콜 모노에틸 에테르, 트리에틸렌글리콜 모노이소프로필 에테르, 트리에틸렌글리콜 모노부틸 에테르, 폴리에틸렌글리콜 모노메틸 에테르, 폴리에틸렌글리콜 모노부틸 에테르, 프로필렌글리콜 모노메틸 에테르, 디프로필렌글리콜 모노메틸 에테르, 트리프로필렌글리콜 모노메틸 에테르 등의 알킬렌글리콜 모노알킬 에테르; 및 테트라하이드로퍼푸릴 알코올; 등을 들 수 있으며, 4-하이드록시메틸-1,3-디옥솔란, 4-하이드록시메틸-2,2-디메틸-1,3-디옥솔란, 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, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Isopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monobutyl Alkylene glycol monoalkyl ethers such as ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether; And tetrahydrofurfuryl alcohol; And 4-hydroxymethyl-1,3-dioxolane, 4-hydroxymethyl-2,2-dimethyl-1,3-dioxolane, 4-hydroxyethyl-2,2-dimethyl- and the like. 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-디메틸이소부틸아미드(DMIB), N,N-디메틸아크릴아미드(DMAR), N,N-디메틸메타크릴아미드, N,N-디에틸포름아미드, N,N-디에틸아세트아미드(DEAC), N,N-디에틸프로피온아미드, N,N-디에틸이소부틸아미드, N,N-디에틸아크릴아미드, 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-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 화합물을 들 수 있으며, 이들은 단독으로 또는 2종 이상을 혼합하여 사용할 수 있으나, 역시 이에 한정되지 않는다.The aprotic polar solvents include, for example, N, N-dimethylpropionamide (DMPA), N, N-dimethylisobutylamide (DMIB), N, N-dimethylacrylamide (DMAR), N, N-dimethylmethacrylamide, N, N-diethylformamide, N, N-diethylacetamide (DEAC), N, N-diethylpropionamide, N, N-diethylisobutylamide, N, N-diethylacrylamide, N , N-diethylmethacrylamide, 3-methoxy-N, N-dimethylpropionamide (MDMP) and 3-butoxy-N, N-dimethylpropionamide, N, N-diethylformamide (DEF), Dialkylamide compounds such as N, N-dimethylformamide (DMF); Mono such as N-methylformamide (NMF), N-methylpropionamide (NMPA), N-methylacetamide (NMA), N-ethylacetamide (NEA), and N- (2-hydroxyethyl) acetamide Amide compounds; 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), are mentioned, These can be used individually or in mixture of 2 or more types, It is not limited to this also.
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 아미드계 화합물, 알칼리성 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 plays a role of dissolving the organic material remaining in the mask together with the amide compound and the alkaline compound represented by the formula (1), and also facilitates the removal of the cleaning solution by water in the rinse process of deionized water after washing. By minimizing the resorption / reattachment of the removed organic material or may play a role in improving the removal power of a 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. 구체적으로, 세정 공정에서 휘발되어 공정 사용량이 많아 지고, 작업 환경에 악영향을 미치는 현상을 억제할 수 있으므로 바람직하다.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. Specifically, it is preferable because it is volatilized in the washing step, the amount of the process used increases, and the phenomenon which adversely affects the working environment can be suppressed.
본 발명의 또 다른 실시형태에 있어서, 상기 수용성 극성용매는 상기 세정액 조성물 전체 100 중량부에 대하여 5 내지 35 중량부, 바람직하게는 5 내지 30 중량부, 더욱 바람직하게는 10 내지 20 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.In another embodiment of the present invention, the water-soluble polar solvent may be included in 5 to 35 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 20 parts by weight based on 100 parts by weight of the total cleaning liquid composition. have. When the water-soluble polar solvent is included in the above range, it is preferable because there is an advantage in that the cleaning liquid composition can be prepared excellent in cleaning power and easy to remove the cleaning liquid by water in the rinsing process of deionized water after washing.
