CN117431551A - Inhibitor-free cleaning agent and method for cleaning conductive member for organic electroluminescent display device using the same - Google Patents

Inhibitor-free cleaning agent and method for cleaning conductive member for organic electroluminescent display device using the same Download PDF

Info

Publication number
CN117431551A
CN117431551A CN202310881172.3A CN202310881172A CN117431551A CN 117431551 A CN117431551 A CN 117431551A CN 202310881172 A CN202310881172 A CN 202310881172A CN 117431551 A CN117431551 A CN 117431551A
Authority
CN
China
Prior art keywords
cleaning agent
inhibitor
ether
conductive member
glycol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310881172.3A
Other languages
Chinese (zh)
Inventor
柳正勋
林永珉
许连
辛性勋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fengyuan Chemical Co ltd
Original Assignee
Fengyuan Chemical Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020230036785A external-priority patent/KR20240012271A/en
Application filed by Fengyuan Chemical Co ltd filed Critical Fengyuan Chemical Co ltd
Publication of CN117431551A publication Critical patent/CN117431551A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
    • B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/04—Coating on selected surface areas, e.g. using masks
    • C23C14/042—Coating on selected surface areas, e.g. using masks using masks
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/042—Coating on selected surface areas, e.g. using masks using masks
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/06—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using emulsions

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention provides an inhibitor-free cleaning agent and a cleaning method using the same, wherein the inhibitor-free cleaning agent comprises alkali salt, water-soluble organic acid salt, organic additives, emulsifying agents and aromatic alcohol, and the content concentration ranges of the water-soluble organic acid salt and the aromatic alcohol are respectively 1g/L to 25g/L and 10g/L to 200g/L.

