WO2019156363A1 - Mask cleaning solution composition - Google Patents

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

Mask Cleaning Liquid Composition

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.

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.

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.

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.

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.

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) is disclosed as a mask cleaning device characterized in that the mixture.

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.

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.

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.

[Preceding technical literature]

[Patent Documents]

(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.)

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.

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.

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.

[Formula 1]

In Chemical Formula 1,

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.

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.

In addition, when the mask is cleaned using the mask cleaning liquid composition according to the present invention, ultrasonic and electrolytic cleaning are unnecessary.

Hereinafter, the present invention will be described in more detail.

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.

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.

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.

[Formula 1]

In Chemical Formula 1,

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.

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.

The above description of the 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. In short, the mask cleaning liquid composition according to the present invention may be formed of a glymeic compound represented by Chemical Formula 1.

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.

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.

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.

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.

In the present invention, the δ _T is (δ _P ² + δ _H ² + δ _D ² ) Can be calculated as ^1/2 .

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

In another embodiment of the present invention, the mask cleaning liquid composition may further comprise a water-soluble polar solvent.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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).

The water may be deionized water (DIW) or ultrapure water in which impurities are reduced as much as possible, but are not limited thereto.

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.

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.

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.

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.

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.

Example  And Comparative example : Preparation of Cleaning Liquid Composition

To prepare a cleaning solution composition according to the Example and Comparative Example according to the configuration and composition of Table 1.

division Glymeic Compound [weight%] Water soluble polar solvent Etc [weight%] Aprotic Polar Solvent [weight%] Quantum polar solvent [weight%] Example 1 DEDG 100 - - - - - - Example 2 DMDG 100 - - - - - - Example 3 DMTG 100 - - - - - - Example 4 MEDG 100 - - - - - - Example 5 PDM 100 - - - - - - Example 6 DPDM 100 - - - - - - Example 7 DEDG 70 - - - - - - DMDG 30 - - - - - - Example 8 PDM 80 - - - - - - DPDM 20 - - - - - - Example 9 DEDG 80 DMPA 20 - - - - Example 10 MEDG 65 DMAC 35 - - - - Example 11 DEDG 70 DEF 30 - - - - Example 12 MEDG 10 DEAC 90 - - - - Example 13 MBDG 20 NEF 80 - - - - Example 14 MBTG 50 NMPA 50 - - - - Example 15 MEDG 65 DMPA 25 EDG 10 - - Example 16 DEDG 50 DMAC 35 HMDMDO 15 - - Example 17 DMDG 80 - - HMD 20 - - Example 18 DMTG 80 - - MDG 20 - - Example 19 PDM 30 DEF 70 - - - - Example 20 DEDG 99.5 - - - - DIW 0.5 Example 21 DMDG 99 - - - - DIW One Example 22 DEDG 98 - - - - DIW 2 Example 23 DMDG 97 - - - - DIW 3 Example 24 DEDG 95 - - - - DIW 5 Example 25 DMDG 90 - - - - DIW 10 Comparative Example 1 - - NMP 100 - - - - Comparative Example 2 - - DMF 100 - - - - Comparative Example 3 - - DMSO 100 - - - - Comparative Example 4 - - PC 100 - - - - Comparative Example 5 - - DEF 100 - - - - Comparative Example 6 - - DMAC 100 - - - - Comparative Example 7 - - NEF 100 - - - - Comparative Example 8 - - NMPA 100 - - - - Comparative Example 9 - - NMF 100 - - - - Comparative Example 10 - - - - EDG 100 - - Comparative Example 11 - - - - MDG 100 - - Comparative Example 12 - - - - MTG 100 - - Comparative Example 13 - - - - MFDG 100 - - Comparative Example 14 - - - - MFTG 100 - - Comparative Example 15 - - DEF 50 MFDG 50 - - Comparative Example 16 - - DMAC 50 MFTG 50 - - Comparative Example 17 - - - - MDG 50 - - - - - - MFG 50 - - Comparative Example 18 - - - - - - Hexane 100 Comparative Example 19 - - - - - - Cyclo pentane 100 Comparative Example 20 MEDG 50 - - - - Cyclo pentane 50 Comparative Example 21 MEDG 80 - - - - Cyclo pentane 20 DEDG: 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

Experimental Example  1: Solubility evaluation of organic light emitting device

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.