본 발명의 또 다른 실시형태에 있어서, 상기 마스크 세정액 조성물은 전체 100 중량부에 대하여 물을 5 중량부 이하로 포함할 수 있다.In 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.
상기 물은 상기 마스크 세정액 조성물 전체 100 중량부에 대하여 바람직하게는 3 중량부 이하로 포함될 수 있다.The water may be included in an amount of preferably 3 parts by weight or less based on 100 parts by weight of the mask cleaning solution composition.
상기 물이 상기 범위 이하로 포함되는 경우 유기 EL(Organic Electro Luminescence)의 제거력 저하를 야기하지 않아 바람직하다.When the water is included below the above range it is preferable not to cause a reduction in the removal 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 아미드계 화합물 및 알칼리성 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 amide compound and the alkaline 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, DMF, DMAC, NMF와 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, DMF, DMAC, and NMF.
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 아미드계 화합물Amide compound 알칼리 화합물Alkali compounds 양자성 극성용매Quantum polar solvent 기타Etc
명칭designation [중량%][weight%] 명칭designation [중량%][weight%] 명칭designation [중량%][weight%] 명칭designation [중량%][weight%]
실시예 1Example 1 DMPADMPA 9090 NMEANMEA 1010 -- -- -- --
실시예 2Example 2 DMPADMPA 8989 NMEANMEA 1010 H2OH 2 O 1One
실시예 3Example 3 DMPADMPA 8787 NMEANMEA 1010 H2OH 2 O 33
실시예 4Example 4 DMPADMPA 8585 NMEANMEA 1010 -- -- H2OH 2 O 55
실시예 5Example 5 DMPADMPA 8383 NMEANMEA 1010 H2OH 2 O 77
실시예 6Example 6 DMPADMPA 99.999.9 KOHKOH 0.10.1 -- -- -- --
실시예 7Example 7 DMPADMPA 9696 TMAHTMAH 1One -- -- H2OH 2 O 33
실시예 8Example 8 DMACDMAC 9090 MEAMEA 1010 -- -- -- --
실시예 9Example 9 DMACDMAC 99.999.9 MEAMEA 0.10.1 -- -- -- --
실시예 10Example 10 DMACDMAC 98.998.9 MEAMEA 0.10.1 -- -- H2OH 2 O 1One
실시예 11Example 11 DMFDMF 9090 NMEANMEA 1010 -- -- -- --
실시예 12Example 12 DMFDMF 99.999.9 NMEANMEA 0.10.1 -- -- -- --
실시예 13Example 13 NMFNMF 9090 MEAMEA 1010 -- -- -- --
실시예 14Example 14 NMFNMF 99.999.9 NaOHNaOH 0.10.1 -- -- -- --
실시예 15Example 15 DMPADMPA 8080 NMEANMEA 55 DEDGDEDG 1515 -- --
실시예 16Example 16 DMPADMPA 79.579.5 NMEANMEA 55 DEDGDEDG 1515 H2OH 2 O 0.50.5
실시예 17Example 17 DMPADMPA 7575 NMEANMEA 55 DEDGDEDG 1515 H2OH 2 O 55
실시예 18Example 18 DMPADMPA 6060 NMEANMEA 1010 DEDGDEDG 3030 -- --
실시예 19Example 19 DMPADMPA 6060 NMEANMEA 1010 DEDGDEDG 2323 H2OH 2 O 77
실시예 20Example 20 DMPADMPA 9494 KOHKOH 1One MEDGMEDG 55 -- --
실시예 21Example 21 DMACDMAC 8080 MEAMEA 55 DMIDMI 1515 -- --
실시예 22Example 22 DMFDMF 6060 NMEANMEA 1010 EDGEDG 3030 -- --
실시예 23Example 23 DMPADMPA 8080 TMAHTMAH 1One DEDGDEDG 1515 H2OH 2 O 44
비교예 1Comparative Example 1 DMDADMDA 100100 -- -- -- -- -- --
비교예 2Comparative Example 2 DMPADMPA 5050 -- -- DMTGDMTG 5050 -- --
비교예 3Comparative Example 3 -- -- NaOHNaOH 100100 -- -- -- --
비교예 4Comparative Example 4 -- -- MEAMEA 100100 -- -- -- --
비교예 5Comparative Example 5 -- -- NMEANMEA 100100 -- -- -- --
비교예 6Comparative Example 6 -- -- DGADGA 100100 -- -- -- --
비교예 7Comparative Example 7 -- -- AEEAAEEA 100100 -- -- -- --