Description

Inhibitor-free cleaning agent and method for cleaning conductive member for organic electroluminescent display device using the same
Technical Field
The present disclosure relates to a cleaning agent containing no inhibitor and a method for cleaning a conductive member for an organic electroluminescent display device using the same.
Background
The demand for display devices that output image information is increasing in various ways, and thus various flat panel display devices such as LCD (Liquid Crystal Display, hereinafter referred to as liquid crystal display device) or PDP (Plasma Display Panel), OLED (Organic Luminescent Emission Diode, hereinafter referred to as organic electroluminescent display device), VFD (Vacuum Fluorescent Display), and the like have been studied, developed, and used.
Among these flat panel Display devices, an organic electroluminescent Display device uses an organic light emitting layer, which is a self-luminous element that emits light from a phosphor by recombination of electrons and holes, and is excellent in Display characteristics such as Contrast Ratio (Contrast Ratio) and response speed (response time) and easy to realize a Flexible Display (Flexible Display), and is attracting attention as an optimal next-generation Display.
The organic electroluminescent display device (Organic light emitting diode display device) is formed by arranging a plurality of pixel regions in a matrix form, each of which has a micropattern formed therein, such as a driving element for driving each pixel, and the like.
In addition, the organic electroluminescent display device is a self-luminous element, and a separate light source used in a liquid crystal display device as a non-luminous element is not required, so that light and thin can be realized. Further, compared with the liquid crystal display device, the liquid crystal display device has the advantages of excellent visual angle and contrast, favorable power consumption, realization of direct current low-voltage driving, high response speed, strong external impact resistance because the internal components are solid, and wide use temperature range.
In general, the formation process of such organic electroluminescent display devices includes deposition and patterning processes of various substances on a substrate using conductive members such as metal masks. The metal mask used in the deposition and patterning processes may be contaminated with organic substances and the like, which may cause defects in the organic electroluminescent display device, and thus a cleaning process of the metal mask is further required.
In addition, as the mask process of the organic electroluminescent display device is improved, an organic mask and an inorganic mask are separately used, but a manner of depositing an organic layer and an inorganic layer using the same mask is being developed. However, even if the organic layer and the inorganic layer are deposited using the same mask, the mask cleaning process has a problem in that the organic cleaning and the inorganic cleaning need to be separately performed when using the conventional mask cleaning solution.
Disclosure of Invention
Technical problem
An embodiment is directed to providing a conductive member cleaning solution for use in an organic electroluminescent display device manufacturing process, which can be treated by a single process using one cleaning solution when cleaning organic and inorganic deposits of a conductive member used in an organic electroluminescent display device manufacturing process.
Further, an embodiment is directed to providing a conductive member cleaning solution used in a manufacturing process of an organic electroluminescent display device, which cleans organic and inorganic substances attached to a conductive member through a single process treatment, so that productivity can be improved and cost can be reduced.
Further, an embodiment aims to provide a conductive member cleaning liquid used in a manufacturing process of an organic electroluminescent display device, which can be more effectively cleaned.
Further, an embodiment is directed to providing a conductive member cleaning solution used in a manufacturing process of an organic electroluminescent display device, which can significantly reduce a product reject ratio caused by unwashed deposits and reduce Running costs by improving a cleaning performance degradation phenomenon caused by continuous use of a cleaning solution (cleaning agent).
Further, an embodiment is directed to providing a conductive member cleaning solution used in a manufacturing process of an organic electroluminescent display device, by shortening a cleaning time required for cleaning deposits of a conductive member by a conventional cleaning solution, more products are cleaned in the same time, so that productivity of products can be increased.
Further, an embodiment is directed to providing a conductive member cleaning agent used in a manufacturing process of an organic electroluminescent display device, which can significantly reduce a product reject ratio caused by degassing (outtake) of a cleaning solution remaining in a conductive member in a deposition apparatus by improving a phenomenon of remaining the cleaning solution on the conductive member in a process of washing the conductive member with Water (Water ring) and drying after cleaning a deposit of the conductive member.
Another embodiment is directed to a cleaning method for removing organic and inorganic substances attached to a conductive member used in a manufacturing process of an organic electroluminescent display device using the cleaning agent.
Technical proposal
One embodiment provides an Inhibitor-free (Inhibitor-free) cleaner comprising an alkali salt, a water-soluble organic acid salt, an organic additive, an emulsifier, and an aromatic alcohol, the water-soluble organic acid salt and the aromatic alcohol being present in a concentration range of 1g/L to 25g/L and 10g/L to 200g/L, respectively.
The concentration of the alkali salt may be in the range of 10g/L to 200g/L.
The concentration of the organic additive may be in the range of 50g/L to 500g/L.
The concentration of the emulsifier may be in the range of 50g/L to 300g/L.
The aromatic alcohol may be represented by the following chemical formula 1.
[ chemical formula 1]
In the above-mentioned chemical formula 1,
R 1 is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkoxy group,
n is an integer of 0 to 5,
L 1 is a substituted or unsubstituted C1 to C20 alkylene group or is represented by the following formula L,
[ chemical formula L ]
In the above-mentioned chemical formula L, a compound represented by the formula L,
L 2 is a substituted or unsubstituted C1 to C10 alkylene,
m is an integer of 1 to 10.
The aromatic alcohol can have only one hydroxyl group.
The aromatic alcohol may comprise Benzyl alcohol (Benzyl alcohol), 4-methoxybenzyl alcohol (4-Methoxybenzyl alcohol), 4-methylbenzyl alcohol (4-Methylbenzyl alcohol), 2,6-dimethylbenzyl alcohol (2, 6-Dimethylbenzyl alcohol), 4-ethoxybenzyl alcohol (4-Ethoxybenzyl alcohol), 4-isopropylbenzyl alcohol (4-Isopropylbenzyl alcohol), 4-butoxybenzyl alcohol (4-Butoxybenzyl alcohol), 2-Phenoxyethanol (2-Phenoxyethanol), 2-Methyl-1-Phenyl-2-propanol (2-Methyl-1-Phenyl-2-propanol), 1-Phenyl-1-propanol (1-Phenyl-1-propanol), or a combination thereof.
The base salt may comprise a hydroxide salt, a carbonate salt, a silicate salt, a phosphate salt, an ammonium salt, or a combination thereof.
The water-soluble organic acid salt may comprise a citrate salt, a succinate salt, an acetate salt, an oxalate salt, a glycolate salt, a gluconate salt, a tartrate salt, or a combination thereof.
The organic additive may comprise N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), dimethyl sulfoxide (Dimethyl sulfoxide, DMSO), tetrahydrofurfuryl alcohol (Tetrahydrofurfuryl alcohol, THFA), 1,3-Dimethyl-2-imidazolidinone (1, 3-Dimethyl-2-imidazolidinone), amide (Amide) compounds, C1 to C20 alkanols (Alkanol), C1 to C20 alkanolamines (Alkanol amine), glycol ethers (Glycol ether), or combinations thereof.
The Amide (Amide) compound may comprise dimethylacetamide (N, N-Dimethyl acetamide, DMAC), diethylacetamide (N, N-Diethyl acetamide, DEAC), dimethylformamide (N, N-Dimethyl formamide, DMF), diethylformamide (N, N-Diethyl formamide, DEF), dimethylpropionamide (N, N-Dimethyl propionamide, DMPA), diethylpropionamide (N, N-Diethyl propionamide, DEPA), dimethylacrylamide (N, N-Dimethyl acryamide, DMAA), diethylacrylamide (N, N-Diethyl acryamide, DEAA), or a combination thereof.
The Glycol Ether (glycoether) may comprise ethylene Glycol monomethyl Ether (Ethylene Glycol Monomethyl Ether; methyl Glycol, MG), diethylene Glycol monomethyl Ether (Diethylene Glycol Monomethyl Ether; methyl Di Glycol, MDG), triethylene Glycol monomethyl Ether (Triethylene Glycol Monomethyl Ether; methyl Tri Glycol, MTG), polyethylene Glycol monomethyl Ether (Polyethylene Glycol Monomethyl Ether; methyl Poly Glycol, MPG), ethylene Glycol monoisopropyl Ether (Ethylene Glycol Monoisopropyl Ether; iso-Propyl Glycol, iPG), ethylene Glycol monobutyl Ether (Ethylene Glycol Monobutyl Ether; butyl Glycol, BG), diethylene Glycol monobutyl Ether (Diethylene GlycolMonobutyl Ether; butyl Di Glycol, BDG), triethylene Glycol monobutyl Ether (Triethylene Glycol MonobutylEther; butyl Tri Glycol, BTG), ethylene Glycol monoisopropyl Ether (Ethylene Glycol Monoisopropyl Ether; iso-Butyl Glycol, iBG), diethylene Glycol monoisobutyl Ether (Diethylene Glycol onoisobutyl Ether; iso-Butyl Di Glycol, iBDG), ethylene Glycol monohexyl Ether (Ethylene Glycol Monohexyl Ether; hexyl Glycol, heG), diethylene Glycol monohexyl Ether (Diethylene Glycol Monohexyl Ether; hexyl Glycol, he75; butyl Di Glycol, BDG), triethylene Glycol monobutyl Ether (Triethylene Glycol MonobutylEther; butyl Tri Glycol, BTG), ethylene Glycol monoisopropyl Ether (Ethylene Glycol Monoisopropyl Ether; iso-Butyl Glycol, iBG), diethylene Glycol monohexyl Ether (Diethylene Glycol onoisobutyl Ether; iso-Butyl Glycol Di Glycol, iBDG), ethylene Glycol monohexyl Ether (Ethylene Glycol Monohexyl Ether; hexyl-2, hexyl Glycol, hexyl 2, DG 2-ethyl Ether (63-6-35), ethylene Glycol monohexyl Ether (63-35, 6-ethyl Glycol, ethylene Glycol) Ether (35), diethylene Glycol monophenyl ether (Diethylene Glycol Monophenyl Ether; phenyl Di Glycol, phDG), propylene Glycol monomethyl ether (Propylene Glycol Monomethyl Ether; methyl Propylene Glycol, MFG), dipropylene Glycol monoethyl ether (Dipropylene Glycol Monomethyl Ether; methyl Propylene Di Glycol, MFDG), tripropylene Glycol monomethyl ether (Tripropylene Glycol Monomethyl Ether; methyl Propylene Tri Glycol, MFTG), propylene Glycol monobutyl ether (Propylene Glycol Monobutyl Ether; butyl Propylene Glycol, BFG), dipropylene Glycol monobutyl ether (Dipropylene Glycol Monobutyl Ether; butyl Propylene Di Glycol, BFDG), propylene Glycol monomethyl ether acetate (Propylene Glycol Monomethyl Ether Acetate; methyl Propylene Glycol Acetate, MFG-AC), or combinations thereof.
The emulsifier may comprise Monoethanolamine (MEA), triethanolamine (TEA), aminoethylethanolamine (AEEA), glycerol (glycol), polyethylene glycol (PEG), polypropylene glycol (PPG), or a combination thereof.
The inhibitor-free cleaning agent may also comprise a surfactant.
The inhibitor-free cleaning agent may also comprise water.
The inhibitor-free cleaning agent may be a cleaning agent for cleaning a conductive member used in a manufacturing process of an organic electroluminescent display device.
The conductive member may include a Fine Metal Mask (FMM), an Open Metal Mask (OMM), or a combination thereof.