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.

division Solubility Assessment Mask 1 separated organic material Mask 2 separated organic material Mask 3 separated organic material Example 1 5 minutes 6 minutes 15 minutes Example 2 6 minutes 6 minutes 15 minutes Example 3 7 minutes 7 minutes 15 minutes Example 4 6 minutes 5 minutes 15 minutes Example 5 7 minutes 8 minutes 17 minutes Example 6 8 minutes 7 minutes 17 minutes Example 7 7 minutes 7 minutes 15 minutes Example 8 8 minutes 8 minutes 15 minutes Example 9 5 minutes 5 minutes 12 minutes Example 10 5 minutes 4 minutes 13 minutes Example 11 5 minutes 4 minutes 12 minutes Example 12 10 minutes 8 minutes 12 minutes Example 13 10 minutes 6 minutes 25 minutes Example 14 8 minutes 5 minutes 25 minutes Example 15 4 minutes 16 minutes 12 minutes Example 16 5 minutes 14 minutes 13 minutes Example 17 4 minutes 15 minutes 20 minutes Example 18 5 minutes 14 minutes 20 minutes Example 19 6 minutes 6 minutes 12 minutes Example 20 5 minutes 6 minutes 15 minutes Example 21 6 minutes 6 minutes 15 minutes Example 22 6 minutes 6 minutes 15 minutes Example 23 6 minutes 6 minutes 15 minutes Example 24 8 minutes 7 minutes 17 minutes Example 25 10 minutes 14 minutes 30 minutes Comparative Example 1 5 minutes 5 minutes 12 minutes Comparative Example 2 10 minutes 30 minutes 30 minutes Comparative Example 3 10 minutes 40 minutes 30 minutes Comparative Example 4 40 minutes 40 minutes 60 minutes Comparative Example 5 10 minutes 30 minutes 20 minutes Comparative Example 6 10 minutes 40 minutes 20 minutes Comparative Example 7 11 minutes 45 minutes 30 minutes Comparative Example 8 12 minutes 55 minutes 30 minutes Comparative Example 9 11 minutes 50 minutes 35 minutes Comparative Example 10 30 minutes 30 minutes 60 minutes Comparative Example 11 30 minutes 30 minutes 60 minutes Comparative Example 12 30 minutes 30 minutes 60 minutes Comparative Example 13 30 minutes 30 minutes 60 minutes Comparative Example 14 30 minutes 30 minutes 60 minutes Comparative Example 15 40 minutes 40 minutes 30 minutes Comparative Example 16 35 minutes 45 minutes 30 minutes Comparative Example 17 40 minutes 40 minutes 60 minutes Comparative Example 18 More than 60 minutes More than 60 minutes More than 60 minutes Comparative Example 19 More than 60 minutes More than 60 minutes More than 60 minutes Comparative Example 20 40 minutes 45 minutes 60 minutes Comparative Example 21 30 minutes 35 minutes 40 minutes 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)

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.

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.

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.

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.

Experimental Example  2: Evaluation of dissolution stability of organic light emitting device

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.

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.

Evaluation criteria are as follows.

No change in the transparency of the chemical when evaluated visually: ◎

Slightly increased turbidity when evaluated visually (transparent): ○

Increased turbidity (opacity) when visually assessed: △

Sediment Generated By Visual Evaluation: ×

division Melt stability Mask 1 separated organic material Mask 2 separated organic material Mask 3 separated organic material 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 Example 5 ○ △ ○ Comparative Example 6 ○ △ ○ Comparative Example 7 ○ △ △ Comparative Example 8 ○ x △ Comparative Example 9 ○ △ △ Comparative Example 10 ○ △ × Comparative Example 11 △ △ × Comparative Example 12 △ △ × Comparative Example 13 △ △ × Comparative Example 14 △ △ × Comparative Example 15 ○ △ △ Comparative Example 16 ○ △ △ Comparative Example 17 △ △ × Comparative Example 18 × × × Comparative Example 19 × × × Comparative Example 20 △ △ × Comparative Example 21 △ △ △ 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)

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.

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.

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)

To include a glyme compound represented by the formula (1), Mask cleaning liquid composition, containing no nonpolar solvent: [Formula 1]

In Chemical Formula 1, 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 method of claim 1, 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 The method of claim 1, 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. The method of claim 1, Mask cleaning liquid composition further comprising a water-soluble polar solvent. The method of claim 4, wherein 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. The method of claim 4, wherein 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. The method of claim 1, The mask cleaning liquid composition comprising less than 7 parts by weight of water based on 100 parts by weight of the total. The method of claim 7, wherein The mask cleaning liquid composition comprising 5 parts by weight or less based on 100 parts by weight of the total water. The method of claim 8, The mask cleaning liquid composition comprising the water in 3 parts by weight or less based on 100 parts by weight of the total. The method of claim 1, The mask cleaning liquid composition is to clean the mask used in the organic material vacuum deposition process.