비교예 8Comparative Example 8 -- -- NMEANMEA 5050 EDGEDG 5050 -- --
비교예 9Comparative Example 9 -- -- KOHKOH 3030 DMIDMI 7070 -- --
비교예 10Comparative Example 10 -- -- -- -- DEDGDEDG 100100 -- --
비교예 11Comparative Example 11 -- -- -- -- MDGMDG 100100 -- --
비교예 12Comparative Example 12 -- -- -- -- DMIDMI 100100 -- --
비교예 13Comparative Example 13 -- -- -- -- EDGEDG 100100 -- --
비교예 14Comparative Example 14 -- -- -- -- DMDGDMDG 100100 -- --
비교예 15Comparative Example 15 -- -- -- -- DMTGDMTG 100100 -- --
실험예Experimental Example 1: 유기발광소자 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 4종의 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, four masks in which the organic material used as the light emitting layer and the electron / hole transporting layer included in the organic light emitting device are separately adsorbed according to a conventional deposition process ( Material: Invar) was evaluated for solubility.
증착 공정 후 마스크로부터 유기소재를 분리한 후, 막자 사발을 이용하여 파우더 형태를 만들고, 224㎛ 체로 분리하였다. 제조한 마스크 세정액 조성물의 중량으로 0.015%의 유기소재를 50ml 비커를 사용하여 상온에서 파우더를 녹인 후 실시예 및 비교예 에 따른 마스크 세정액 조성물(약액)의 용해성(파우더 녹는 속도, 분단위 측정)을 평가 하여 하기 표 2에 나타내었다.After separating the organic material from the mask after the deposition process, using a mortar and pestle to form a powder, separated into a 224㎛ sieve. After dissolving the powder at room temperature using a 50 ml beaker of 0.015% organic material by weight of the prepared mask cleaning liquid composition, the solubility (powder melting rate, minute unit measurement) of the mask cleaning liquid composition (chemical solution) according to Examples and Comparative Examples was measured. 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 Mask 4분리 유기소재Mask 4 separated organic materials
실시예 1Example 1 6분6 minutes 6분6 minutes 25분25 minutes 불용해Insoluble
실시예 2Example 2 6분6 minutes 6분6 minutes 25분25 minutes 불용해Insoluble
실시예 3Example 3 6분6 minutes 6분6 minutes 25분25 minutes 불용해Insoluble
실시예 4Example 4 6 분6 mins 7 분7 mins 27 분27 mins 불용해Insoluble
실시예 5Example 5 7 분7 mins 8 분8 mins 31분31 minutes 불용해Insoluble
실시예 6Example 6 6분6 minutes 6분6 minutes 28분28 minutes 불용해Insoluble
실시예 7Example 7 6분6 minutes 6 분6 mins 30 분30 minutes 불용해Insoluble
실시예 8Example 8 6 분6 mins 6 분6 mins 35 분35 mins 불용해Insoluble
실시예 9Example 9 7 분7 mins 5 분5 minutes 30 분30 minutes 불용해Insoluble
실시예 10Example 10 7 분7 mins 5 분5 minutes 31 분31 mins 불용해Insoluble
실시예 11Example 11 8 분8 mins 8 분8 mins 30 분30 minutes 불용해Insoluble
실시예 12Example 12 8 분8 mins 8 분8 mins 30 분30 minutes 불용해Insoluble
실시예 13Example 13 7 분7 mins 10 분10 minutes 40 분40 mins 불용해Insoluble
실시예 14Example 14 9 분9 mins 10 분10 minutes 40 분40 mins 불용해Insoluble
실시예 15Example 15 6 분6 mins 4 분4 mins 15 분15 mins 불용해Insoluble
실시예 16Example 16 6 분6 mins 4 분4 mins 15 분15 mins 불용해Insoluble
실시예 17Example 17 6 분6 mins 5 분5 minutes 17 분17 mins 불용해Insoluble
실시예 18Example 18 4 분4 mins 6 분6 mins 20 분20 minutes 불용해Insoluble