Another embodiment is directed to a cleaning method for removing organic and inorganic substances attached to a conductive member used in a manufacturing process of an organic electroluminescent display device, the method comprising: a step of preparing a conductive member to which an organic substance and an inorganic substance are attached; a step of immersing the conductive member in the cleaning agent; a step of maintaining the temperature of the cleaning agent at 20 ℃ to 90 ℃; and a step of cleaning the conductive member by simple dipping, supplying ultrasonic waves, CDA (clean dry air) and/or electric current.
Specific details of other aspects of the invention are included in the following detailed description.
Effects of the invention
The conductive member cleaning agent used in the manufacturing process of the organic electroluminescent display device according to one embodiment has a first effect in that it can treat organic and inorganic deposits of the conductive member used in the manufacturing process by a single process using one solution.
The conductive member cleaning agent used in the manufacturing process of the organic electroluminescent display device according to one embodiment has a second effect in that the organic and inorganic substances attached to the conductive member are cleaned by a single process treatment, so that productivity can be improved and cost can be reduced.
The conductive member cleaning agent used in the manufacturing process of the organic electroluminescent display device according to one embodiment has a third effect in that cleaning can be performed more effectively.
The conductive member cleaning agent used in the organic electroluminescent display device manufacturing process according to one embodiment has a fourth effect in that it can significantly reduce the product reject ratio caused by unwashed deposits and reduce the Running cost by improving the cleaning performance degradation phenomenon caused by the continuous use of the cleaning agent.
The conductive member cleaning agent used in the manufacturing process of the organic electroluminescent display device according to one embodiment has a fifth effect in that more products are cleaned in the same time by shortening the cleaning time required for cleaning the conductive member deposit, so that the product productivity can be increased.
The conductive member cleaning agent used in the process of manufacturing the organic electroluminescent display device according to one embodiment has a sixth effect in that it can remarkably reduce the defective rate of products caused by degassing (removal) of the cleaning agent remaining in the conductive member in the deposition apparatus by improving the phenomenon of the cleaning agent remaining on the conductive member in the process of washing (Water ring) and drying after cleaning the deposit of the conductive member to remove the cleaning agent remaining in the conductive member.
Drawings
Fig. 1 is a drawing showing a method of cleaning a conductive member used in a manufacturing process of an organic electroluminescent display device by simply dipping the conductive member in a cleaning agent (cleaning liquid) according to an embodiment.
Fig. 2 is a drawing showing a method of cleaning by providing ultrasonic waves after immersing a conductive member used in a manufacturing process of an organic electroluminescent display device in a cleaning agent (cleaning liquid) according to an embodiment.
Fig. 3 is a drawing showing a method of cleaning a conductive member used in a manufacturing process of an organic electroluminescent display device by immersing the conductive member in a cleaning agent (cleaning liquid) according to an embodiment and then supplying CDA (clean dry air).
Fig. 4 is a drawing showing a method of cleaning a conductive member used in a manufacturing process of an organic electroluminescent display device by supplying an electric current after immersing the conductive member in a cleaning agent (cleaning liquid) according to an embodiment.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments, but only controls the scope of the claims.
The embodiments of the present invention may be modified in various ways, and the scope of the present invention is not limited to the embodiments described below. Furthermore, embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art. Accordingly, the shape and size of the display elements may be exaggerated in the drawings for more clarity of description, and the same elements are denoted by the same reference numerals in the drawings.
Throughout the specification, when a portion is described as "comprising" a certain component, unless otherwise specified, it is meant that other components may also be included, and are not excluded.
In this specification, "alkyl" means C1 to C20 alkyl, "alkenyl" means C2 to C20 alkenyl, "cycloalkenyl" means C3 to C20 cycloalkenyl, "heterocycloalkenyl" means C3 to C20 heterocycloalkenyl, "aryl" means C6 to C20 aryl, "aralkyl" means C7 to C20 aralkyl, "alkylene" means C1 to C20 alkylene, "arylene" means C6 to C20 arylene, "alkylaryl" means C7 to C20 alkylarylene, "heteroarylene" means C3 to C20 heteroarylene, "alkyleneoxy" means C1 to C20 alkyleneoxy.
In this specification, unless otherwise indicated, "substituted" means that at least one hydrogen atom is substituted with a halogen atom (F, cl, br, I), a hydroxyl group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.
In this specification, unless otherwise defined, "combination" means mixing or copolymerization.
In the chemical formulas in the present specification, unless otherwise defined, when a bond is not drawn to a position where the bond is to be drawn, it means that a hydrogen atom is bonded to the position.
The process of forming the organic electroluminescent display device includes deposition and patterning processes of various substances on a substrate. In particular, in order to form the organic electroluminescent display device, an organic light emitting material pattern generating red light, green light, and blue light must be formed on a substrate. In addition, a metal electrode pattern such as a cathode of the organic light emitting diode must be formed on the substrate. At this time, a metal mask is disposed on the substrate, and the organic light emitting material pattern, the electrode pattern, or the like is formed using the metal mask.
The metal mask is a conductor made of Invar (Invar) or stainless steel. For the metal mask, a plurality of times may be used in order to form the organic light emitting material pattern, and a plurality of times may be used in order to form the electrode pattern.
At this time, organic substances such as substances for the organic light emitting material pattern or the like are attached to the metal mask or inorganic substances such as substances for the electrode pattern or the like are attached thereto, and thus, defects may be caused in the manufacture of the organic electroluminescent display device. That is, an organic light emitting material pattern different from a pattern to be formed may be formed on the substrate due to the adhesion of an organic or inorganic substance, and when an electrode pattern is formed, an organic layer and an inorganic layer may be formed to be laminated.
As examples of the organic substance, there may be also an organic light emitting material pattern substance, a residue of a photoresist used for manufacturing the metal mask, a residue of an adhesive tape used for packaging the metal mask, a residue that may adhere during the moving or cleaning, and the like. Further, as an example of the inorganic substance, a substance formed into an electrode pattern, or the like may be mentioned. In addition, various organic or inorganic substances may be attached to the metal mask.
A cleaning agent according to one embodiment, which comprises, as an inhibitor-free agent, an alkali salt, a water-soluble organic acid salt, an organic additive, an emulsifier, and an aromatic alcohol. At this time, the content concentration ranges of the water-soluble organic acid salt and the aromatic alcohol are 1g/L to 25g/L and 10g/L to 200g/L, respectively.
When the conductive member is continuously cleaned using a conventional cleaning liquid for removing organic and inorganic substances attached to the conductive member used in the manufacturing process of the organic electroluminescent display device, there is a problem in that cleaning performance is rapidly deteriorated. Due to this problem, the time required for cleaning is delayed, and unwashed deposits or residues are also present after cleaning, thus continuing to cause poor products. Further, as described below, since the conventional cleaning liquid contains inhibitors, it is difficult to continue to use for a long period of time, and eventually a new cleaning liquid must be frequently replaced, so that the Running cost (Running cost) must be increased.
As described above, the phenomenon that the cleaning performance is rapidly deteriorated due to the continuous use of the conventional cleaning liquid is caused by the concentration of the Inhibitor (Inhibitor) which is a component of the conventional cleaning liquid. As a chemical reaction inhibitor (suppressor), an inhibitor is added to a conventional cleaning liquid to prevent the surface of a conductive member from being corroded by the cleaning liquid or damaged by an excessive reaction, but at the same time, a negative effect of slowing down the cleaning speed of an inorganic substance attached to the conductive member occurs. The degree of the decrease in the washing speed varies depending on the kind of the inhibitor, but in general, the larger the amount of the inhibitor, the more the chemical reaction inhibiting ability becomes, and thus the washing time of the inorganic substance becomes slower. The main substances used as inhibitors are thiourea, 1,2, 3-benzotriazole, a pyridyl compound which may be a nitrogen or sulfur compound having an unshared electron pair, or an organic cyclic compound, etc.
The electroconductive member cleaning liquid used in the manufacturing process of the organic electroluminescent display device is generally used for several days to several weeks, during which the Water (Water) and a part of the highly volatile components of the cleaning liquid are evaporated, so that concentration of the cleaning liquid occurs. In the concentration process of the cleaning liquid, the alkali salt, the water-soluble organic acid salt and the inhibitor are solid substances or low-volatility components as raw materials, and almost no evaporation occurs. The total volume is reduced because the water and a part of the highly volatile components of the cleaning liquid are evaporated, but the alkali salt, the water-soluble organic acid salt, the inhibitor are hardly evaporated, and thus the concentration becomes relatively high. Therefore, as the conventional cleaning liquid is more and more concentrated for a long time, the concentration of the inhibitor becomes high, so that the cleaning speed becomes rapidly slow, and there occurs a phenomenon that unwashed deposits or residues are present.
In order to solve the problems of the conventional cleaning liquid as described above, the present inventors completed the component analysis of the conventional cleaning liquid, and confirmed that the inhibitor component in the conventional cleaning liquid is a problem, the inhibitor was removed, so that the phenomenon of rapid deterioration of cleaning performance due to concentration of the inhibitor caused by the long-time continuous use of the cleaning liquid can be improved. Further, it is possible to reduce a decrease in cleaning speed caused by continuous use of the cleaning liquid and a defective rate of products caused by unwashed deposits or residues, and it is possible to use a longer time since the replacement period of the cleaning liquid becomes long, so that it is also possible to save Running costs (Running costs).
On the other hand, as the conductive member used in the manufacturing process of the organic electroluminescent display device, invar or SUS (Steel Use Stainless) metal composed of an iron (Fe) alloy is mainly used, and in an environment where the concentration of alkali salt in the composition of the cleaning liquid is high, corrosion or damage due to excessive reaction may occur. In general, ferroalloy metals are easily corroded to be damaged in an Acid (Acid) environment, but a passivation film is formed on the metal surface to avoid damage in an alkali environment. However, even if a passivation film is formed in a high concentration of alkali salt exceeding 200g/L, the alkali environment cannot be sustained in a high concentration, and the passivation film is gradually destroyed, and corrosion or damage caused by excessive reaction may be caused to the ferroalloy metal. Accordingly, the present inventors have restricted the electroconductive member cleaning liquid used in the organic electroluminescent display device manufacturing process to an alkaline environment instead of an Acid (Acid) environment, in which case, since the concentration of the alkali salt is not a high concentration exceeding 200g/L (since the concentration of the alkali salt is 200g/L or less), the electroconductive member used in the organic electroluminescent display device manufacturing process can be protected from the cleaning liquid even without using an inhibitor.
Further, the cleaning agent according to one embodiment maintains the alkaline environment as described above, so that damage to the conductive member by the conventional cleaning agent containing the inhibitor can be prevented even if the inhibitor is not contained, and in one embodiment, the concentration ranges of the water-soluble organic acid salt and the aromatic alcohol, which constitute the components of the cleaning agent, are defined to be 1g/L to 25g/L and 10g/L to 200g/L, respectively, so that the cleaning agent (cleaning agent) component containing no inhibitor is optimized.
Further, the cleaning agent according to one embodiment further contains an aromatic alcohol, specifically an aromatic alcohol represented by chemical formula 1 below, as compared with a conventional cleaning solution for removing organic and inorganic substances attached to a conductive member used in a manufacturing process of an organic electroluminescent display device. The aromatic alcohol represented by chemical formula 1 improves the productivity of the product and improves the detergency of the organic matter and the washability (Water washability) of the cleaning liquid, thereby serving to reduce the defective rate of the product.
The first effect is to disperse the organic matter. For the organic material which is broken by being dispersed by the aromatic alcohol represented by chemical formula 1, the organic additive is more rapidly dissolved because of a wider reaction surface area, so that the cleaning time of the conductive member used in the manufacturing process of the organic electroluminescent display device can be shortened. Therefore, more conductive members can be cleaned in the same time, so that the productivity of products can be increased, and the parts of the conductive members which are structurally difficult to clean can be cleaned more easily, so that the defect of organic matter residue after cleaning can be remarkably reduced. The organic substances remaining in the conductive member become impurities in the deposition apparatus for producing a product, which may cause defective products, and thus it is necessary to minimize the residual phenomenon.
The second effect is to improve the water washability (Water washability). After cleaning organic and inorganic substances of a conductive member used in a manufacturing process of an organic electroluminescent display device, cleaning liquid is attached to a surface of the conductive member, a metal overlapping portion, and a solder joint portion. In order to remove the cleaning liquid attached to the conductive member, as a next process, a process of washing the conductive member with washing Water (Water) will be performed. In this process, the conventional cleaning liquid is not easily washed off at the metal overlapping portion and the solder joint portion of the conductive member to remain, resulting in defects. As described above, if the cleaning liquid remains on the metal overlapped portion and the solder joint portion of the conductive member, the organic and inorganic substances deposited on the product may be damaged by evaporation in the deposition apparatus for producing the product, possibly resulting in defective products. On the other hand, the cleaning agent according to one embodiment further contains the aromatic alcohol represented by chemical formula 1 to promote cleaning of the metal overlapped portion of the conductive member, the solder joint portion, to be more easily removed by the cleaning water, thereby reducing the phenomenon of cleaning liquid residue, and can significantly reduce product defects.
Hereinafter, constituent elements constituting the inhibitor-free cleaning agent according to one embodiment will be described in further detail.
Water-soluble salts of organic acids
As a component that plays a role of preventing pH shock of the cleaning agent according to one embodiment, preventing hydroxide precipitation of metal ions, assisting in removing organic and inorganic substances, the water-soluble organic acid salt may include citrate, succinate, acetate, oxalate, glycolate, gluconate, tartrate, or a combination thereof, or the like. For example, the water-soluble organic acid salt may be one or a mixture of two selected from citrate, succinate, acetate, oxalate, glycolate, gluconate and tartrate, and gluconate is preferable from the viewpoint of stability of the cleaning agent, but is not limited thereto. Here, the salt may be an alkali metal such as sodium or potassium or an alkaline earth metal such as calcium or barium.
For example, the water-soluble organic acid salt may be exemplified by potassium citrate (Potassium citrate), sodium citrate (Sodium citrate), potassium succinate (Potassium succinate), sodium succinate (Sodium succinate), potassium acetate (Potassium acetate), sodium acetate (Sodium acetate), potassium oxalate (Potassium oxalate), sodium oxalate (Sodium oxalate), potassium glycolate (Potassium glycolate), sodium glycolate (Sodium glycolate), potassium gluconate (Potassioum gluconate), sodium gluconate (Sodium gluconate), potassium tartrate (Potassium tartrate), sodium tartrate (Sodium tartrate), and the like, but is not limited thereto.
Furthermore, in the inhibitor-free cleaning agent component according to one embodiment, the concentration of the water-soluble organic acid salt should range from 1g/L to 25g/L, for example, may range from 1g/L to 12g/L. If the concentration of the water-soluble organic acid salt is less than 1g/L, the pH of the cleaning agent suddenly changes or hydroxide precipitate is generated, and if the concentration of the water-soluble organic acid salt is more than 25g/L, excessive reaction with organic and inorganic substances occurs, possibly impairing the dissolution stability, and thus may be undesirable. In any case, when the concentration of the water-soluble organic acid salt is more than 25g/L, it may be more suitable for the inhibitor-containing cleaning agent than the non-inhibitor-containing cleaning agent due to the deterioration of the dissolution stability of the organic and inorganic substances. This is because, as a chemical reaction inhibitor, the inhibitor suppresses excessive reaction of organic substances and inorganic substances. That is, in order for the cleaning agent according to one embodiment to be an inhibitor-free cleaning agent, it is preferable that the concentration of the water-soluble organic acid salt is kept at 25g/L or less, for example, 20g/L or less, for example, 15g/L or less, for example, 12g/L or less.
Aromatic alcohol
As a component for increasing the reaction surface area by dispersing the organic substance, thereby shortening the dissolution time and improving the washability (Water washability) to reduce the phenomenon of the detergent remaining on the conductive member used in the manufacturing process of the organic electroluminescent display device, the aromatic alcohol can be represented by the following chemical formula 1.
[ chemical formula 1]
In the above-mentioned chemical formula 1,
R 1 is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkoxy group,
n is an integer of 0 to 5,
L 1 is a substituted or unsubstituted C1 to C20 alkylene group or is represented by the following formula L,
[ chemical formula L ]
In the above-mentioned chemical formula L, a compound represented by the formula L,
L 2 is a substituted or unsubstituted C1 to C10 alkylene,
m is an integer of 1 to 10.
For example, for the aromatic alcohol, the aromatic alcohol specifically represented by the above chemical formula 1 can have only one hydroxyl group. The aromatic alcohol having two or more hydroxyl groups (represented by the above chemical formula 1) also plays a role in preventing corrosion of metal substances, and is therefore disadvantageous in terms of cleaning rate and also in terms of washability, and it may be preferable that the aromatic alcohol represented by the above chemical formula 1 has one hydroxyl group. That is, when the aromatic alcohol (represented by the above chemical formula 1) has two or more hydroxyl groups, the cleaning power and the water washability may be lowered because of the excellent effect of preventing corrosion of the metal substances, as compared with the case where the number of hydroxyl groups is one.
For example, the aromatic alcohol may be one or a mixture of two selected from Benzyl alcohol (Benzyl alcohol), 4-methoxybenzyl alcohol (4-Methoxybenzyl alcohol), 4-methylbenzyl alcohol (4-Methylbenzyl alcohol), 2,6-dimethylbenzyl alcohol (2, 6-Dimethylbenzyl alcohol), 4-ethoxybenzyl alcohol (4-Ethoxybenzyl alcohol), 4-isopropylbenzyl alcohol (4-Isopropylbenzyl alcohol), 4-butoxybenzyl alcohol (4-Butoxybenzyl alcohol), 2-Phenoxyethanol (2-phenoxythanol), 2-Methyl-1-Phenyl-2-propanol (2-Methyl-1-Phenyl-2-propanol) and 1-Phenyl-1-propanol (1-Phenyl-1-propanol), and Benzyl alcohol (Benzyl alcohol) may be preferable from the viewpoint of stability of the cleaning agent, but is not limited thereto.
Furthermore, in the inhibitor-free cleaning agent component according to one embodiment, the concentration of the aromatic alcohol may preferably range from 10g/L to 200g/L. If the concentration of the aromatic alcohol is less than 10g/L, product defects may occur due to degassing (outlining) in the deposition apparatus due to the relatively high amount of cleaning agent remaining in the conductive member used in the manufacturing process of the organic electroluminescent display device. If the concentration of the aromatic alcohol is more than 200g/L, the dissolution stability of the inorganic substance may be impaired, and thus may be undesirable.
Alkali salt