실시예 19Example 19 6 분6 mins 7 분7 mins 23 분23 mins 불용해Insoluble
실시예 20Example 20 6분6 minutes 8 분8 mins 22 분22 mins 불용해Insoluble
실시예 21Example 21 5 분5 minutes 5 분5 minutes 21 분21 mins 불용해Insoluble
실시예 22Example 22 10 분10 minutes 10 분10 minutes 25 분25 mins 불용해Insoluble
실시예 23Example 23 5 분5 minutes 5 분5 minutes 18 분18 mins 불용해Insoluble
비교예 1Comparative Example 1 45 분45 mins 60 분60 mins 120 분120 minutes 불용해Insoluble
비교예 2Comparative Example 2 25 분25 mins 20 분20 minutes 60 분60 mins 불용해Insoluble
비교예 3Comparative Example 3 55 분55 mins 55 분55 mins 100 분100 mins 불용해Insoluble
비교예 4Comparative Example 4 50 분50 minutes 50 분50 minutes 120 분120 minutes 불용해Insoluble
비교예 5Comparative Example 5 55 분55 mins 55 분55 mins 120 분120 minutes 불용해Insoluble
비교예 6Comparative Example 6 120 분120 minutes 120 분120 minutes 180 분180 minutes 불용해Insoluble
비교예 7Comparative Example 7 80 분80 minutes 80 분80 minutes 140 분140 minutes 불용해Insoluble
비교예 8Comparative Example 8 60 분60 mins 60 분60 mins 120 분120 minutes 불용해Insoluble
비교예 9Comparative Example 9 40 분40 mins 40 분40 mins 100 분100 mins 불용해Insoluble
비교예 10Comparative Example 10 25 분25 mins 30 분30 minutes 100 분100 mins 불용해Insoluble
비교예 11Comparative Example 11 30 분30 minutes 25 분25 mins 120 분120 minutes 불용해Insoluble
비교예 12Comparative Example 12 35 분35 mins 40 분40 mins 65 분65 minutes 불용해Insoluble
비교예 13Comparative Example 13 40 분40 mins 45 분45 mins 80 분80 minutes 불용해Insoluble
비교예 14Comparative Example 14 45 분45 mins 50 분50 minutes 85 분85 minutes 불용해Insoluble
비교예 15Comparative Example 15 50 분50 minutes 50 분50 minutes 120 분120 minutes 불용해Insoluble
Mask 1 흡착 물질: 2-(9,9-Spirobifluoren-2-yl)-9,9-spirobifluorene(BSBF), Mask 2 흡착 물질: biphenyl-3,3'-diyl)bis(diphenylphosphine oxide) (BiPh-m-BiDPO), Mask 3 흡착 물질: 3-(6-diphenylphosphinylnaphth-2-yl)-1,10-phenanthroline (Phen-m-PhDPO), Mask 4 흡착 물질: Bis[2-(2-pyridinyl-N)phenyl-C](2,4-pentanedionato-O2,O4)iridium(III)Mask 1 adsorbent: 2- (9,9-Spirobifluoren-2-yl) -9,9-spirobifluorene (BSBF), mask 2 adsorbent: biphenyl-3,3'-diyl) bis (diphenylphosphine oxide) (BiPh- m-BiDPO), Mask 3 adsorbent: 3- (6-diphenylphosphinylnaphth-2-yl) -1,10-phenanthroline (Phen-m-PhDPO), Mask 4 adsorbent: Bis [2- (2-pyridinyl-N ) phenyl-C] (2,4-pentanedionato-O2, O4) iridium (III)
실험예Experimental Example 2: 세정액의 유기  2: organic of cleaning liquid 파티클particle 제거성Removability 평가 evaluation
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 4종의 마스크(재질: Invar)에 대한 세정액의 유기 파티클 제거성 평가를 실시하였다.In order to confirm the cleaning effect of the mask cleaning liquid compositions according to the Examples and Comparative Examples, four masks in which the organic material used as the light emitting layer and the electron / hole transporting layer included in the organic light emitting device are separately adsorbed according to a conventional deposition process ( Material: Invar) was evaluated to remove the organic particles of the cleaning liquid.