As a component for dissolving the inorganic substance and the organic substance having an ester functional group, a hydroxide salt, a carbonate salt, a silicate salt, or a phosphate salt, an ammonium salt, or a combination thereof can be cited. For example, the alkali salt may be at least one selected from the group consisting of a hydroxide salt, a carbonate salt, a silicate salt, a phosphate salt, and an ammonium salt, or a mixture of both, and a hydroxide salt may be preferable from the viewpoint of stability of the cleaning agent, but is not necessarily limited thereto. Here, the salt may be an alkali metal such as sodium or potassium or an alkaline earth metal such as calcium or barium.
For example, the alkali salt may be exemplified by potassium hydroxide (Potassium hydroxide), sodium hydroxide (Sodium hydroxide), potassium carbonate (Potassium carbonate), sodium carbonate (Sodium carbonate), potassium silicate (Potassium silicate), sodium silicate (Sodium silicate), potassium phosphate (Potassium phosphate), sodium phosphate (Sodium phosphate), ammonium carbonate (Ammonium carbonate), and the like, but is not limited thereto.
Furthermore, in the inhibitor-free cleaning agent component according to one embodiment, the concentration of the alkali salt may preferably range from 10g/L to 200g/L. If the concentration of the alkali salt is less than 10g/L, the washing speed becomes slow, and organic and inorganic substances cannot be washed rapidly. If the concentration of the alkali salt is more than 200g/L, conductive members used in the manufacturing process of the organic electroluminescent display device may be damaged, and thus may be not preferable.
Organic additives
As the component for dissolving the organic substance, N-methyl-2-pyrrolidone, NMP, N-ethyl-2-pyrrolidone, NEP, dimethyl sulfoxide (Dimethyl sulfoxide, DMSO), tetrahydrofurfuryl alcohol (Tetrahydrofurfuryl alcohol, THFA), 1,3-Dimethyl-2-imidazolidinone (1, 3-Dimethyl-2-imidozolide), an Amide (Amide) compound, an Alkanol (alcanol) having 1 to 20 (C1 to C20), an Alkanol amine (alcanol amine) having 1 to 20 (C1 to C20), a Glycol ether (Glycol ether), or a combination thereof, and the like can be cited. For example, the organic additive may be one or a mixture of two selected from N-methyl-2-pyrrolidone, NMP, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (Dimethyl sulfoxide, DMSO), tetrahydrofurfuryl alcohol (Tetrahydrofurfuryl alcohol, THFA), 1,3-Dimethyl-2-imidazolidinone (1, 3-Dimethyl-2-imidozolide), an Amide (Amide) compound, an Alkanol (alcanol) having 1 to 20 (C1 to C20), an alkanolamine (alcanol amine) having 1 to 20 (C1 to C20), and a Glycol ether (Glycol ether), which may be preferable from the viewpoint of stability of the cleaning agent, but is not limited thereto.
For example, the Amide (Amide) compound may be exemplified by dimethylacetamide (N, N-Dimethyl acetamide, DMAC), diethylacetamide (N, N-Diethyl acetamide, DEAC), dimethylformamide (N, N-Dimethyl formamide, DMF), diethylformamide (N, N-Diethyl formamide, DEF), dimethylpropionamide (N, N-Dimethyl propionamide, DMPA), diethylpropionamide (N, N-Diethyl propionamide, DEPA), dimethylacrylamide (N, N-Dimethyl acryamide, DMAA), diethylacrylamide (N, N-Diethyl acryamide, DEAA), etc., but is not limited thereto.
For example, the Glycol Ether (glycoether) may be exemplified by ethylene Glycol monomethyl Ether (Ethylene Glycol Monomethyl Ether; methyl Glycol, MG), diethylene Glycol monomethyl Ether (Diethylene Glycol Monomethyl Ether; methyl Di Glycol, MDG), triethylene Glycol monomethyl Ether (Triethylene Glycol Monomethyl Ether; methyl Tri Glycol, MTG), polyethylene Glycol monomethyl Ether (Polyethylene Glycol Monomethyl Ether; methyl Poly Glycol, MPG), ethylene Glycol monoisopropyl Ether (Ethylene Glycol Monoisopropyl Ether; iso-Propyl Glycol, iPG), ethylene Glycol monobutyl Ether (Ethylene Glycol Monobutyl Ether; butyl Glycol, BG), diethylene Glycol monobutyl Ether (Diethylene GlycolMonobutyl Ether; butyl Di Glycol, BDG), triethylene Glycol monobutyl Ether (Triethylene Glycol MonobutylEther; butyl Tri Glycol, BTG), ethylene Glycol monoisopropyl Ether (Ethylene Glycol Monoisopropyl Ether; iso-Butyl Glycol, iBG), diethylene Glycol monoisobutyl Ether (Diethylene Glycol onoisobutyl Ether; iso-Butyl Di Glycol, iBDG), ethylene Glycol monohexyl Ether (Ethylene Glycol Monohexyl Ether; hexyl Glycol, heG), diethylene Glycol monohexyl Ether (Diethylene Glycol Monohexyl Ether; hexyl Glycol, he75; butyl Di Glycol, BDG), triethylene Glycol monobutyl Ether (Triethylene Glycol MonobutylEther; butyl Tri Glycol, BTG), ethylene Glycol monoisopropyl Ether (Ethylene Glycol Monoisopropyl Ether; iso-Butyl Glycol, iBG), diethylene Glycol monohexyl Ether (Diethylene Glycol onoisobutyl Ether; iso-Butyl Glycol Di Glycol, iBDG), ethylene Glycol monohexyl Ether (Ethylene Glycol Monohexyl Ether; hexyl-2, hexyl Glycol, hexyl 2, DG 2-ethyl Ether (63-6-35), ethylene Glycol monohexyl Ether (63-35, 6-ethyl Glycol, ethylene Glycol) Ether (35), diethylene Glycol monophenyl ether (Diethylene Glycol Monophenyl Ether; phenyl Di Glycol, phDG), propylene Glycol monomethyl ether (Propylene Glycol Monomethyl Ether; methyl Propylene Glycol, MFG), dipropylene Glycol monoethyl ether (Dipropylene Glycol Monomethyl Ether; methyl Propylene Di Glycol, MFDG), tripropylene Glycol monomethyl ether (Tripropylene Glycol Monomethyl Ether; methyl Propylene Tri Glycol, MFTG), propylene Glycol monobutyl ether (Propylene Glycol Monobutyl Ether; butyl Propylene Glycol, BFG), dipropylene Glycol monobutyl ether (Dipropylene Glycol Monobutyl Ether; butyl Propylene Di Glycol, BFDG), propylene Glycol monomethyl ether acetate (Propylene Glycol Monomethyl Ether Acetate; methyl Propylene Glycol Acetate, MFG-AC), and the like, but are not limited thereto.
Furthermore, in the inhibitor-free cleaning agent component according to one embodiment, the concentration of the organic additive may preferably range from 50g/L to 500g/L. If the concentration of the organic additive is less than 50g/L, the washing speed becomes slow, and the organic matters cannot be washed rapidly. If the concentration of the organic additive is more than 500g/L, the dissolution stability of the inorganic substance may be impaired, and thus may be undesirable.
Emulsifying agent
As the component having a mediating effect for mixing the alkali salt and the organic additive, the emulsifier may contain Monoethanolamine (MEA), triethanolamine (TEA), aminoethylethanolamine (AEEA), glycerol (Glycerol), polyethylene glycol (PEG), polypropylene glycol (PPG), or a combination thereof, or the like. For example, the emulsifier may be one or a mixture of two selected from Monoethanolamine (MEA), triethanolamine (TEA), aminoethylethanolamine (AEEA), glycerol (Glycerol), polyethylene glycol (PEG) and polypropylene glycol (PPG), and Triethanolamine (Triethanolamine) may be preferable from the viewpoint of stability of the cleaning agent, but is not limited thereto.
Furthermore, in the inhibitor-free cleaning agent component according to one embodiment, the concentration of the emulsifier may preferably range from 50g/L to 300g/L. If the concentration of the emulsifier is less than 50g/L, the alkali salt and the organic additive are not mixed. If the concentration of the emulsifier is more than 300g/L, there is a difficulty in management due to an increase in viscosity of the cleaning agent, and thus it may be not preferable.
Other ingredients
The cleaning agent according to one embodiment, that is, the cleaning agent for removing organic and inorganic substances adhering to the conductive member used in the manufacturing process of the organic electroluminescent display device may further comprise a surfactant.
For example, the surfactant may further include at least one or more selected from anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. When the cleaning agent according to one embodiment further contains the surfactant as described above, the surface tension of the cleaning agent is reduced, and permeability can be improved.
For example, the anionic surfactant may be a monoalkyl sulfate, an alkyl polyoxyethylene sulfate, an alkylbenzene sulfonate, a monoalkyl phosphate, etc., the cationic surfactant may be a dialkyl dimethyl ammonium salt, an alkyl benzyl ammonium salt, etc., the nonionic surfactant may be a polyoxyethylene alkyl ether, a fatty acid sorbitan ester, a fatty acid diethanolamine, an alkyl monoglyceride ether, etc., and the amphoteric surfactant may be an alkyl sulfobetaine, an alkyl carboxybetaine, etc., but is not limited thereto.
The cleaning agent may further comprise water. That is, the ingredients are dissolved in water, thereby facilitating the formulation of the inhibitor-free cleaning agent according to one embodiment. The water is preferably water from which ionic substances and impurities are removed, and may be, for example, ion-exchanged water, pure water, ultrapure water, or the like.
The temperature of the cleaning agent may be 20 ℃ or higher, for example, 20 ℃ to 90 ℃, for example, 40 ℃ to 90 ℃, for example, 50 ℃ to 90 ℃. When the temperature of the cleaning agent according to one embodiment is controlled within the range, organic and inorganic substances adhering to the conductive member used in the manufacturing process of the organic electroluminescent display device can be most effectively removed. That is, the inhibitor-free cleaning agent may be a cleaning agent for cleaning a conductive member used in the manufacturing process of the organic electroluminescent display device.
The conductive member may include a Fine Metal Mask (FMM), an Open Metal Mask (OMM), or a combination thereof.
According to another embodiment, there is provided a cleaning method using the cleaning agent, in particular, a cleaning method using the cleaning agent to remove organic and inorganic substances adhering to a conductive member used in a manufacturing process of an organic electroluminescent display device.
Specifically, a cleaning method for removing organic and inorganic substances adhering to a conductive member used in a manufacturing process of an organic electroluminescent display device according to another embodiment includes: a step of preparing a conductive member to which an organic substance and an inorganic substance are attached; a step of immersing the conductive member in the cleaning agent; a step of maintaining the temperature of the cleaning agent at 20 ℃ to 90 ℃; and a step of cleaning the conductive member by simple dipping, supplying ultrasonic waves, CDA (clean dry air) and/or electric current.
Hereinafter, a cleaning method using the cleaning agent according to an embodiment will be described with reference to the accompanying drawings. The repeated description of the cleaning agent described above may be omitted. Fig. 1 to 4 are drawings for describing a cleaning method using a cleaning agent according to an embodiment, respectively.
Fig. 1 is a view showing a cleaning method of cleaning a conductive member by simply immersing the conductive member in a cleaning agent (cleaning liquid).
Fig. 2 shows a cleaning method in which an electroconductive member is immersed in a cleaning agent (cleaning liquid) and then subjected to ultrasonic cleaning.
Fig. 3 is a view showing a cleaning method in which a conductive member is immersed in a cleaning agent (cleaning liquid) and then CDA (clean dry air) is supplied to clean the conductive member.
Fig. 4 is a view showing a cleaning method in which a conductive member is immersed in a cleaning agent (cleaning liquid) and then subjected to cleaning by supplying an electric current.
Among the four cleaning methods, a cleaning method of supplying current for cleaning, which needs to be further described, will be described in detail with reference to fig. 4.
Referring to fig. 4, a cleaning method according to another embodiment may utilize a cleaning agent 20 according to one embodiment. In addition, the cleaning method may clean the conductive member 10 used in the manufacturing process of the organic electroluminescent display device using the cleaning agent 20 and the cleaning device. The cleaning method may be performed by electrolysis. At this time, the cleaning device includes an electrolytic cell 100, a power supply device 200, a terminal 300, and an electrode 400. The cleaning method is described in further detail below.
First, the conductive member 10 used in the manufacturing process of the organic electroluminescent display device is prepared. For example, the step of preparing the conductive member 10 is to arrange the conductive member 10 on a substrate for forming an organic electroluminescent display device, and sequentially form a pattern composed of the organic substance and a pattern composed of the inorganic substance on the substrate using the conductive member 10. Then, the conductive member 10 is separated from the substrate.
That is, the conductive member 10 used in the manufacturing process of the organic electroluminescent display device may be a metal mask for forming an organic light emitting material pattern or an electrode pattern. Therefore, an organic substance or an inorganic substance may be attached to the conductive member 10. In addition, the conductive member 10 may be made of invar or stainless steel.
The electrolytic cell 100 is filled with a cleaning agent 20. As described above, the cleaning agent 20 may be, for example, an aqueous solution containing an alkali salt, a water-soluble organic acid salt, an organic additive, an emulsifier, an aromatic alcohol, and water. At this time, the alkali salt may form conductive ions by electrolysis.
The conductive member 10 may be connected to the terminal 300. The terminal 300 is electrically connected to the power supply device 200 and to the conductive member 10. At this time, the terminal 300 may have a clamp shape. Then, the conductive member 10 is immersed in the cleaning agent 20.
In addition, the electrode 400 is immersed in the cleaning agent 20. The electrode 400 is electrically connected to the power supply device 200 and receives a voltage from the power supply device 200. The electrode 400 may be formed of any one selected from iridium oxide, titanium, platinum, and nickel.
The power supply device 200 may apply a voltage to the conductive member 10 to be cleaned through the terminal 300. In addition, the power supply device 200 may apply a voltage to the electrode 400. For example, the power supply device 200 applies a negative voltage to the conductive member 10 and a positive voltage to the electrode 400. In contrast, the power supply device 200 may apply a positive voltage to the conductive member 10 and a negative voltage to the electrode 400.
The power supply device 200 can cause a current to flow through the conductive member 10 and the electrode 400 by applying a voltage to the conductive member 10 and the electrode 400. At this time, the current density is 1 to 12A/dm 2 May flow through the conductive member 10 and the electrode 400.
When a voltage is applied to the conductive member 10 immersed in the cleaning agent 20 and the electrode 400 and a current flows, bubbles are generated on the surface of the conductive member 10. By the bubbles, the organic and inorganic substances adhering to the conductive member 10 can be electrolytically cleaned.
Specifically, when a negative voltage is applied to the conductive member 10 and a positive voltage is applied to the electrode 400, hydrogen bubbles are generated on the surface of the conductive member 10 as shown in [ reaction formula 1 ].
[ reaction type 1]
2H + +2e→H 2
In addition, as shown in [ equation 2], oxygen bubbles are generated on the surface of the electrode 400.
[ reaction type 2]
4OH - →4e+O 2 +H 2 O
The organic and inorganic substances attached to the conductive member 10 can be physically removed by the hydrogen bubbles. In addition, the organic and inorganic substances attached to the conductive member 10 can be chemically removed by the cleaning agent 20.
That is, the conductive member 10 having the organic and inorganic substances attached thereto can be removed by immersing the conductive member in the cleaning agent 20, but can be removed more quickly and effectively by electrolysis.
For example, when electrolysis is used, there is an effect that even residues of magnesium (Mg) and silver (Ag) which are not easily removed by merely immersing in the cleaning agent 20 can be removed. In addition, the time for removing the organic and inorganic substances can be shortened.
Referring to the [ equation 1] and the [ equation 2], the hydrogen bubbles are generated twice as much as the oxygen bubbles. Therefore, when a negative voltage is applied to the conductive member 10, organic substances and inorganic substances can be more effectively removed. In addition, since hydrogen ions are removed from the surface of the conductive member 10, the electrolyte adjacent to the surface of the conductive member 10 may have stronger basicity than other portions.
Further, by using ultrasonic waves together at the time of electrolytic cleaning, the cleaning time can be further shortened.
Therefore, by the cleaning agent 20 according to one embodiment and the cleaning method using the cleaning agent 20, the organic substance and the inorganic substance attached to the conductive member 10 used in the manufacturing process can be cleaned by a single process using one solution. In addition, in this way, productivity can be improved and cost can be reduced, and cleaning can be performed more effectively. In particular, since the cleaning is performed using the cleaning agent without any inhibitor, i) the product reject ratio caused by unwashed deposits and the Running cost (Running cost) can be remarkably reduced by improving the phenomenon of degradation of cleaning performance caused by the continuous use of the cleaning agent containing the conventional inhibitor, ii) the product productivity can be improved by greatly shortening the cleaning time required for cleaning the conductive member deposits, and cleaning more products in the same time, iii) the product reject ratio caused by degassing (outlining) of the cleaning agent remaining in the conductive member in the deposition apparatus can be remarkably reduced by improving the phenomenon of residual cleaning agent on the conductive member during the cleaning of the conductive member deposits after the Water ring and drying to clean the cleaning agent remaining in the conductive member.
Preferred embodiments of the present invention are described below. However, the following embodiment is only one preferred embodiment of the present invention, and the present invention is not limited to the following embodiment.
Example (example)
Residue removal time and metal mask washing effect
Experimental example 1
The experimental conditions are as follows.
First, the cleaning agent is in the form of an aqueous solution at 20℃and comprises 40g/L of potassium hydroxide salt, potassium citrate salt, 150g/L of ethylene glycol monomethyl ether, 100g/L of triethanolamine and benzyl alcohol. The change in the removal rate of the photoresist residue was observed by changing the contents of the potassium citrate salt and benzyl alcohol as shown in tables 1 and 2 below.
Applying a voltage to the metal mask and the electrode by a power supply device so as to be 1.5A/dm 2 Is passed through a metal mask made of invar.
Photoresist may adhere to the metal mask.
After removing the photoresist residue by applying a voltage to the metal mask having the photoresist attached thereto, the metal mask having the photoresist residue removed was washed with washing water, and how well the cleaning agent attached to the metal mask was washed with the washing water was observed.
The results according to experimental example 1 in tables 1 and 2 below were visually observed with SEM equipment. The results are expressed below.
Residue removal effect
O (good): the photoresist residue removal time is less than 2 minutes
Delta (normal): the photoresist residue removal time is more than 2 minutes and less than 10 minutes
X (bad): the photoresist residue removal time is more than 10 minutes
Effect of washing with water
O (good): the residual cleaning agent was found to be 1% or less of the metal mask area
Delta (normal): the residual cleaning agent was found to be more than 1% and less than 10% of the metal mask area
X (bad): the residual cleaning agent was found to be 10% or more of the metal mask area
TABLE 1
TABLE 2
Experimental example 2
The results are shown in tables 3 and 4 below, except that 5g/L of the inhibitor (thiourea) was added in the example used in Experimental example 1.
TABLE 3
TABLE 4
Experimental example 3
The results are shown in tables 5 and 6 below, except that 2-methyl-1-phenyl-2-propanol was used in place of benzyl alcohol in the example of Experimental example 1.
TABLE 5
TABLE 6
Experimental example 4
The results are shown in tables 7 and 8 below, except that 4-hydroxybenzyl alcohol was used in place of benzyl alcohol in the example of Experimental example 1, which was the same as in Experimental example 1.
TABLE 7
TABLE 8
Experimental example 5
The results are shown in tables 9 and 10 below, except that the metal mask to which the photoresist was attached was simply immersed in the cleaning agent used in the example of experimental example 1 instead of supplying the current.
TABLE 9
TABLE 10
Experimental example 6
The results are shown in tables 11 and 12 below, except that the metal mask to which the photoresist was attached was immersed in the cleaning agent used in the example of experimental example 1 and ultrasonic waves were applied instead of applying the current.
TABLE 11
TABLE 12
Experimental example 7
The results are shown in tables 13 and 14 below, except that CDA (clean dry air) is supplied after immersing the metal mask to which the photoresist was attached in the cleaning agent for the example of experimental example 1 instead of supplying the current.
TABLE 13
TABLE 14
From the above-described experimental examples 1 and 2, it was confirmed that the cleaning agent according to one embodiment can very rapidly remove the photoresist, although it does not contain an inhibitor, and further has excellent water washability. Further, it was confirmed from the above-mentioned experimental examples 3 and 4 that the same level of effect was obtained even if benzyl alcohol was replaced with 2-methyl-1-phenyl-2-propanol as the aromatic alcohol, but the residue removing effect and the water washing effect were halved when 4-hydroxybenzyl alcohol having two hydroxyl groups was used. Further, it was confirmed from experimental examples 5 to 7 that the residue removing effect and the corrosion effect were all at the same level even if any of simple dipping, ultrasonic wave supply, CDA (clean dry air) supply and electric current supply were used as the cleaning method.
The present invention can be implemented in various ways and is not limited to the above-described embodiments, and it will be understood by those skilled in the art that the present invention can be implemented in other specific ways without changing the technical idea or essential features of the present invention. Accordingly, it should be understood that the above-described embodiments are illustrative and not intended to limit the present invention.
Description of the reference numerals
10. Conductive member
20. Cleaning agent (cleaning liquid)
100. Electrolytic cell
200. Power supply device
300. Terminal for connecting a plurality of terminals
400. Electrode