세정액 조성물의 유기파티클 제거효과를 확인하기 위하여 증착 공정 후 마스크로부터 유기소재를 분리한 후, 실험예 1과 동일한 방법으로 막자 사발을 이용하여 파우더 형태를 만들고 제조한 마스크 세정액 조성물의 중량으로 0.05%의 유기소재를 NMP에 1시간 소니케이터를 이용하여 균일하게 분산시킨 후 1.5×1.5 크기의 Invar 위에 떨어뜨린 다음 100℃ 오븐에서 1 시간동안 건조시켰다. 상기 기판을 상온에서 각 조성물(약액)에 20초간 침적시킨 후, 세정을 거쳐 육안평가와 광학현미경을 이용하여 평가하였다. 그 결과를 하기의 표 3에 나타냈으며 육안으로 관찰 시, 매우 양호는 ◎, 양호는 ○, 보통은 △, 안됨은 ×로 표시하였다.In order to confirm the organic particle removal effect of the cleaning liquid composition, after separating the organic material from the mask after the deposition process, in the same manner as in Experimental Example 1 to make a powder form using a pestle of the mask cleaning liquid composition of 0.05% by weight The organic material was uniformly dispersed in NMP using a sonicator for 1 hour, dropped onto 1.5 × 1.5 Invar, and dried in an oven at 100 ° C. for 1 hour. The substrate was immersed in each composition (chemical liquid) for 20 seconds at room temperature, and then washed and evaluated by visual evaluation and an optical microscope. The results are shown in Table 3 below. When visually observed, very good is indicated by ◎, good is ○, usually △, and no as ×.
구분division 세정력Cleaning power
Mask 1분리 유기소재Mask 1 separated organic material Mask 2분리 유기소재Mask 2 separated organic material Mask 3분리 유기소재Mask 3 separated organic material Mask 4분리 유기소재Mask 4 separated organic materials
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 ◎◎ ◎◎ ◎◎ ◎◎
비교예 1Comparative Example 1 ○○ △△ △△ △△
비교예 2Comparative Example 2 ○○ ○○ △△ △△
비교예 3Comparative Example 3 △△ △△ △△ △△
비교예 4Comparative Example 4 △△ △△ ×× ××
비교예 5Comparative Example 5 △△ △△ xx ××
비교예 6Comparative Example 6 xx xx xx ××
비교예 7Comparative Example 7 △△ △△ xx ××
비교예 8Comparative Example 8 xx xx xx ××
비교예 9Comparative Example 9 xx △△ △△ ××
비교예 10Comparative Example 10 ○○ ○ ○ △ △ ××
비교예 11Comparative Example 11 △△ △△ ×× ××
비교예 12Comparative Example 12 △△ ×× ×× ××
비교예 13Comparative Example 13 ×× ×× ×× ××
비교예 14Comparative Example 14 ×× ×× ×× ××
비교예 15Comparative Example 15 ×× × × × × ××
Mask 1 흡착 물질: 2-(9,9-Spirobifluoren-2-yl)-9,9-spirobifluorene(BSBF), Mask 2 흡착 물질: biphenyl-3,3'-diyl)bis(diphenylphosphine oxide) (BiPh-m-BiDPO), Mask 3 흡착 물질: 3-(6-diphenylphosphinylnaphth-2-yl)-1,10-phenanthroline (Phen-m-PhDPO), Mask 4 흡착 물질: Bis[2-(2-pyridinyl-N)phenyl-C](2,4-pentanedionato-O2,O4)iridium(III)Mask 1 adsorbent: 2- (9,9-Spirobifluoren-2-yl) -9,9-spirobifluorene (BSBF), mask 2 adsorbent: biphenyl-3,3'-diyl) bis (diphenylphosphine oxide) (BiPh- m-BiDPO), Mask 3 adsorbent: 3- (6-diphenylphosphinylnaphth-2-yl) -1,10-phenanthroline (Phen-m-PhDPO), Mask 4 adsorbent: Bis [2- (2-pyridinyl-N ) phenyl-C] (2,4-pentanedionato-O2, O4) iridium (III)
상기 표 2에서 실시예 1 내지 20과 비교예 3 내지 15를 보면 화학식 1로 표시되는 아미드계 화합물이 포함되었을 때 마스크 1 내지 3의 흡착 물질에 대한 용해력이 우수하다는 것을 확인할 수 있다. 표 3에서 실시예 1 내지 20과 비교예 1, 2를 비교하였을 때 알칼리성 화합물이 포함되어있는 경우 우수한 세정력을 확보할 수 있음을 알 수 있고, 화학식 1로 표시되는 아미드 계열이 포함되지 않은 비교예의 경우 제거성이 우수하지 않음을 알 수 있다.Looking at Examples 1 to 20 and Comparative Examples 3 to 15 in Table 2, when the amide compound represented by Formula 1 is included, it can be confirmed that the solvent 1 to 3 has excellent solubility in the adsorbent. Comparing Examples 1 to 20 and Comparative Examples 1 and 2 in Table 3, it can be seen that excellent cleaning power can be obtained when an alkaline compound is included, and the comparative example does not include the amide series represented by Formula 1 It can be seen that the removal is not excellent.

Claims (10)

  1. 하기 화학식 1로 표시되는 아미드계 화합물; 및Amide-based compounds represented by the formula (1); And
    알칼리성 화합물을 포함하는 마스크 세정액 조성물:Mask cleaning liquid composition comprising an alkaline compound:
    [화학식 1][Formula 1]
    Figure PCTKR2019000231-appb-I000003
    Figure PCTKR2019000231-appb-I000003
    상기 화학식 1에서,In Chemical Formula 1,
    R1 및 R2는 각각 독립적으로 수소, 메틸기 또는 에틸기이고,R1 and R2 are each independently hydrogen, a methyl group or an ethyl group,
    R3는 수소; 또는 C1 내지 C4의 알콕시기로 치환 또는 비치환된 C1 내지 C4의 포화 또는 C2 내지 C4의 불포화 탄화수소기이며,R3 is hydrogen; Or a C1 to C4 saturated or C2 to C4 unsaturated hydrocarbon group unsubstituted or substituted with a C1 to C4 alkoxy group,
    단, R1 및 R2가 메틸기인 경우,Provided that when R1 and R2 are methyl groups,
    R3는 C1 내지 C4의 알콕시기로 치환 또는 비치환된 C2 내지 C4의 포화 또는 불포화 탄화수소기이다.R 3 is a C 2 to C 4 saturated or unsaturated hydrocarbon group unsubstituted or substituted with a C 1 to C 4 alkoxy group.
  2. 제1항에 있어서,The method of claim 1,
    상기 화학식 1로 표시되는 아미드계 화합물은 N,N-디메틸프로피온아미드, N,N-디메틸이소부틸아미드, N,N-디메틸아크릴아미드, N,N-디메틸메타크릴아미드, N-에틸포름아미드, N,N-디에틸포름아미드, N,N-디에틸아세트아미드, N,N-디에틸프로피온아미드, N,N-디에틸이소부틸아미드, N,N-디에틸아크릴아미드, N,N-디에틸메타크릴아미드, 3-메톡시-N,N-디메틸프로피온아미드 및 3-부톡시-N,N-디메틸프로피온아미드로 이루어진 군에서 선택되는 1 이상인 것인 마스크 세정액 조성물.Amide-based compound represented by Formula 1 is N, N-dimethylpropionamide, N, N-dimethylisobutylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-ethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-diethylpropionamide, N, N-diethylisobutylamide, N, N-diethylacrylamide, N, N- A mask cleaning liquid composition which is at least one selected from the group consisting of diethyl methacrylamide, 3-methoxy-N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide.
  3. 제1항에 있어서,The method of claim 1,
    상기 알칼리성 화합물은 무기 염기 및 유기 염기로 이루어진 군에서 선택되는 1 이상을 포함하는 것인 마스크 세정액 조성물.The alkaline compound is a mask cleaning liquid composition comprising at least one selected from the group consisting of an inorganic base and an organic base.
  4. 제3항에 있어서,The method of claim 3,
    상기 유기 염기는 아민계 화합물을 포함하는 것인 마스크 세정액 조성물.The organic base is a mask cleaning liquid composition comprising an amine compound.
  5. 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.
  6. 제5항에 있어서,The method of claim 5,
    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.
  7. 제1항에 있어서, The method of claim 1,
    물을 전체 100 중량부에 대하여 5 중량부 이하로 포함하는 것인 마스크 세정액 조성물.The mask cleaning liquid composition comprising less than 5 parts by weight of water based on 100 parts by weight of the total.
  8. 제1항에 있어서,The method of claim 1,
    상기 알칼리성 화합물은 상기 마스크 세정액 조성물 전체 100 중량부에 대하여 0.05 내지 10 중량부로 포함되는 것인 마스크 세정액 조성물.The alkaline compound is a mask cleaning liquid composition that is contained in 0.05 to 10 parts by weight based on 100 parts by weight of the total mask cleaning liquid composition.
  9. 제5항에 있어서, The method of claim 5,
    상기 수용성 극성용매는 상기 마스크 세정액 조성물 전체 100 중량부에 대하여 5 내지 35 중량부로 포함되는 것인 마스크 세정액 조성물.The water-soluble polar solvent is a mask cleaning liquid composition comprising 5 to 35 parts by weight based on 100 parts by weight of the total mask cleaning liquid composition.
  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/KR2019/000231 2018-02-06 2019-01-08 Mask cleaning liquid composition WO2019156364A1 (en)

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KR1020180157345A KR102640141B1 (en) 2018-02-06 2018-12-07 Cleaning solution composition

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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
KR20050054452A (en) * 2003-12-04 2005-06-10 간토 가가꾸 가부시키가이샤 Washing liquid composition and washing method for mask used in vacuum vapor deposition step in production of low molecular weight organic el device
KR100949206B1 (en) * 2002-09-09 2010-03-24 미츠비시 가스 가가쿠 가부시키가이샤 Cleaning composition
KR20120136957A (en) * 2011-06-10 2012-12-20 동우 화인켐 주식회사 A detergent composition for flat panel display device
KR20160145537A (en) * 2014-05-02 2016-12-20 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 Semiconductor element cleaning liquid and cleaning method

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* 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
KR100949206B1 (en) * 2002-09-09 2010-03-24 미츠비시 가스 가가쿠 가부시키가이샤 Cleaning composition
KR20050054452A (en) * 2003-12-04 2005-06-10 간토 가가꾸 가부시키가이샤 Washing liquid composition and washing method for mask used in vacuum vapor deposition step in production of low molecular weight organic el device
KR20120136957A (en) * 2011-06-10 2012-12-20 동우 화인켐 주식회사 A detergent composition for flat panel display device
KR20160145537A (en) * 2014-05-02 2016-12-20 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 Semiconductor element cleaning liquid and cleaning method

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