Claims (18)

1. An inhibitor-free cleaning agent, wherein
The inhibitor-free cleaning agent comprises alkali salt, water-soluble organic acid salt, organic additive, emulsifying agent and aromatic alcohol,
the content concentration ranges of the water-soluble organic acid salt and the aromatic alcohol are 1g/L to 25g/L and 10g/L to 200g/L respectively.
2. The inhibitor-free cleaning agent according to claim 1, wherein,
the concentration of the alkali salt is in the range of 10g/L to 200g/L.
3. The inhibitor-free cleaning agent according to claim 1, wherein,
the content concentration of the organic additive ranges from 50g/L to 500g/L.
4. The inhibitor-free cleaning agent according to claim 1, wherein,
The content concentration of the emulsifier is in the range of 50g/L to 300g/L.
5. The inhibitor-free cleaning agent according to claim 1, wherein,
the aromatic alcohol is represented by the following chemical formula 1:
[ chemical formula 1]
In the above-mentioned chemical formula 1,
R 1 is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkoxy group,
n is an integer of 0 to 5,
L 1 is a substituted or unsubstituted C1 to C20 alkylene group or is represented by the following formula L,
[ chemical formula L ]
In the above-mentioned chemical formula L, a compound represented by the formula L,
L 2 is a substituted or unsubstituted C1 to C10 alkylene,
m is an integer of 1 to 10.
6. The inhibitor-free cleaning agent according to claim 5, wherein,
the aromatic alcohol has only one hydroxyl group.
7. The inhibitor-free cleaning agent according to claim 1, wherein,
the aromatic alcohol comprises benzyl alcohol, 4-methoxybenzyl alcohol, 4-methylbenzyl alcohol, 2, 6-dimethylbenzyl alcohol, 4-ethoxybenzyl alcohol, 4-isopropylbenzyl alcohol, 4-butoxybenzyl alcohol, 2-phenoxyethanol, 2-methyl-1-phenyl-2-propanol, 1-phenyl-1-propanol, or a combination thereof.
8. The inhibitor-free cleaning agent according to claim 1, wherein,
the base salt comprises a hydroxide salt, a carbonate salt, a silicate salt, a phosphate salt, an ammonium salt, or a combination thereof.
9. The inhibitor-free cleaning agent according to claim 1, wherein,
the water-soluble organic acid salt comprises a citrate, succinate, acetate, oxalate, glycolate, gluconate, tartrate, or a combination thereof.
10. The inhibitor-free cleaning agent according to claim 1, wherein,
the organic additive comprises N-methylpyrrolidone, N-ethylpyrrolidone, dimethylsulfoxide, tetrahydrofurfuryl alcohol, 1, 3-dimethyl-2-imidazolidinone, an amide compound, a C1 to C20 alkanol, a C1 to C20 alkanolamine, a glycol ether, or a combination thereof.
11. The inhibitor-free cleaning agent according to claim 10, wherein,
the amide compound comprises dimethylacetamide, diethylacetamide, dimethylformamide, diethylformamide, dimethylpropionamide, diethylpropionamide, dimethylacrylamide, diethylacrylamide, or a combination thereof.
12. The inhibitor-free cleaning agent according to claim 10, wherein,
the glycol ether comprises ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, ethylene glycol monoallyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, or a combination thereof.
13. The inhibitor-free cleaning agent according to claim 1, wherein,
the emulsifier comprises monoethanolamine, triethanolamine, aminoethylethanolamine, glycerol, polyethylene glycol, polypropylene glycol, or a combination thereof.
14. The inhibitor-free cleaning agent according to claim 1, wherein,
the inhibitor-free cleaning agent further comprises a surfactant.
15. The inhibitor-free cleaning agent according to claim 1, wherein,
the inhibitor-free cleaning agent further comprises water.
16. The inhibitor-free cleaning agent according to claim 1, wherein,
the inhibitor-free cleaning agent is used for cleaning conductive parts used in the manufacturing process of the organic electroluminescent display device.
17. The inhibitor-free cleaning agent according to claim 16, wherein,
the conductive features comprise a fine metal mask, an open metal mask, or a combination thereof.
18. A cleaning method for removing organic and inorganic substances adhering to a conductive member used in a manufacturing process of an organic electroluminescent display device, the method comprising:
a step of preparing a conductive member to which an organic substance and an inorganic substance are attached;
a step of immersing the conductive member in the cleaning agent according to any one of claims 1 to 17;
A step of maintaining the temperature of the cleaning agent at 20 ℃ to 90 ℃; and
a step of cleaning the conductive member by simple dipping, supplying ultrasonic waves, CDA (clean dry air) and/or electric current.
CN202310881172.3A 2022-07-20 2023-07-18 Inhibitor-free cleaning agent and method for cleaning conductive member for organic electroluminescent display device using the same Pending CN117431551A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR10-2022-0089842 2022-07-20
KR10-2023-0036785 2023-03-21
KR1020230036785A KR20240012271A (en) 2022-07-20 2023-03-21 Inhibitor-free cleaning agent and method for cleaning conductive members for organic electroluminescent display devices using the same

Publications (1)

Publication Number Publication Date
CN117431551A true CN117431551A (en) 2024-01-23

Family

ID=89546900

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310881172.3A Pending CN117431551A (en) 2022-07-20 2023-07-18 Inhibitor-free cleaning agent and method for cleaning conductive member for organic electroluminescent display device using the same

Country Status (1)

Country Link
CN (1) CN117431551A (en)

Similar Documents

Publication Publication Date Title
KR100948395B1 (en) Cleaning device, method and agent for cleaning conductive member for fabricating organic electro luminescene display device
CN103627400B (en) Molybdenum alloy film and indium oxide film wet etchant component
EP1679361B1 (en) Cleaning agent for substrate and cleaning method
CN102131910B (en) Cleaning composition for removing lead-free solder flux and system for removing lead-free solder flux
CN109563453B (en) Cleaning agent composition for screen printing plate
KR101878496B1 (en) Etching agent compositions for copper-containing materials and methods for etching copper-containing materials
CN1042809C (en) Non-halogen non-rosin type low solid content non-cleaning scaling powder
CN1839355A (en) Stripping and cleaning compositions for microelectronics
EP0426943B1 (en) Agent and method for removing rosinbase solder flux
KR102469931B1 (en) Composition for cleaning a mask, pre-composition for cleaning a mask, and method for manufacturing the same
JP2014055356A (en) Nickel plating solution and method for forming nickel plating layer using the same
CN117431551A (en) Inhibitor-free cleaning agent and method for cleaning conductive member for organic electroluminescent display device using the same
KR102224705B1 (en) The cleaning method of metal mask for organic electroluminescent device and metal mask using the same
JP2007188728A (en) Reproduction method of mask
KR20140091689A (en) Aqueous composition for etching of copper and copper alloys
KR20240012271A (en) Inhibitor-free cleaning agent and method for cleaning conductive members for organic electroluminescent display devices using the same
KR101538939B1 (en) Agent for cleaning conductive member for fabricating organic light emitting diode display device and cleaning method using the same
KR102019962B1 (en) Cleaning solution composition
KR101128865B1 (en) Formulation of cleaner for removing residual flux after reflow and cleaning method by using it
KR20080111268A (en) Cleaning solution composition and cleaning method using the same
KR101758051B1 (en) Stripping composition for color filter
KR101489937B1 (en) Agent for cleaning conductive member for fabricating organic light emitting diode display device and cleaning method using the same
KR20140121196A (en) Etchant composition for copper-containing metal film and etching method using the same
KR101971459B1 (en) Composition for cleaning conductive member for fabricating organic light emitting device and cleaning method using the same
KR100842072B1 (en) Photoresist stripper composition and method of stripping photoresist using the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination