WO2020066979A1 - 有機機能膜付き基板の製造方法 - Google Patents
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- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
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- B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
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- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
- H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
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- H10K59/122—Pixel-defining structures or layers, e.g. banks
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a method for manufacturing a substrate with an organic functional film.
- an organic functional film made of an organic compound is used as a light emitting layer and a charge injection layer.
- the hole injection layer is responsible for transferring charges between the anode and the hole transport layer or the light emitting layer, and plays an important function for achieving low voltage driving and high luminance of the organic EL element.
- the method of forming the hole injection layer is roughly classified into a dry process typified by a vapor deposition method and a wet process typified by a spin coating method. When comparing these processes, the wet process is flatter in a larger area. A highly efficient thin film can be manufactured efficiently.
- a partition (bank) is generally provided so as to surround a region where the layer is formed, and an opening of the partition is provided.
- Organic functional ink is applied in the section.
- pile-up phenomenon occurs, in which the ink applied in the opening creeps up on the side surface of the partition wall, and the thickness of the peripheral portion of the coating film in contact with the side surface of the partition wall becomes thicker than the central portion of the coating film. May be.
- Such a creeping phenomenon causes a situation in which the stacking order of the plurality of organic functional layers formed between the electrodes is not adhered to as designed, and a leak current path is formed. As a result, desired element characteristics cannot be realized.
- the crawled-up organic functional layer such as a hole injection layer may cause uneven light emission of the obtained organic EL device.
- Patent Documents 2 and 3 propose means for suppressing the creeping phenomenon.
- a creeping phenomenon has been proposed.
- Demands on techniques for suppressing phenomena are increasing.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for manufacturing a substrate with an organic functional film having an organic functional film having a uniform thickness, in which a creeping phenomenon is suppressed.
- the present inventors have conducted intensive studies to achieve the above object, and as a result of using a solvent containing triethylene glycol as a solvent for the organic functional ink, when the ink was applied to the inside of the partition wall by inkjet coating, The present inventors have found that a thin film in which ink crawling is extremely suppressed can be produced, and the present invention has been completed.
- the present invention 1.
- the method for producing a substrate with an organic functional film according to 1 or 2 wherein the solvent comprises a glycol solvent having a boiling point lower than that of triethylene glycol, 4.
- a method for suppressing crawling wherein a solvent having a content of triethylene glycol of 3 to 17% by mass is used as the organic functional ink; 9.
- An ink for an inkjet method comprising an organic functional material and a solvent containing triethylene glycol, wherein the content of triethylene glycol in the solvent is 3 to 17% by mass.
- FIG. 4 is an explanatory diagram of a method of calculating a pile-up index in an example.
- solid content relating to the organic functional ink means components other than the solvent contained in the ink.
- the charge transporting property is synonymous with the conductivity, and is synonymous with the hole transporting property.
- the method for producing a substrate with an organic functional film according to the present invention is a method for producing a substrate with an organic functional film having a substrate, a partition defining an opening on the substrate, and an organic functional film in the partition.
- Forming an organic functional film, wherein the content of triethylene glycol in the solvent is 3 to 17% by mass.
- the present invention is characterized in that a solvent having a content of triethylene glycol of 3 to 17% by mass is used as a solvent for an organic functional ink (hereinafter, also referred to as an ink solvent).
- an organic functional ink hereinafter, also referred to as an ink solvent.
- the crawling phenomenon of the ink applied in the partition can be effectively suppressed, and the thickness of the formed thin film becomes more uniform.
- the crawling phenomenon is suppressed, and the organic functional film having a uniform film thickness.
- the content of triethylene glycol is preferably 4 to 16% by mass, more preferably 5 to 15% by mass, from the viewpoint of obtaining a substrate with an organic functional film having good reproducibility.
- the ink solvent used in the present invention is not particularly limited as long as the content of triethylene glycol is 3 to 17% by mass, and the remaining (83 to 97% by mass) solvent component is a conventional organic solvent.
- the solvent can be appropriately selected from solvents used for the ink, but in consideration of further increasing the effect of suppressing crawling, the remaining solvent is triethylene at atmospheric pressure (1.013 ⁇ 10 5 Pa).
- a solvent having a boiling point lower than that of glycol (boiling point: 287 ° C.) is preferable, a solvent having a boiling point lower by 10 ° C. or higher is more preferable, a solvent having a boiling point lower by 20 ° C. or higher is still more preferable, and a solvent having a boiling point lower than 30 ° C. is more preferable.
- the ink solvent used in the present invention preferably contains another glycol solvent having a boiling point lower than that of triethylene glycol.
- other glycol solvents include ethylene glycol (boiling point 197 ° C.), propylene glycol (boiling point 188 ° C.), diethylene glycol (boiling point 244 ° C.), dipropylene glycol (boiling point 232 ° C.), tripropylene glycol (boiling point 232 ° C.).
- the total proportion of the other glycol solvent in the ink solvent may be 97% by mass or less, but the creeping phenomenon is suppressed, and a substrate with an organic functional film having an organic functional film with a uniform thickness can be obtained with good reproducibility. From the viewpoint, it is preferably from 5 to 80% by mass, more preferably from 10 to 70% by mass, still more preferably from 15 to 60% by mass, and still more preferably from 20 to 50% by mass. 100% by mass).
- the ink solvent used in the present invention preferably contains a glycol ether solvent having a boiling point lower than that of triethylene glycol.
- a glycol ether solvent include ethylene glycol monopropyl ether (boiling point 151 ° C.), ethylene glycol monohexyl ether (boiling point 208 ° C.), propylene glycol monobutyl ether (boiling point 170 ° C.), diethylene glycol monoethyl ether (boiling point 170 ° C.).
- dipropylene glycol monobutyl ether (boiling point 229 ° C), ethylene glycol monobutyl ether (boiling point 171 ° C), diethylene glycol monobutyl ether (boiling point 230 ° C), diethylene glycol monoisobutyl ether (boiling point 160 ° C), dipropylene glycol monomethyl ether ( Boiling point 188 ° C), propylene glycol monopropyl ether (boiling point 149 ° C), diethylene glycol monopropyl ether (prop Carbitol), diethylene glycol monohexyl ether (hexyl carbitol), 2-ethylhexyl carbitol (boiling point 272 ° C), dipropylene glycol monopropyl ether (boiling point 210 ° C), tripropylene glycol monomethyl ether (boiling point 243 ° C), diethylene glycol mono
- the total proportion of the glycol ether solvent in the ink solvent may be 97% by mass or less, but the creeping phenomenon is suppressed and a viewpoint of obtaining a substrate with an organic functional film having an organic functional film having a uniform thickness with good reproducibility. Therefore, it is preferably from 20 to 90% by mass, more preferably from 30 to 85% by mass, and still more preferably from 40 to 80% by mass (however, the total of all the solvent types used is 100% by mass).
- the ink solvent used in the present invention may include, in addition to the various solvents described above, other solvents conventionally used as ink solvents for the purpose of adjusting viscosity and surface tension, etc. Solvents having a lower boiling point than ethylene glycol are preferred.
- solvents include sulfur-containing solvents such as dimethylsulfoxide and sulfolane; urea solvents such as tetramethylurea and N, N'-dimethylpropyleneurea; amide solvents such as N-methylpyrrolidone, dimethylformamide and dimethylacetamide A halogenated hydrocarbon solvent such as dichloromethane; an ester solvent such as ethyl acetate, n-propyl acetate, n-butyl acetate, ethyl benzoate, methyl benzoate, diethyl fumarate, butyl benzoate; dimethyl carbonate, ethylene carbonate, carbonic acid Carbonate solvents such as propylene; nitrile solvents such as acetonitrile, 3-methoxypropionitrile, 3-ethoxypropionitrile; acetone, acetonylacetone, methyl ethyl ketone, methyl isobutyl ketone, methyl
- the total proportion in the ink solvent is usually less than 10% by mass, and the crawling phenomenon is suppressed, and a substrate with an organic functional film having an organic functional film with a uniform film thickness can be obtained with good reproducibility. From the viewpoint of obtaining, it is preferably less than 5% by mass (however, the total of all the solvent types used is 100% by mass).
- compositions of the ink solvent used in the present invention include a combination of triethylene glycol, diethylene glycol, and triethylene glycol dimethyl ether, and a combination of triethylene glycol, diethylene glycol, triethylene glycol dimethyl ether, and 2-phenoxyethanol. It is not limited.
- the ink solvent preferably does not contain water as a solvent, from the viewpoint of suppressing the creeping phenomenon and obtaining a substrate with an organic functional film having an organic functional film having a uniform thickness with good reproducibility.
- water preferably contains water as a solvent, from the viewpoint of suppressing the creeping phenomenon and obtaining a substrate with an organic functional film having an organic functional film having a uniform thickness with good reproducibility.
- it does not mean that the existence of a trace amount of water contained in the organic solvent used or water contained in the solid content is not denied.
- the present invention is characterized in that an ink solvent having a triethylene glycol content of 3 to 17% by mass is used. Therefore, an organic functional material, a substrate with a partition to which the organic functional material is applied, an ink jet device, and the like. May be appropriately selected from conventionally known various materials and apparatuses. Any organic functional material may be used as long as it is conventionally used as a functional material for an electronic device, and specific examples thereof include a charge transporting polymer and a charge transporting oligomer having a weight average molecular weight of 5,000 to 30,000.
- a charge transporting oligomer is preferable in consideration of obtaining a film having a uniform thickness with good reproducibility by suppressing precipitation and the like in an ink solvent, and improving charge transportability of the organic functional film.
- the molecular weight of the polymer means a weight average molecular weight
- the weight average molecular weight means a weight average molecular weight in terms of polystyrene by gel permeation chromatography.
- the molecular weight of the charge transporting oligomer is usually from 200 to 5,000, but preferably 300 or more, more preferably 400 or more as a lower limit, and preferably 4,000 or less, more preferably 3,000 or less, as an upper limit. It is even more preferably 2,000 or less.
- a monodispersed charge transporting organic compound may be used alone, or two or more different monodispersed charge transporting organic compounds may be used in combination. From the viewpoint of suppressing reproducibility, the number of monodisperse charge-transporting organic compounds used is preferably one to three.
- the organic functional material used in the present invention is preferably an aniline derivative or a thiophene derivative, and more preferably an aniline derivative, because of its excellent solubility in an organic solvent and excellent charge transportability.
- the aniline derivative include, for example, those disclosed in WO 2005/043962, WO 2013/046232, and the like. More specifically, the following formulas (1) and (2) ) And the like.
- the aniline derivative represented by the formula (1) may be an oxidized aniline derivative having a quinone diimine structure represented by the following formula (quinone diimine derivative) in the molecule.
- Examples of a method for oxidizing an aniline derivative to obtain a quinone diimine derivative include the methods described in WO 2008/010474 and WO 2014/1191982.
- R 1 to R 6 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, or an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 1.
- a alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted by Z 2 Represents an NHY 1 , —NY 2 Y 3 , —OY 4 , or —SY 5 group, wherein Y 1 to Y 5 are each independently an alkyl having 1 to 20 carbon atoms which may be substituted by Z 1;
- Z 1 represents a halogen atom, a nitro group
- Z 2 is a halogen atom, a nitro group, a cyano group
- Z 3 is a halogen atom
- k and l are each independently an integer of 1 to 5.
- R 7 to R 10 are each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, and Z 1 .
- an alkoxy group having 1 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or alkynyl having 2 to 20 carbon atoms group may be substituted with Z 2, an aralkyl group or an acyl group having 1 to 20 carbon atoms, an aryl group or a carbon number of 7 to 20 carbon atoms 6 ⁇ 20, R 11 ⁇ R 14 are each Independently, hydrogen atom, phenyl group, naphthyl group, pyridyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, furanyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, thienyl group (these groups are Halogen atom, nitro group, cyano group, hydroxyl group, thiol group,
- R 15 to R 18 are each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, and Z 1 .
- Z 1 and Z 2 represent the same meaning as described above.
- examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- the alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic.
- alkenyl group having 2 to 20 carbon atoms include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, n- Examples thereof include a 1-pentenyl group, an n-1-decenyl group, and an n-1-eicosenyl group.
- alkynyl group having 2 to 20 carbon atoms include ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl, n-3-butynyl Group, 1-methyl-2-propynyl group, n-1-pentynyl group, n-2-pentynyl group, n-3-pentynyl group, n-4-pentynyl group, 1-methyl-n-butynyl group, 2- Methyl-n-butynyl group, 3-methyl-n-butynyl group, 1,1-dimethyl-n-propynyl group, n-1-hexynyl group, n-1-decynyl group, n-1-pentadecynyl group, n- And a 1-eicosinyl group.
- aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, and 2-phenanthryl.
- aralkyl group having 7 to 20 carbon atoms include a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, a naphthylethyl group and a naphthylpropyl group.
- heteroaryl group having 2 to 20 carbon atoms examples include 2-thienyl group, 3-thienyl group, 2-furanyl group, 3-furanyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-imidazolyl group, Examples thereof include a 4-imidazolyl group, a 2-pyridyl group, a 3-pyridyl group, and a 4-pyridyl group.
- haloalkyl group having 1 to 20 carbon atoms examples include a group in which at least one hydrogen atom of the above alkyl group having 1 to 20 carbon atoms is substituted with a halogen atom. Among them, a fluoroalkyl group is preferable, and a perfluoro group is preferable. Alkyl groups are more preferred.
- Specific examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoropropyl group, a 2,2,3,3,3- Pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group, nonafluorobutyl group, 4,4,4-trifluoro Butyl group, undecafluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 2,2,3,3,4,4,5,5-octafluoro Pentyl group, tridecafluorohexyl group, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl group, 2,2,3,3,4,4,5 , 5,6,6
- alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, c-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy group, n-pentoxy group, n-hexoxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-eicosa Nyloxy group and the like.
- thioalkoxy (alkylthio) group having 1 to 20 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, s-butylthio, t-butylthio, and the like.
- n-pentylthio group n-hexylthio group, n-heptylthio group, n-octylthio group, n-nonylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetra Decylthio, n-pentadecylthio, n-hexadecylthio, n-heptadecylthio, n-octadecylthio, n-nonadecylthio, n-eicosanylthio and the like.
- acyl group having 1 to 20 carbon atoms include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.
- R 1 to R 6 each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by Z 1 , or a carbon atom having 6 to 6 carbon atoms which may be substituted by Z 2.
- 20 aryl groups, —NHY 1 , —NY 2 Y 3 , —OY 4 , or —SY 5 are preferable, and in this case, Y 1 to Y 5 have 1 to 1 carbon atoms which may be substituted by Z 1.
- An alkyl group having 10 or an aryl group having 6 to 10 carbon atoms which may be substituted with Z 2 is preferable, and an alkyl group having 1 to 6 carbon atoms which may be substituted with Z 1 or substituted with Z 2.
- a phenyl group is more preferred, and an alkyl group having 1 to 6 carbon atoms or a phenyl group is even more preferred.
- R 1 to R 6 are more preferably a hydrogen atom, a fluorine atom, a methyl group, a phenyl group or a diphenylamino group (—NY 2 Y 3 in which Y 2 and Y 3 are phenyl groups), and R 1 to R 4 Is a hydrogen atom, and R 5 and R 6 are more preferably a hydrogen atom or a diphenylamino group at the same time.
- Z 1 is preferably a halogen atom or an aryl group having 6 to 10 carbon atoms which may be substituted by Z 3 , and more preferably a fluorine atom or a phenyl group. More preferably, it is not present (that is, it is an unsubstituted group), and Z 2 is preferably a halogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with Z 3 .
- a fluorine atom or an alkyl group having 1 to 6 carbon atoms is more preferable, and the absence of the same (that is, an unsubstituted group) is even more preferable.
- Z 3 is preferably a halogen atom, more preferably a fluorine atom, and even more preferably absent (that is, an unsubstituted group).
- k and l are preferably k + 1 ⁇ 8, and more preferably k + 1 ⁇ 5.
- R 7 to R 10 are preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, Hydrogen atoms are more preferred. Further, in consideration of increasing the solubility of the aniline derivative represented by the formula (2) in the solvent and improving the uniformity of the obtained thin film, it is preferable that both R 11 and R 13 are hydrogen atoms.
- R 11 and R 13 are both hydrogen atoms
- R 12 and R 14 are each independently a phenyl group (this phenyl group is a halogen atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a phosphoric acid group) Group, sulfonic acid group, carboxyl group, alkoxy group having 1 to 20 carbon atoms, thioalkoxy group having 1 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 20 carbon atoms, 2 to 2 carbon atoms (It may be substituted with an alkenyl group having 20, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms.) Or a group represented by the above formula (H4), where
- m is preferably 2 to 4 in consideration of the availability of the compound, ease of production, cost and the like, and more preferably 2 or 3 in consideration of enhancing the solubility in a solvent. Considering the balance among the availability, ease of production, production cost, solubility in a solvent, transparency of the obtained thin film, and the like, 2 is optimal.
- aniline derivative represented by the formulas (1) and (2) a commercially available product or a product produced by a known method such as the method described in each of the above publications may be used. Also in this case, it is preferable to use one purified by recrystallization, vapor deposition, or the like before preparing the organic functional ink. By using a purified product, the characteristics of an electronic device having a thin film obtained from the ink can be further improved. In the case of purification by recrystallization, for example, 1,4-dioxane, tetrahydrofuran or the like can be used as a solvent.
- organic functional material charge transporting substance represented by the formulas (1) and (2)
- one kind of compound selected from the compounds represented by the formulas (1) and (2) ie, The molecular weight distribution may have a degree of dispersion of 1) alone or in combination of two or more compounds.
- DPA represents a diphenylamino group.
- the organic functional ink used in the present invention may contain a dopant substance for the purpose of improving the charge transport ability thereof, in addition to the organic functional materials such as the aniline derivative described above, depending on the use of the obtained functional film.
- the dopant substance is not particularly limited as long as it is soluble in at least one kind of solvent used in the ink, and any of an inorganic dopant substance and an organic dopant substance can be used.
- the inorganic and organic dopant substances may be used alone or in combination of two or more.
- the function as the dopant material is first manifested, for example, when a part of the molecule comes off due to an external stimulus such as heating during baking.
- it may be a substance capable of improving, for example, an arylsulfonic acid ester compound in which a sulfonic acid group is protected by a group which is easily eliminated.
- the molecular weight of an organic dopant such as an arylsulfonic acid compound or an arylsulfonic acid ester compound is not particularly limited, but is preferable in consideration of solubility in an organic solvent when used together with the aniline derivative used in the present invention. Is 4000 or less, more preferably 3000 or less, and even more preferably 2000 or less.
- heteropolyacid is preferable as the inorganic dopant substance.
- Heteropolyacid typically has a structure in which a hetero atom is located at the center of a molecule, represented by a Keggin-type chemical structure represented by the formula (H1) or a Dawson-type chemical structure represented by the formula (H2), It is a polyacid obtained by condensing isopolyacid, which is an oxygen acid such as vanadium (V), molybdenum (Mo), and tungsten (W), with oxygen acid of a different element.
- oxygen acid such as vanadium (V), molybdenum (Mo), and tungsten (W)
- Examples of such different types of oxyacids include oxyacids of silicon (Si), phosphorus (P), and arsenic (As).
- heteropolyacid examples include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, phosphorus tungstomolybdic acid, and the like, and these may be used alone or in combination of two or more. Good. These heteropoly acids are available as commercial products, and can also be synthesized by known methods. In particular, when one kind of heteropolyacid is used, the one kind of heteropolyacid is preferably phosphotungstic acid or phosphomolybdic acid, and phosphotungstic acid is most suitable. When two or more heteropoly acids are used, one of the two or more heteropoly acids is preferably phosphotungstic acid or phosphomolybdic acid, more preferably phosphotungstic acid.
- Heteropolyacids in quantitative analysis such as elemental analysis, are those having a large or small number of elements from the structure represented by the general formula, even those obtained as a commercial product, or known synthetic As long as it is appropriately synthesized according to the method, it can be used in the present invention. That is, for example, phosphotungstic acid is generally represented by the chemical formula H 3 (PW 12 O 40 ) ⁇ nH 2 O, and phosphomolybdic acid is generally represented by the chemical formula H 3 (PMo 12 O 40 ) ⁇ nH 2 O.
- the mass of the heteropolyacid defined in the present invention is not the mass of pure phosphotungstic acid (phosphotungstic acid content) in a synthetic product or a commercial product, but a commercially available product and a known synthetic polytungstic acid. In the form that can be isolated by the method, it means the total mass in the state containing water of hydration and other impurities.
- the amount of the heteropolyacid used can be about 0.001 to 50.0, preferably about 0.01 to 20.0, more preferably about 0.01 to 20.0, by mass, based on the organic functional material 1 such as an aniline derivative. Is about 0.1 to 10.0.
- a tetracyanoquinodimethane derivative or a benzoquinone derivative can be used as the organic dopant substance.
- the tetracyanoquinodimethane derivative include 7,7,8,8-tetracyanoquinodimethane (TCNQ) and halotetracyanoquinodimethane represented by the formula (H3).
- benzoquinone derivative examples include tetrafluoro-1,4-benzoquinone (F4BQ), tetrachloro-1,4-benzoquinone (chloranil), tetrabromo-1,4-benzoquinone, 2,3-dichloro-5, 6-dicyano-1,4-benzoquinone (DDQ) and the like.
- R 500 to R 503 each independently represent a hydrogen atom or a halogen atom, but at least one is a halogen atom, preferably at least two are halogen atoms, and at least three are halogen atoms. More preferably, all are halogen atoms.
- the halogen atom include the same as described above, but a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable.
- halotetracyanoquinodimethane examples include 2-fluoro-7,7,8,8-tetracyanoquinodimethane, 2-chloro-7,7,8,8-tetracyanoquinodimethane 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane, 2,5-dichloro-7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetra Chloro-7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) and the like.
- the use amount of the tetracyanoquinodimethane derivative and the benzoquinone derivative is preferably 0.0001 to 100 equivalents, more preferably 0.01 to 50 equivalents, and still more preferably 1 to 100 equivalents to the organic functional material such as the aniline derivative. 20 equivalents.
- arylsulfonic acid compound examples include benzenesulfonic acid, tosylic acid, p-styrenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, p-dodecylbenzenesulfonic acid, and dihexylbenzene.
- arylsulfonic acid compound examples include an arylsulfonic acid compound represented by the formula (H4) or (H5).
- a 1 represents O or S, and O is preferred.
- a 2 represents a naphthalene ring or an anthracene ring, preferably a naphthalene ring.
- a 3 represents a divalent to tetravalent perfluorobiphenyl group, p represents the number of bonds between A 1 and A 3, and is an integer satisfying 2 ⁇ p ⁇ 4, where A 3 is perfluorobiphenyldiyl Group, preferably a perfluorobiphenyl-4,4'-diyl group, and p is preferably 2.
- q represents the number of sulfonic acid groups bonded to A 2 and is an integer satisfying 1 ⁇ q ⁇ 4, and 2 is most preferable.
- a 4 to A 8 each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 2 to 20 carbon atoms.
- halogenated alkyl group having 1 to 20 carbon atoms examples include trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 3,3,3-trifluoropropyl 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4 , 4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, 1,1,2,2,3,3,4,4,4-nonafluorobutyl and the like.
- halogenated alkenyl group having 2 to 20 carbon atoms examples include perfluorovinyl, perfluoropropenyl (perfluoroallyl), perfluorobutenyl group and the like.
- examples of the halogen atom and the alkyl group having 1 to 20 carbon atoms include the same as described above, and the halogen atom is preferably a fluorine atom.
- a 4 to A 8 represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkenyl halide having 2 to 10 carbon atoms.
- at least three of A 4 to A 8 are preferably a fluorine atom, and are preferably a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms.
- an alkyl fluoride group or an alkenyl fluoride group having 2 to 5 carbon atoms and at least three of A 4 to A 8 are fluorine atoms, and a hydrogen atom, a fluorine atom, a cyano group, More preferably, it is a perfluoroalkyl group having 1 to 5 carbon atoms or a perfluoroalkenyl group having 1 to 5 carbon atoms, and A 4 , A 5 and A 8 are fluorine atoms.
- a perfluoroalkyl group is a group in which all of the hydrogen atoms of an alkyl group are substituted with fluorine atoms
- a perfluoroalkenyl group is a group in which all of the hydrogen atoms of an alkenyl group are substituted with fluorine atoms.
- R represents the number of sulfonic acid groups bonded to the naphthalene ring and is an integer satisfying 1 ⁇ r ⁇ 4, preferably 2 to 4, and most preferably 2.
- the amount of the arylsulfonic acid compound to be used is preferably about 0.01 to 20.0, more preferably 0.4 to 5.0 in terms of the amount (mol) of the organic functional material 1 such as an aniline derivative. It is about.
- the arylsulfonic acid compound may be a commercially available product, but can also be synthesized by a known method described in International Publication No. WO 2006/025342, International Publication No. 2009/096352, and the like.
- examples of the aryl sulfonic acid ester compound include an aryl sulfonic acid ester compound disclosed in International Publication No. 2017/217455, an aryl sulfonic acid ester compound disclosed in International Publication No. 2017/217457, and Japanese Patent Application No. 2017-243631.
- the above-mentioned arylsulfonic acid ester compounds and the like are mentioned, and specifically, those represented by any of the following formulas (H6) to (H8) are preferable.
- n is an integer that satisfies 1 ⁇ n ⁇ 4, but is preferably 2.
- a 11 is an m-valent group derived from perfluorobiphenyl.
- a 12 is —O— or —S—, preferably —O—.
- a 13 is a (n + 1) -valent group derived from naphthalene or anthracene, preferably a group derived from naphthalene.
- R s1 to R s4 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R s5 is an optionally substituted 2 to 20 carbon atoms. Is a monovalent hydrocarbon group.
- linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl and the like. And an alkyl group having 1 to 3 carbon atoms is preferred.
- the monovalent hydrocarbon group having 2 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl.
- Alkyl groups such as groups; and aryl groups such as phenyl, naphthyl and phenanthryl groups.
- R s1 to R s4 is a straight-chain alkyl group having 1 to 3 carbon atoms, and the remainder is a hydrogen atom, or R s1 is a straight-chain alkyl group having 1 to 3 carbon atoms. And it is preferred that R s2 to R s4 are hydrogen atoms. In this case, the straight-chain alkyl group having 1 to 3 carbon atoms is preferably a methyl group.
- R s5 is preferably a straight-chain alkyl group having 2 to 4 carbon atoms or a phenyl group.
- a 14 is an optionally substituted m-valent hydrocarbon group having 6 to 20 carbon atoms and containing one or more aromatic rings, wherein the hydrocarbon group is one or more of A group obtained by removing m hydrogen atoms from a hydrocarbon compound having 6 to 20 carbon atoms including an aromatic ring.
- a hydrocarbon compound having 6 to 20 carbon atoms including an aromatic ring.
- examples of such a hydrocarbon compound include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, and phenanthrene.
- part or all of the hydrogen atoms may be further substituted with a substituent.
- Examples of such a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a nitro atom.
- a 14 is preferably a group derived from benzene, biphenyl and the like.
- a 15 is —O— or —S—, preferably —O—.
- a 16 is an (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the aromatic hydrocarbon group is located on the (n + 1) -valent aromatic ring of the aromatic hydrocarbon compound having 6 to 20 carbon atoms. This is a group obtained by removing two hydrogen atoms. Examples of such aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, and pyrene. Among them, A 16 is preferably a group derived from naphthalene or anthracene, and more preferably a group derived from naphthalene.
- R s6 and R s7 are each independently a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group, and R s8 is a linear or branched monovalent aliphatic hydrocarbon group. It is a hydrocarbon group. However, the total number of carbon atoms of R s6 , R s7 and R s8 is 6 or more. The upper limit of the total number of carbon atoms of R s6 , R s7 and R s8 is not particularly limited, but is preferably 20 or less, more preferably 10 or less.
- linear or branched monovalent aliphatic hydrocarbon group examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, n-octyl, Alkyl groups having 1 to 20 carbon atoms such as 2-ethylhexyl and decyl groups; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, Examples thereof include an alkenyl group having 2 to 20 carbon atoms such as a hexenyl group.
- R s6 is preferably a hydrogen atom
- R s7 and R s8 are each independently preferably an alkyl group having 1 to 6 carbon atoms.
- R s9 to R s13 each independently represent a hydrogen atom, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, Or a halogenated alkenyl group having 2 to 10 carbon atoms.
- the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, Examples include t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups.
- the halogenated alkyl group having 1 to 10 carbon atoms is not particularly limited as long as part or all of the hydrogen atoms of the alkyl group having 1 to 10 carbon atoms are substituted with halogen atoms.
- Specific examples include trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3 , 3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, , 2,3,3,4,4,4-heptafluorobutyl, 1,1,2,2,3,3,4,4,4-nonafluorobutyl and the like.
- the halogenated alkenyl group having 2 to 10 carbon atoms is not particularly limited as long as part or all of the hydrogen atoms of the alkenyl group having 2 to 10 carbon atoms are substituted with halogen atoms.
- Specific examples include perfluorovinyl, perfluoro-1-propenyl, perfluoro-2-propenyl, perfluoro-1-butenyl, perfluoro-2-butenyl, and perfluoro-3-butenyl groups.
- R s9 a nitro group, a cyano group, a halogenated alkyl group having 1 to 10 carbon atoms and an alkenyl halide group having 2 to 10 carbon atoms are preferable, and a nitro group, a cyano group, and a carbon atom having 1 to 4 carbon atoms are preferable.
- a nitro group, a cyano group, a trifluoromethyl group and a perfluoropropenyl group are more preferable.
- R s10 to R s13 a halogen atom is preferable, and a fluorine atom is more preferable.
- a 17 is —O—, —S— or —NH—, preferably —O—.
- a 18 is an (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the aromatic hydrocarbon group is located on the (n + 1) -valent aromatic ring of the aromatic hydrocarbon compound having 6 to 20 carbon atoms. This is a group obtained by removing two hydrogen atoms. Examples of such aromatic hydrocarbon compounds include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, and pyrene. Among these, A 18 is preferably a group derived from naphthalene or anthracene, and more preferably a group derived from naphthalene.
- R s14 to R s17 are each independently a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms.
- the monovalent aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n
- An alkyl group having 1 to 20 carbon atoms such as heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl group; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl
- Examples thereof include an alkenyl group having 2 to 20 carbon atoms such as -2-prop
- An alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 20 carbon atoms is preferable.
- An alkyl group having 10 is more preferred, and an alkyl group having 1 to 8 carbon atoms is even more preferred.
- R s18 is a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or OR s19 .
- R s19 is an optionally substituted monovalent hydrocarbon group having 2 to 20 carbon atoms. Examples of the linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms for R s18 include the same as described above.
- R s18 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. Even more preferred.
- Examples of the monovalent hydrocarbon group having 2 to 20 carbon atoms for R s19 include the above-mentioned monovalent aliphatic hydrocarbon groups other than the methyl group, and aryl groups such as phenyl, naphthyl, and phenanthryl groups. Among them, R s19 is preferably a linear alkyl group having 2 to 4 carbon atoms or a phenyl group.
- Examples of the substituent which the monovalent hydrocarbon group may have include a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group and a cyano group.
- Suitable arylsulfonic acid ester compounds include, but are not limited to, the following.
- the amount of the arylsulfonic acid ester compound to be used is preferably about 0.01 to 20.0, more preferably about 0.05 to 15 with respect to the organic functional material 1 such as an aniline derivative in terms of the amount of the substance (molar). It is.
- an arylsulfonic acid compound in consideration of effectively suppressing the creeping phenomenon when the organic functional ink is applied to the inside of the partition wall formed on the substrate by the ink jet method, an arylsulfonic acid compound, an arylsulfone It is preferable to use at least one kind of acid ester compound, and it is more preferable to use an arylsulfonic acid compound.
- the solid content concentration of the organic functional ink used in the present invention is usually about 0.1 to 20.0% by mass, and preferably 0.5 to 10% in consideration of improving the applicability of the ink. It is about 0% by mass, more preferably about 1.0 to 5.0% by mass.
- the solid content concentration is appropriately set in consideration of the thickness of the functional film to be formed and the like.
- the viscosity of the organic functional ink cannot be unequivocally defined because it varies depending on the amount of droplets dropped by the ink jet method, but it is usually 15 mPa ⁇ s or less at 25 ° C., preferably 10 mPa ⁇ s or less.
- the surface tension of the organic functional ink is usually 20 to 50 mN / m at 25 ° C., preferably 25 to 45 mN / m, more preferably 37 to 42 mN / m.
- the viscosity is a value measured by a TVE-25 viscometer manufactured by Toki Sangyo Co., Ltd.
- the surface tension is a value measured by an automatic surface tensiometer CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.
- the viscosity and surface tension of the organic functional ink can be adjusted by changing the type of the above-mentioned ink solvent, the ratio thereof, the solid content concentration, and the like in consideration of various factors such as a desired film thickness.
- the method for preparing the organic functional ink is not particularly limited, and for example, a method in which an organic functional material such as the above-described aniline derivative is dissolved in an ink solvent (mixed solvent) containing triethylene glycol. And a method of dissolving an organic functional material in triethylene glycol and then mixing other solvents.
- a dopant is used, the order of addition is arbitrary.
- the organic functional ink from the viewpoint of obtaining a thinner film with higher flatness with good reproducibility, after dissolving the organic functional material, the dopant substance, etc. in the organic solvent, using a filter of the order of sub-micrometer, etc. It is desirable to filter by filtration.
- the substrate with a partition to which the above-mentioned organic functional ink is applied is not particularly limited as long as it is a substrate on which a predetermined pattern is formed by a known photoresist method or the like.
- a plurality of openings defined by the partition walls exist on the substrate.
- the size of the opening is 100 to 210 ⁇ m on the long side and 40 ⁇ m ⁇ 100 ⁇ m on the short side, and the bank taper angle is 20 to 80 °.
- the material of the substrate is not particularly limited, but in the present invention, a transparent electrode material represented by indium tin oxide (ITO) and indium zinc oxide (IZO) used as an anode material of an electronic device;
- ITO indium tin oxide
- IZO indium zinc oxide
- Metal anode materials composed of metals such as aluminum, gold, silver, copper, indium, or alloys thereof; polymer anode materials such as polythiophene derivatives and polyaniline derivatives having high charge transporting properties; Those subjected to a flattening treatment are preferable.
- the above-described organic functional ink is applied to the partition walls of the partition wall-equipped substrate by an inkjet method using a known inkjet apparatus, and then the pressure is reduced, and further, if necessary, the solvent is removed from the organic functional ink applied to the partition walls.
- an electronic element such as an organic EL element can be manufactured.
- the heating / firing atmosphere during and after the inkjet application is not particularly limited, and may be any of an air atmosphere, an inert gas atmosphere such as nitrogen, and a reduced pressure, and may be any of those under an organic functional material such as an aniline derivative.
- a functional film having good characteristics may be obtained with good reproducibility by heating and baking in an air atmosphere.
- the degree of pressure reduction (degree of vacuum) at the time of pressure reduction is not particularly limited as long as the ink solvent evaporates, but in the present invention, it is usually 1,000 Pa or less, preferably 100 Pa or less, more preferably 50 Pa or less, and even more preferably 25 Pa or less. And more preferably 10 Pa or less.
- the decompression time is not particularly limited as long as the solvent evaporates, but is usually about 0.1 to 60 minutes, preferably about 1 to 30 minutes.
- the temperature is appropriately set within a range of about 100 to 260 ° C. in consideration of the use of the obtained functional film, the type of solvent, the boiling point, and the like.
- the temperature is preferably about 140 to 250 ° C., and preferably 145 to 250 ° C., from the viewpoint of enhancing the charge transport property of the functional film. About 240 ° C. is more preferable.
- two or more steps of temperature change may be applied for the purpose of developing a higher uniform film forming property or promoting the reaction on the substrate. Heating may be performed using an appropriate device such as a hot plate or an oven.
- the thickness of the organic functional film produced in the present invention is not particularly limited, but is preferably 5 to 300 nm when used as a hole injection layer, a hole transport layer or a hole injection transport layer of an organic EL device.
- a method of changing the film thickness there are a method of changing a solid concentration in the organic functional ink, a method of changing a solution amount on a substrate at the time of application, and the like.
- the electronic device produced by the present invention is obtained by applying an organic functional ink containing an organic functional material and a solvent containing 3 to 17% by mass of triethylene glycol to the inside of the partition wall of the substrate with the partition wall by the inkjet method.
- a substrate with an organic functional film produced by removing the solvent by reducing the pressure and as a specific example, has a pair of electrodes, a partition of a predetermined pattern on the surface of at least one of the electrodes. Are formed, and a substrate provided with an organic functional film formed by applying the above-mentioned organic functional ink by an ink-jet method or the like and various functional films formed thereon is provided inside the partition.
- the electrode on which the partition walls are formed is an anode
- the organic functional film is a hole injection layer or a hole injection transport layer formed on the anode.
- Organic EL devices having the configurations (a) to (f) are suitable, but are not limited thereto.
- the organic functional film produced from the organic functional ink containing the aniline derivative described above can be used as a hole injection layer, a hole transport layer, and a hole injection transport layer in an organic EL device. Since it is applied to the inside of the formed partition wall by an inkjet method, it is used as a hole injection layer or a hole injection transport layer, and is particularly preferably used as a hole injection layer.
- A anode / hole injection layer / hole transport layer / emission layer / electron transport layer / electron injection layer / cathode
- b anode / hole injection layer / hole transport layer / emission layer / electron injection transport layer / Cathode
- c anode / hole injection / transport layer / emission layer / electron transport layer / electron injection layer / cathode
- d anode / hole injection / transport layer / emission layer / electron injection / transport layer / cathode
- e anode / positive Hole injection layer / hole transport layer / emission layer / cathode
- f anode / hole injection / transport layer / emission layer / cathode
- an electron block layer or the like may be provided between the light emitting layer and the anode, and a hole (hole) block layer or the like may be provided between the light emitting layer and the cathode, if necessary.
- the hole injection layer, the hole transport layer, or the hole injection / transport layer may also have a function as an electron blocking layer or the like, and the electron injection layer, the electron transport layer, or the electron injection / transport layer may be a hole (hole). It may have a function as a block layer or the like.
- an arbitrary functional layer can be provided between the respective layers as required, other than between the anode and the hole injection layer or the hole injection transport layer.
- Hole injection layer “hole transport layer” and “hole injection transport layer” are layers formed between the light emitting layer and the anode, and transport holes from the anode to the light emitting layer. It has a function, when only one layer of a hole transporting material is provided between the light emitting layer and the anode, it is a “hole injection transport layer”, and between the light emitting layer and the anode, When two or more layers of the hole transporting material are provided, a layer close to the anode is a “hole injection layer”, and the other layers are a “hole transport layer”.
- the hole injection (transport) layer a thin film that is excellent not only in the ability to receive holes from the anode but also in the ability to inject holes into the hole transport (emission) layer is used.
- Electrode injection layer is layers formed between the light emitting layer and the cathode and have a function of transporting electrons from the cathode to the light emitting layer.
- an electron injecting and transporting layer When only one layer of an electron transporting material is provided between the light emitting layer and the cathode, it is an “electron injecting and transporting layer”, and the layer of the electron transporting material is provided between the light emitting layer and the cathode.
- the “electron injection layer” is an organic layer having a light-emitting function, and includes a host material and a dopant material when a doping system is employed.
- the host material mainly has a function of promoting recombination of electrons and holes and confining excitons in the light-emitting layer, and the dopant material efficiently emits excitons obtained by the recombination.
- a host material has a function of mainly confining excitons generated by a dopant in a light-emitting layer.
- An example of a method for manufacturing an OLED element having a hole injection layer composed of a thin film obtained from the organic functional ink is as follows.
- the electrode is preferably subjected to cleaning with alcohol, pure water, or the like, or surface treatment such as UV ozone treatment or oxygen-plasma treatment in advance within a range that does not adversely affect the electrode.
- a hole injection layer is formed on the anode substrate on which partition walls of a predetermined pattern have been formed in advance by using the above-mentioned organic functional ink by the above method. This is introduced into a vacuum evaporation apparatus, and a hole transport layer, a light emitting layer, an electron transport layer / hole block layer, an electron injection layer, and a cathode metal are sequentially deposited.
- a hole transporting layer forming composition including a hole transporting polymer and a light emitting layer forming composition including a light emitting polymer are included. These layers are formed using a wet process. Note that, if necessary, an electron block layer may be provided between the light emitting layer and the hole transport layer.
- anode material examples include a transparent electrode represented by indium tin oxide (ITO) and indium zinc oxide (IZO), and a metal anode composed of a metal represented by aluminum, an alloy thereof, and the like. Those subjected to a flattening treatment are preferable. A polythiophene derivative or a polyaniline derivative having a high charge transporting property can also be used.
- the other metal constituting the metal anode includes, but is not limited to, gold, silver, copper, indium and alloys thereof.
- Materials for forming the hole transport layer include (triphenylamine) dimer derivatives, [(triphenylamine) dimer] spiro dimer, N, N′-bis (naphthalen-1-yl) -N, N′-bis (Phenyl) -benzidine ( ⁇ -NPD), 4,4 ′, 4 ′′ -tris [3-methylphenyl (phenyl) amino] triphenylamine (m-MTDATA), 4,4 ′, 4 ′′ -tris [1 -Naphthyl (phenyl) amino] triphenylamine (1-TNATA) and the like, and 5,5 ′′ -bis- ⁇ 4- [bis (4-methylphenyl) amino] phenyl ⁇ -2,2 ′: Oligothiophenes such as 5 ′, 2 ′′ -terthiophene (BMA-3T) are exemplified.
- Materials for forming the light emitting layer include metal complexes such as 8-hydroxyquinoline aluminum complexes, metal complexes of 10-hydroxybenzo [h] quinoline, bisstyrylbenzene derivatives, bisstyrylarylene derivatives, (2-hydroxyphenyl) benzo.
- Low molecular light emitting materials such as thiazole metal complexes and silole derivatives; poly (p-phenylenevinylene), poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene], poly (3-alkyl A system in which a light emitting material and an electron transfer material are mixed with a polymer compound such as thiophene) and polyvinyl carbazole.
- the light emitting layer When the light emitting layer is formed by vapor deposition, the light emitting layer may be co-deposited with a light emitting dopant.
- a light emitting dopant a metal complex such as tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3 ) may be used.
- naphthacene derivatives such as rubrene, quinacridone derivatives, and condensed polycyclic aromatic rings such as perylene.
- Materials for forming the electron transport layer / hole block layer include oxydiazole derivatives, triazole derivatives, phenanthroline derivatives, phenylquinoxaline derivatives, benzimidazole derivatives, and pyrimidine derivatives.
- Materials for forming the electron injection layer include metal oxides such as lithium oxide (Li 2 O), magnesium oxide (MgO), and alumina (Al 2 O 3 ), lithium fluoride (LiF), and sodium fluoride (NaF). And the like.
- the cathode material include aluminum, magnesium-silver alloy, aluminum-lithium alloy and the like.
- tris (phenylpyrazole) iridium or the like can be given.
- the luminescent polymer examples include polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylenevinylene) (MEH- Polyphenylene vinylene derivatives such as PPV); polythiophene derivatives such as poly (3-alkylthiophene) (PAT); and polyvinyl carbazole (PVCz).
- polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylenevinylene) (MEH- Polyphenylene vinylene derivatives such as PPV)
- polythiophene derivatives such as poly (3-alkylthiophene) (PAT); and polyvinyl carbazole (PVCz).
- the materials constituting the anode and the cathode and the layers formed between them differ depending on whether a device having a bottom emission structure or a top emission structure is manufactured. Therefore, a material is appropriately selected in consideration of this point.
- a transparent anode is used on the substrate side, and light is extracted from the substrate side
- a reflective anode made of metal is used, and in a direction opposite to the substrate. Since light is extracted from a certain transparent electrode (cathode) side, for example, as for the anode material, a transparent anode such as ITO is used when manufacturing a device having a bottom emission structure, and an aluminum is used when manufacturing a device having a top emission structure. / Nd and the like are used, respectively.
- the organic EL device of the present invention may be sealed together with a water catching agent, if necessary, according to a standard method, in order to prevent deterioration in characteristics.
- the pile-up index which will be described later, is usually 60% or more, preferably 63% or more, more preferably 66% or more, still more preferably 69% or more, and more preferably 72% or more. Up can be suppressed.
- the method for manufacturing a substrate with an organic functional film and an electronic element of the present invention is suitably used for manufacturing an electronic element in which a hole injection layer or a hole injection transport layer is formed by an inkjet method as described above.
- Photoelectric conversion element, organic thin-film solar cell, organic perovskite photoelectric conversion element, organic integrated circuit, organic field-effect transistor, organic thin-film transistor, organic light-emitting transistor, organic optical inspection device, organic photoreceptor, organic electric field quenching element, light-emitting electrochemical cell It can also be used when forming a charge transporting thin film by an inkjet method at the time of manufacturing electronic devices such as quantum dot light emitting diodes, quantum lasers, organic laser diodes, and organic plasmon light emitting devices.
- MMA methyl methacrylate
- HEMA 2-hydroxyethyl methacrylate
- HPMA 4-hydroxyphenyl methacrylate
- HPMA-QD condensation reaction of 1 mol of 4-hydroxyphenyl methacrylate with 1.1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride
- CHMI N-cyclohexylmaleimide
- PFHMA 2- (perfluorohexyl) ethyl methacrylate
- MAA AIBN methacrylate: ⁇ , ⁇ ′-azobisisobutyronitrile
- QD1 ⁇ , ⁇ , ⁇ ′-tris
- Compound GT-401 synthesized by a condensation reaction of 1 mol of 4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene and 1.5 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride:
- the thin film was immersed in a 1.0 mass% TMAH aqueous solution for 120 seconds to perform development, and then the thin film was washed with running water using ultrapure water for 20 seconds.
- the thin film on which the rectangular pattern was formed was subjected to post-baking (heating at a temperature of 230 ° C. for 30 minutes) to be cured, whereby a substrate with partition walls was produced.
- TEG / TEGDME / DEG-2-PE 10/45/25/20 (mass ratio)
- An organic functional ink was obtained in the same manner as in Comparative Preparation Example 1-3, except that the amount of TEG used was 2 g and the amount of TEGDME was 9 g.
- Comparative Example 1-1 Comparative Example 1-1, except that the organic functional ink prepared in Comparative Preparation Example 1-2 was used instead of the organic functional ink prepared in Comparative Preparation Example 1-1.
- An organic functional film was formed in the same manner as in Example 1 to obtain a substrate with an organic functional film. Discharge was performed such that the film thickness near the center of the opening of the organic functional film was 80 nm.
- Examples 1-4 to 1-6, Comparative Examples 1-3 to 1-4 An organic functional film was formed in the same manner as in Comparative Example 1-1, except that the organic functional inks prepared in Preparation Examples 1-4 to 1-6 and Comparative Preparation Examples 1-3 to 1-4 were used, respectively. A substrate with an organic functional film was obtained. The organic functional film obtained was discharged so that the film thickness near the center of the opening was 60 nm.
- the pile-up index was determined for the organic functional films formed in the above Examples and Comparative Examples. Table 1 shows the results. As shown in FIG. 1, the pile-up index is obtained when the width of the partition (bank) is A ⁇ m and the range of the film thickness of + 10% from the thickness at the center of the partition (bank) is B ( ⁇ m). It was determined as B / A ⁇ 100 (%).
- the pile-up index was all 70% for the organic functional film formed in the partition by inkjet coating using an organic functional ink containing an ink solvent having a TEG content of 3 to 17% by mass. It can be seen that the creeping-up phenomenon of the organic functional ink can be effectively suppressed.
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Abstract
Description
正孔注入層の形成方法は、蒸着法に代表されるドライプロセスと、スピンコート法に代表されるウェットプロセスとに大別され、これら各プロセスを比べると、ウェットプロセスの方が大面積に平坦性の高い薄膜を効率的に製造できる。それゆえ、有機ELディスプレイの大面積化が進められている現在、ウェットプロセスで形成可能な正孔注入層が望まれており、ウェットプロセスで成膜可能な正孔注入層に関する技術の報告がなされている(例えば特許文献1参照)。
この際、開口部内に塗布されたインクが隔壁の側面を這い上がり、隔壁の側面と接触する塗膜周縁部の厚みが塗膜中央部よりも厚くなる、いわゆる這い上がり(パイルアップ)現象が発生することがある。
このような這い上がり現象は、電極間に形成された複数の有機機能層の積層順が設計通りに順守されず、リーク電流路が形成されるという事態を引き起こす。その結果、所望の素子特性が実現できないこととなる。また、這い上がった正孔注入層等の有機機能層は、得られる有機EL素子の発光ムラを引き起こし得る。
1. 基板と、この基板上に開口部を規定する隔壁と、この隔壁内に有機機能膜とを有する有機機能膜付き基板の製造方法であって、有機機能材料と、トリエチレングリコールを含む溶媒とを含む有機機能インクを前記隔壁内にインクジェット法で塗布する工程と、減圧することで、前記隔壁内に塗布された有機機能インクから溶媒を除去して有機機能膜を形成する工程と、
を備え、前記溶媒中のトリエチレングリコールの含有量が、3~17質量%であることを特徴とする有機機能膜付き基板の製造方法、
2. 前記減圧することにより溶媒成分を除去した後、加熱する工程を備える1の有機機能膜付き基板の製造方法、
3. 前記溶媒が、トリエチレングリコールよりも沸点の低いグリコール溶媒を含む1または2の有機機能膜付き基板の製造方法、
4. 前記溶媒が、トリエチレングリコールよりも沸点の低いグリコールエーテル溶媒を含む1~3のいずれかの有機機能膜付き基板の製造方法、
5. 前記溶媒が、トリエチレングリコール、ジエチレングリコールおよびトリエチレングリコールジメチルエーテルを含む1~4のいずれかの有機機能膜付き基板の製造方法、
6. 前記有機機能材料が、アニリン誘導体である1~5のいずれかの有機機能膜付き基板の製造方法、
7. 1~6の製造方法によって得られた有機機能膜付き基板の上に、さらに有機機能層を作製する工程を含む電子素子の製造方法、
8. 基板と、この基板上に開口部を規定する隔壁と、この隔壁内に有機機能膜とを有する有機機能膜付き基板を製造するにあたって、
有機機能材料と、溶媒とを含む有機機能インクを前記隔壁内にインクジェット法で塗布する際に前記有機機能インクが前記隔壁内を這い上がる現象を抑制する這い上がり抑制方法であって、
前記有機機能インクとして、トリエチレングリコールの含有量が3~17質量%である溶媒を用いることを特徴とする這い上がり抑制方法、
9. 基板と、この基板上に開口部を規定する隔壁と、この隔壁内に有機機能膜とを有する有機機能膜付き基板を製造する際に、前記隔壁内にインクジェット法で塗布されるインクジェット法用インクであって、
有機機能材料と、トリエチレングリコールを含む溶媒とを含み、この溶媒中のトリエチレングリコールの含有量が、3~17質量%であることを特徴とするインクジェット法用インク
を提供する。
本発明に係る有機機能膜付き基板の製造方法は、基板と、この基板上に開口部を規定する隔壁と、この隔壁内に有機機能膜とを有する有機機能膜付き基板の製造方法であって、有機機能材料と、トリエチレングリコールを含む溶媒とを含む有機機能インクを隔壁内にインクジェット法で塗布する工程と、減圧することで、隔壁内に塗布された有機機能インクから溶媒を除去して有機機能膜を形成する工程と、を備え、溶媒中のトリエチレングリコールの含有量が、3~17質量%であることを特徴とする。
このようなその他のグリコール溶媒の具体例としては、エチレングリコール(沸点197℃)、プロピレングリコール(沸点188℃)、ジエチレングリコール(沸点244℃)、ジプロピレングリコール(沸点232℃)、トリプロピレングリコール(沸点273℃)、ヘキシレングリコール(沸点197℃)、1,2-ブタンジオール(沸点193℃)、2,3-ブタンジオール(沸点182℃)、1,3-ブタンジオール(沸点207℃)、1,4-ブタンジオール(沸点228℃)、1,5-ペンタンジオール(沸点239℃)等が挙げられ、これらはそれぞれ単独で用いても、2種以上組み合わせて用いてもよい。
インク溶媒中におけるその他のグリコール溶媒の総割合は、97質量%以下であればよいが、這い上がり現象が抑制され、均一な膜厚の有機機能膜を有する有機機能膜付き基板を再現性よく得る観点から、5~80質量%が好ましく、10~70質量%がより好ましく、15~60質量%がより一層好ましく、20~50質量%がさらに好ましい(ただし、使用する全ての溶媒種の合計は100質量%である)。
このようなグリコールエーテル溶媒の具体例としては、エチレングリコールモノプロピルエーテル(沸点151℃)、エチレングリコールモノヘキシルエーテル(沸点208℃)、プロピレングリコールモノブチルエーテル(沸点170℃)、ジエチレングリコールモノエチルエーテル(沸点196℃)、ジプロピレングリコールモノブチルエーテル(沸点229℃)、エチレングリコールモノブチルエーテル(沸点171℃)、ジエチレングリコールモノブチルエーテル(沸点230℃)、ジエチレングリコールモノイソブチルエーテル(沸点160℃)、ジプロピレングリコールモノメチルエーテル(沸点188℃)、プロピレングリコールモノプロピルエーテル(沸点149℃)、ジエチレングリコールモノプロピルエーテル(プロピルカルビトール)、ジエチレングリコールモノヘキシルエーテル(ヘキシルカルビトール)、2-エチルヘキシルカルビトール(沸点272℃)、ジプロピレングリコールモノプロピルエーテル(沸点210℃)、トリプロピレングリコールモノメチルエーテル(沸点243℃)、ジエチレングリコールモノメチルエーテル(沸点193℃)、トリプロピレングリコールモノブチルエーテル(沸点274℃)、2-フェノキシエタノール(沸点245℃)等のグリコールモノエーテル溶媒;エチレングリコールジメチルエーテル(沸点84℃)、エチレングリコールジエチルエーテル(沸点121℃)、エチレングリコールジブチルエーテル(沸点202℃)、ジエチレングリコールジメチルエーテル(沸点162℃)、ジエチレングリコールジエチルエーテル(沸点188℃)、プロピレングリコールジメチルエーテル(沸点97℃)、プロピレングリコールジエチルエーテル(沸点124℃)、プロピレングリコールジブチルエーテル、ジプロピレングリコールメチル-n-プロピルエーテル(沸点203℃)、ジプロピレングリコールジメチルエーテル(沸点175℃)、ジプロピレングリコールジエチルエーテル(沸点221℃)、ジプロピレングリコールジブチルエーテル(沸点296℃)、トリエチレングリコールジメチルエーテル(沸点216℃)、トリエチレングリコールブチルメチルエーテル(沸点261℃)、テトラエチレングリコールジメチルエーテル(沸点276℃)等のグリコールジエーテル溶媒などが挙げられ、これらはそれぞれ単独で用いても、2種以上組み合わせて用いてもよい。
インク溶媒中におけるグリコールエーテル溶媒の総割合は、97質量%以下であればよいが、這い上がり現象が抑制され、均一な膜厚の有機機能膜を有する有機機能膜付き基板を再現性よく得る観点から、20~90質量%が好ましく、30~85質量%がより好ましく、40~80質量%がより一層好ましい(ただし、使用する全ての溶媒種の合計は100質量%である)。
また、トリエチレングリコールおよびその他のグリコール溶媒とグリコールエーテル溶媒との比は、好ましくは、トリエチレングリコールおよびその他のグリコール溶媒の合計質量:グリコールエーテル溶媒の質量=1:1.1~2.5、より好ましくは1:1.2~2.4である。
さらに、トリエチレングリコールとその他のグリコール溶媒との比は、好ましくは、トリエチレングリコール:その他のグリコール溶媒=1:1.3~10.0、より好ましくは1:1.3~8.0である。
その他の溶媒の具体例としては、ジメチルスルホキシド、スルホラン等の含硫黄溶媒;テトラメチルウレア、N,N’-ジメチルプロピレンウレア等のウレア溶媒;N-メチルピロリドン、ジメチルホルムアミド、ジメチルアセトアミド等のアミド溶媒;ジクロロメタン等のハロゲン化炭化水素溶媒;酢酸エチル、酢酸n-プロピル、酢酸n-ブチル、安息香酸エチル、安息香酸メチル、フマル酸ジエチル、安息香酸ブチル等のエステル溶媒;炭酸ジメチル、炭酸エチレン、炭酸プロピレン等のカーボネート溶媒;アセトニトリル、3-メトキシプロピオニトリル、3-エトキシプロピオニトリル等のニトリル溶媒;アセトン、アセトニルアセトン、メチルエチルケトン、メチルイソブチルケトン、メチルイソブテニルケトン、2-ヘキサノン、2-ペンタノン、アセトフェノン、エチルフェニルケトン、シクロヘキサノン、シクロペンタノン等のケトン溶媒;メタノール、エタノール、トリフルオロエタノール、n-プロパノール、イソプロパノール、n-ブタノール、t-ブタノール、ベンジルアルコール、2-(ベンジルオキシ)エタノール等のアルコール溶媒;テトラヒドロフラン、テトラヒドロピラン、ジオキサン、メチルアニソール、ジメチルアニソール、エチルアニソール、ブチルフェニルエーテル、ブチルアニソール、ペンチルアニソール、ヘキシルアニソール、ヘプチルアニソール、オクチルアニソール、フェノキシトルエン等のエーテル溶媒;トルエン、キシレン、ペンチルベンゼン、ヘキシルベンゼン、ヘプチルベンゼン、オクチルベンゼン、ノニルベンゼン、シクロヘキシルベンゼン、テトラリン等の芳香族炭化水素溶媒などが挙げられ、これらはそれぞれ単独で用いても、2種以上組み合わせて用いてもよい。
その他の溶媒を用いる場合、インク溶媒中におけるその総割合は、通常10質量%未満であり、這い上がり現象が抑制され、均一な膜厚の有機機能膜を有する有機機能膜付き基板を再現性よく得る観点から、好ましく5質量%未満である(ただし、使用する全ての溶媒種の合計は100質量%である)。
有機機能材料としては、従来、電子素子の機能材料として用いられるものであればよく、その具体例として重量平均分子量が5,000~30,000の電荷輸送性ポリマーや電荷輸送性オリゴマーが挙げられるが、インク溶媒中での析出等を抑制して均一な膜厚の膜を再現性よく得ること、有機機能膜の電荷輸送性を向上させること等を考慮すると、電荷輸送性オリゴマーが好ましい。なお、ポリマーの分子量は重量平均分子量を意味し、重量平均分子量はゲルパーミエーションクロマトグラフィーによるポリスチレン換算重量平均分子量を意味する。
電荷輸送性オリゴマーの分子量は、通常200~5,000であるが、下限として好ましくは300以上、より好ましくは400以上であり、上限として好ましくは4,000以下、より好ましくは3,000以下、より一層好ましくは2,000以下である。
電荷輸送性オリゴマーとしては、単分散の電荷輸送性有機化合物を1種単独で用いることもでき、異なる単分散の電荷輸送性有機化合物を2種以上組み合わせて用いてもよいが、這い上がり現象を再現性よく抑制する観点から、用いる単分散の電荷輸送性有機化合物は、好ましくは1~3種である。
アニリン誘導体の具体例としては、例えば、国際公開第2005/043962号、国際公開第2013/042623号等に開示されたものなどが挙げられ、より具体的には、下記式(1)および(2)で示されるものなどが挙げられる。
炭素数1~20のアルキル基としては、直鎖状、分岐鎖状、環状のいずれでもよく、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、s-ブチル基、t-ブチル基、n-ペンチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、n-ノニル基、n-デシル基等の炭素数1~20の直鎖または分岐鎖状アルキル基;シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、ビシクロブチル基、ビシクロペンチル基、ビシクロヘキシル基、ビシクロヘプチル基、ビシクロオクチル基、ビシクロノニル基、ビシクロデシル基等の炭素数3~20の環状アルキル基などが挙げられる。
その具体例としては、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、ペンタフルオロエチル基、2,2,2-トリフルオロエチル基、ヘプタフルオロプロピル基、2,2,3,3,3-ペンタフルオロプロピル基、2,2,3,3-テトラフルオロプロピル基、2,2,2-トリフルオロ-1-(トリフルオロメチル)エチル基、ノナフルオロブチル基、4,4,4-トリフルオロブチル基、ウンデカフルオロペンチル基、2,2,3,3,4,4,5,5,5-ノナフルオロペンチル基、2,2,3,3,4,4,5,5-オクタフルオロペンチル基、トリデカフルオロヘキシル基、2,2,3,3,4,4,5,5,6,6,6-ウンデカフルオロヘキシル基、2,2,3,3,4,4,5,5,6,6-デカフルオロヘキシル基、3,3,4,4,5,5,6,6,6-ノナフルオロヘキシル基等が挙げられる。
特に、R1~R6は、水素原子、フッ素原子、メチル基、フェニル基またはジフェニルアミノ基(Y2およびY3がフェニル基である-NY2Y3)がより好ましく、R1~R4が水素原子であり、かつ、R5およびR6が同時に水素原子またはジフェニルアミノ基がより一層好ましい。
また、Z3は、ハロゲン原子が好ましく、フッ素原子がより好ましく、存在しないこと(すなわち、非置換の基であること)がより一層好ましい。
kおよびlとしては、式(1)で表されるアニリン誘導体の溶解性を高める観点から、好ましくは、k+l≦8であり、より好ましくは、k+l≦5である。
また、式(2)で表されるアニリン誘導体の溶媒に対する溶解性を高めるとともに、得られる薄膜の均一性を高めることを考慮すると、R11およびR13が共に水素原子であることが好ましい。
特に、R11およびR13が共に水素原子であり、R12およびR14が、それぞれ独立して、フェニル基(このフェニル基は、ハロゲン原子、ニトロ基、シアノ基、水酸基、チオール基、リン酸基、スルホン酸基、カルボキシル基、炭素数1~20のアルコキシ基、炭素数1~20のチオアルコキシ基、炭素数1~20のアルキル基、炭素数1~20のハロアルキル基、炭素数2~20のアルケニル基、炭素数2~20のアルキニル基、炭素数6~20のアリール基、炭素数7~20のアラルキル基、または炭素数1~20のアシル基で置換されていてもよい。)、または上記式(H4)で表される基であることが好ましく、R11およびR13が、共に水素原子であり、R12およびR14が、それぞれ独立して、フェニル基、またはR19’およびR20’が共にフェニル基である下記式(3′)で表される基であることがより好ましく、R11およびR13が、共に水素原子であり、R12およびR14が、共にフェニル基であることがより一層好ましい。
また、mとしては、化合物の入手容易性、製造の容易性、コスト面などを考慮すると、2~4が好ましく、溶媒への溶解性を高めることを考慮すると、2または3がより好ましく、化合物の入手容易性、製造の容易性、製造コスト、溶媒への溶解性、得られる薄膜の透明性等のバランスを考慮すると、2が最適である。
また、無機系および有機系のドーパント物質は、1種類単独で用いてもよく、2種類以上組み合わせて用いてもよい。
さらに、ドーパント物質は、インクから固体膜である有機機能膜を得る過程で、例えば焼成時の加熱といった外部からの刺激によって、例えば分子内の一部が外れることによってドーパント物質としての機能が初めて発現または向上するようになる物質、例えばスルホン酸基が脱離しやすい基で保護されたアリールスルホン酸エステル化合物であってもよい。
ヘテロポリ酸とは、代表的に式(H1)で表されるKeggin型あるいは式(H2)で表されるDawson型の化学構造で示される、ヘテロ原子が分子の中心に位置する構造を有し、バナジウム(V)、モリブデン(Mo)、タングステン(W)等の酸素酸であるイソポリ酸と、異種元素の酸素酸とが縮合してなるポリ酸である。このような異種元素の酸素酸としては、主にケイ素(Si)、リン(P)、ヒ素(As)の酸素酸が挙げられる。
特に、1種類のヘテロポリ酸を用いる場合、その1種類のヘテロポリ酸は、リンタングステン酸またはリンモリブデン酸が好ましく、リンタングステン酸が最適である。また、2種類以上のヘテロポリ酸を用いる場合、その2種類以上のヘテロポリ酸の1つは、リンタングステン酸またはリンモリブデン酸が好ましく、リンタングステン酸がより好ましい。
なお、ヘテロポリ酸は、元素分析等の定量分析において、一般式で示される構造から元素の数が多いもの、または少ないものであっても、それが市販品として入手したもの、あるいは、公知の合成方法にしたがって適切に合成したものである限り、本発明において用いることができる。
すなわち、例えば、一般的には、リンタングステン酸は化学式H3(PW12O40)・nH2Oで、リンモリブデン酸は化学式H3(PMo12O40)・nH2Oでそれぞれ示されるが、定量分析において、この式中のP(リン)、O(酸素)またはW(タングステン)もしくはMo(モリブデン)の数が多いもの、または少ないものであっても、それが市販品として入手したもの、あるいは、公知の合成方法にしたがって適切に合成したものである限り、本発明において用いることができる。この場合、本発明に規定されるヘテロポリ酸の質量とは、合成物や市販品中における純粋なリンタングステン酸の質量(リンタングステン酸含量)ではなく、市販品として入手可能な形態および公知の合成法にて単離可能な形態において、水和水やその他の不純物等を含んだ状態での全質量を意味する。
テトラシアノキノジメタン誘導体の具体例としては、7,7,8,8-テトラシアノキノジメタン(TCNQ)や、式(H3)で表されるハロテトラシアノキノジメタンなどが挙げられる。
また、ベンゾキノン誘導体の具体例としては、テトラフルオロ-1,4-ベンゾキノン(F4BQ)、テトラクロロ-1,4-ベンゾキノン(クロラニル)、テトラブロモ-1,4-ベンゾキノン、2,3-ジクロロ-5,6-ジシアノ-1,4-ベンゾキノン(DDQ)などが挙げられる。
ハロゲン原子としては上記と同じものが挙げられるが、フッ素原子または塩素原子が好ましく、フッ素原子がより好ましい。
A2は、ナフタレン環またはアントラセン環を表すが、ナフタレン環が好ましい。
A3は、2~4価のパーフルオロビフェニル基を表し、pは、A1とA3との結合数を示し、2≦p≦4を満たす整数であるが、A3がパーフルオロビフェニルジイル基、好ましくはパーフルオロビフェニル-4,4’-ジイル基であり、かつ、pが2であることが好ましい。
qは、A2に結合するスルホン酸基数を表し、1≦q≦4を満たす整数であるが、2が最適である。
その他、ハロゲン原子、炭素数1~20のアルキル基の例としては上記と同様のものが挙げられるが、ハロゲン原子としては、フッ素原子が好ましい。
なお、パーフルオロアルキル基とは、アルキル基の水素原子全てがフッ素原子に置換された基であり、パーフルオロアルケニル基とは、アルケニル基の水素原子全てがフッ素原子に置換された基である。
アリールスルホン酸化合物は市販品を用いてもよいが、国際公開第2006/025342号、国際公開第2009/096352号等に記載の公知の方法で合成することもできる。
A12は、-O-または-S-であるが、-O-が好ましい。
A13は、ナフタレンまたはアントラセンから誘導される(n+1)価の基であるが、ナフタレンから誘導される基が好ましい。
Rs1~Rs4は、それぞれ独立して、水素原子、または直鎖状もしくは分岐鎖状の炭素数1~6のアルキル基であり、Rs5は、置換されていてもよい炭素数2~20の1価炭化水素基である。
炭素数2~20の1価炭化水素基は、直鎖状、分岐鎖状、環状のいずれでもよく、その具体例としては、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、t-ブチル基等のアルキル基;フェニル、ナフチル、フェナントリル基等のアリール基などが挙げられる。
また、Rs5としては、炭素数2~4の直鎖アルキル基またはフェニル基が好ましい。
このような炭化水素化合物としては、ベンゼン、トルエン、キシレン、エチルベンゼン、ビフェニル、ナフタレン、アントラセン、フェナントレン等が挙げられる。
なお、上記炭化水素基は、その水素原子の一部または全部が、更に置換基で置換されていてもよく、このような置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ニトロ基、シアノ基、ヒドロキシ基、アミノ基、シラノール基、チオール基、カルボキシ基、スルホン酸エステル基、リン酸基、リン酸エステル基、エステル基、チオエステル基、アミド基、1価炭化水素基、オルガノオキシ基、オルガノアミノ基、オルガノシリル基、オルガノチオ基、アシル基、スルホ基等が挙げられる。
これらの中でも、A14としては、ベンゼン、ビフェニル等から誘導される基が好ましい。
A16は、炭素数6~20の(n+1)価の芳香族炭化水素基であり、この芳香族炭化水素基は、炭素数6~20の芳香族炭化水素化合物の芳香環上から(n+1)個の水素原子を取り除いて得られる基である。
このような芳香族炭化水素化合物としては、ベンゼン、トルエン、キシレン、ビフェニル、ナフタレン、アントラセン、ピレン等が挙げられる。
中でも、A16としては、ナフタレンまたはアントラセンから誘導される基が好ましく、ナフタレンから誘導される基がより好ましい。
上記直鎖状または分岐鎖状の1価脂肪族炭化水素基の具体例としては、メチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、t-ブチル、n-ヘキシル、n-オクチル、2-エチルヘキシル、デシル基等の炭素数1~20のアルキル基;ビニル、1-プロペニル、2-プロペニル、イソプロペニル、1-メチル-2-プロペニル、1-ブテニル、2-ブテニル、3-ブテニル、ヘキセニル基等の炭素数2~20のアルケニル基などが挙げられる。
これらの中でも、Rs6は水素原子が好ましく、Rs7およびRs8は、それぞれ独立して、炭素数1~6のアルキル基が好ましい。
炭素数1~10のアルキル基は、直鎖状、分岐鎖状、環状のいずれでもよく、その具体例としては、メチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、s-ブチル、t-ブチル、n-ペンチル、シクロペンチル、n-ヘキシル、シクロヘキシル、n-ヘプチル、n-オクチル、n-ノニル、n-デシル基等が挙げられる。
Rs10~Rs13としては、ハロゲン原子が好ましく、フッ素原子がより好ましい。
A18は、炭素数6~20の(n+1)価の芳香族炭化水素基であり、この芳香族炭化水素基は、炭素数6~20の芳香族炭化水素化合物の芳香環上から(n+1)個の水素原子を取り除いて得られる基である。
このような芳香族炭化水素化合物としては、ベンゼン、トルエン、キシレン、ビフェニル、ナフタレン、アントラセン、ピレン等が挙げられる。
これらの中でも、A18としては、ナフタレンまたはアントラセンから誘導される基が好ましく、ナフタレンから誘導される基がより好ましい。
1価脂肪族炭化水素基の具体例としては、メチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、s-ブチル、t-ブチル、n-ペンチル、シクロペンチル、n-ヘキシル、シクロヘキシル、n-ヘプチル、n-オクチル、n-ノニル、n-デシル、n-ウンデシル、n-ドデシル基等の炭素数1~20のアルキル基;ビニル、1-プロペニル、2-プロペニル、イソプロペニル、1-メチル-2-プロペニル、1-ブテニル、2-ブテニル、3-ブテニル、ヘキセニル基等の炭素数2~20のアルケニル基などが挙げられるが、炭素数1~20のアルキル基が好ましく、炭素数1~10のアルキル基がより好ましく、炭素数1~8のアルキル基がより一層好ましい。
Rs18の直鎖状または分岐状の炭素数1~20の1価脂肪族炭化水素基としては、上記と同様のものが挙げられる。
Rs18が1価脂肪族炭化水素基である場合、Rs18は、炭素数1~20のアルキル基が好ましく、炭素数1~10のアルキル基がより好ましく、炭素数1~8のアルキル基がより一層好ましい。
Rs19の炭素数2~20の1価炭化水素基としては、前述した1価脂肪族炭化水素基のうちメチル基以外のもののほか、フェニル、ナフチル、フェナントリル基等のアリール基などが挙げられる。
これらの中でも、Rs19は、炭素数2~4の直鎖アルキル基またはフェニル基が好ましい。
なお、上記1価炭化水素基が有していてもよい置換基としては、フッ素原子、炭素数1~4のアルコキシ基、ニトロ基、シアノ基等が挙げられる。
有機機能インクの粘度は、インクジェット法で滴下する液滴の量等に応じて異なるため一概に規定できないが、通常、25℃で15mPa・s以下であり、好ましく10mPa・s以下である。
また、有機機能インクの表面張力は、通常25℃で20~50mN/mであるが、好ましくは25~45mN/m、より好ましくは37~42mN/mである。
なお、粘度は、東機産業(株)製、TVE-25形粘度計で測定した値である。表面張力は、協和界面科学(株)製、自動表面張力計CBVP-Z型で測定した値である。
有機機能インクの粘度と表面張力は、所望の膜厚等の各種要素を考慮して、上述したインク溶媒の種類やそれらの比率、固形分濃度等を変更することで調整可能である。
また、ドーパントを用いる場合、その添加順序も任意である。
なお、有機機能インクの調製の際に、より平坦性の高い薄膜を再現性よく得る観点から、有機機能材料、ドーパント物質等を有機溶媒に溶解させた後、サブマイクロメートルオーダーのフィルター等を用いて濾過することが望ましい。
通常、開口部の大きさは、長辺100~210μm、短辺40μm×100μmであり、バンクテーパー角度は20~80°である。
基板の材質としては、特に限定されるものではないが、本発明では、電子素子の陽極材料として用いられるインジウム錫酸化物(ITO)、インジウム亜鉛酸化物(IZO)に代表される透明電極材料;アルミニウム、金、銀、銅、インジウム等に代表される金属、またはこれらの合金等から構成される金属陽極材料;高電荷輸送性を有するポリチオフェン誘導体やポリアニリン誘導体等のポリマー陽極材料などが挙げられ、平坦化処理を行ったものが好ましい。
この際、インクジェット塗布時および塗布後の加熱・焼成雰囲気は特に限定されるものではなく、大気雰囲気、窒素等の不活性ガス雰囲気、減圧下のいずれでもよいが、アニリン誘導体等の有機機能材料とともに用いるドーパント物質の種類によっては、大気雰囲気下で加熱・焼成することで、良好な特性を有する機能膜が再現性よく得られる場合がある。
減圧時間も、溶媒が蒸発する限り特に制限はないが、通常、0.1~60分程度であり、1~30分程度が好ましい。
なお、加熱・焼成の際、より高い均一成膜性を発現させたり、基板上で反応を進行させたりする目的で、2段階以上の温度変化をつけてもよい。加熱は、例えば、ホットプレートやオーブン等、適当な機器を用いて行えばよい。
上述したアニリン誘導体を含む有機機能インクから作製された有機機能膜は、有機EL素子において、正孔注入層、正孔輸送層、正孔注入輸送層として用い得るが、本発明では、陽極上に形成された隔壁内にインクジェット法によって塗布されるため、正孔注入層または正孔注入輸送層として用いられ、特に、正孔注入層として好適に用いられる。
(a)陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/電子注入層/陰極
(b)陽極/正孔注入層/正孔輸送層/発光層/電子注入輸送層/陰極
(c)陽極/正孔注入輸送層/発光層/電子輸送層/電子注入層/陰極
(d)陽極/正孔注入輸送層/発光層/電子注入輸送層/陰極
(e)陽極/正孔注入層/正孔輸送層/発光層/陰極
(f)陽極/正孔注入輸送層/発光層/陰極
「電子注入層」、「電子輸送層」および「電子注入輸送層」とは、発光層と陰極との間に形成される層であって、電子を陰極から発光層へ輸送する機能を有するものであり、発光層と陰極の間に、電子輸送性材料の層が1層のみ設けられる場合、それが「電子注入輸送層」であり、発光層と陰極の間に、電子輸送性材料の層が2層以上設けられる場合、陰極に近い層が「電子注入層」であり、それ以外の層が「電子輸送層」である。
「発光層」とは、発光機能を有する有機層であって、ドーピングシステムを採用する場合、ホスト材料とドーパント材料を含んでいる。このとき、ホスト材料は、主に電子と正孔の再結合を促し、励起子を発光層内に閉じ込める機能を有し、ドーパント材料は、再結合で得られた励起子を効率的に発光させる機能を有する。燐光素子の場合、ホスト材料は主にドーパントで生成された励起子を発光層内に閉じ込める機能を有する。
予め所定パターンの隔壁が形成された陽極基板上に、上記の方法により、上記有機機能インクを用いて正孔注入層を形成する。これを真空蒸着装置内に導入し、正孔輸送層、発光層、電子輸送層/ホールブロック層、電子注入層、陰極金属を順次蒸着する。あるいは、当該方法において蒸着で正孔輸送層と発光層を形成する代わりに、正孔輸送性高分子を含む正孔輸送層形成用組成物と発光性高分子を含む発光層形成用組成物を用いてウェットプロセスによってこれらの層を形成する。なお、必要に応じて、発光層と正孔輸送層との間に電子ブロック層を設けてよい。
なお、金属陽極を構成するその他の金属としては、金、銀、銅、インジウムやこれらの合金等が挙げられるが、これらに限定されるわけではない。
また、蒸着で発光層を形成する場合、発光性ドーパントと共蒸着してもよく、発光性ドーパントとしては、トリス(2-フェニルピリジン)イリジウム(III)(Ir(ppy)3)等の金属錯体や、ルブレン等のナフタセン誘導体、キナクリドン誘導体、ペリレン等の縮合多環芳香族環等が挙げられる。
陰極材料としては、アルミニウム、マグネシウム-銀合金、アルミニウム-リチウム合金等が挙げられる。
電子ブロック層を形成する材料としては、トリス(フェニルピラゾール)イリジウム等が挙げられる。
通常、ボトムエミッション構造の素子では、基板側に透明陽極が用いられ、基板側から光が取り出されるのに対し、トップエミッション構造の素子では、金属からなる反射陽極が用いられ、基板と反対方向にある透明電極(陰極)側から光が取り出されることから、例えば陽極材料について言えば、ボトムエミッション構造の素子を製造する際はITO等の透明陽極を、トップエミッション構造の素子を製造する際はAl/Nd等の反射陽極を、それぞれ用いる。
〔装置〕
試料の物性測定は、下記の条件のもとで下記の装置を使用して行った。
(1)数平均分子量(Mn)および重量平均分子量(Mw)
下記条件下でのゲルパーミエーションクロマトグラフィーにより、ポリスチレン換算値として測定した。
・クロマトグラフ:(株)島津製作所製GPC装置 LC-20AD
・カラム:Shodex KF-804Lおよび803L(昭和電工(株)製)およびTSK-GEL(東ソー(株)製)を直列接続
・溶離液:テトラヒドロフラン(10mmol/Lの臭化リチウム-水和物(LiBr・H2O)を含有)
・流速:1ml/分
・カラム温度:40℃
(2)インクジェット装置およびインクジェットヘッド(インクの塗布)
・インクジェット装置:クラスターテクノロジー製 WAVE BUILDER(型番:PIJD-1)およびinkjetlado
・インクジェットヘッド:クラスターテクノロジー製 PIJ-25NSET
〔試薬〕
以下で用いる略号の意味は、次のとおりである。
MMA:メチルメタクリレート
HEMA:2-ヒドロキシエチルメタクリレート
HPMA:4-ヒドロキシフェニルメタクリレート
HPMA-QD:4-ヒドロキシフェニルメタクリレート1molと、1,2-ナフトキノン-2-ジアジド-5-スルホニルクロリド1.1molの縮合反応によって合成される化合物
CHMI:N-シクロヘキシルマレイミド
PFHMA:2-(パーフルオロヘキシル)エチルメタクリレート
MAA:メタクリル酸
AIBN:α,α’-アゾビスイソブチロニトリル
QD1:α,α,α’-トリス(4-ヒドロキシフェニル)-1-エチル-4-イソプロピルベンゼン1molと、1,2-ナフトキノン-2-ジアジド-5-スルホニルクロリド1.5molの縮合反応によって合成される化合物
GT-401:ブタンテトラカルボン酸テトラ(3,4-エポキシシクロヘキシルメチル)修飾ε-カプロラクトン(商品名:エポリードGT-401((株)ダイセル製))
PGME:プロピレングリコールモノメチルエーテル
PGMEA:プロピレングリコールモノメチルエーテルアセテート
CHN:シクロヘキサノン
TMAH:テトラメチルアンモニウムヒドロキシド
TEG:トリエチレングリコール
TEGDME:トリエチレングリコールジメチルエーテル
DEG:ジエチレングリコール
2-PE:2-フェノキシエタノール
BEHP:ビス(2-エチルヘキシル)フタレート
(1)アクリル重合体の合成
[合成例1]
MMA10.0g、HEMA12.5g、CHMI20.0g、HPMA2.50g、MAA5.00g、およびAIBN3.20gをPGME79.8gに溶解し、60~100℃にて20時間反応させることにより、アクリル重合体溶液(固形分濃度40質量%)を得た(P1)。得られたアクリル重合体P1のMnは3,700、Mwは6,100であった。
HPMA-QD2.50g、PFHMA7.84g、MAA0.70g、CHMI1.46g、およびAIBN0.33gをCHN51.3gに溶解し、110℃にて20時間撹拌して反応させることにより、アクリル重合体溶液(固形分濃度20質量%)を得た(P2)。得られたアクリル重合体P2のMnは4,300、Mwは6,300であった。
[製造例1]
合成例1で得られたP1 5.04g、合成例2で得られたP2 0.05g、QD1 0.40g、GT-401 0.09gおよびPGMEA6.42gを混合し、室温で3時間撹拌して均一な溶液とし、ポジ型感光性樹脂組成物を得た。
[製造例2]
(株)テクノビジョン製UV-312を用いて10分間オゾン洗浄したITO-ガラス基板上に、スピンコーターを用いて、製造例1で得られたポジ型感光性樹脂組成物を塗布した後、基板をホットプレート上でのプリベーク(温度100℃で120秒間加熱)に付して、膜厚1.2μmの薄膜を形成した。この薄膜に、長辺200μm、短辺100μmの長方形が多数描かれたパターンのマスクを介して、キヤノン(株)製紫外線照射装置PLA-600FAにより、紫外線(365nmにおける光強度:5.5mW/cm2)を一定時間照射した。その後、薄膜を1.0質量%TMAH水溶液に120秒間浸漬して現像を行った後、超純水を用いて薄膜の流水洗浄を20秒間行った。次いで、この長方形パターンが形成された薄膜をポストベーク(温度230℃で30分間加熱)に付して硬化させ、隔壁付基板を作製した。
[比較調製例1-1]TEG/TEGDME/DEG=2/68/30(質量比)
TEG0.4g、TEGDME13.6gおよびDEG6gの混合溶媒に、式(c)で表されるオリゴアニリン化合物0.102gおよび式(S1)で表されるアリールスルホン酸化合物0.202gを入れ、ホットスターラーを用いて50℃で3時間撹拌した。得られた溶液を、孔径0.2μmのPTFEシリンジフィルターでろ過し、有機機能インクを得た。
TEGの使用量を1gとし、TEGDMEの使用量を13gとした以外は、比較調製例1-1と同様の方法で有機機能インクを得た。
TEGの使用量を2gとし、TEGDMEの使用量を12gとした以外は、比較調製例1-1と同様の方法で有機機能インクを得た。
TEGの使用量を3gとし、TEGDMEの使用量を11gとした以外は、比較調製例1-1と同様の方法で有機機能インクを得た。
TEGの使用量を4gとし、TEGDMEの使用量を10gとした以外は、比較調製例1-1と同様の方法で有機機能インクを得た。
TEG0.4g、TEGDME10.6g、DEG5gおよび2-PE4gの混合溶媒を用いた以外は、実施例1-1と同様の方法で有機機能インクを得た。
TEGの使用量を1gとし、TEGDMEの使用量を10gとした以外は、比較調製例1-3と同様の方法で有機機能インクを得た。
TEGの使用量を2gとし、TEGDMEの使用量を9gとした以外は、比較調製例1-3と同様の方法で有機機能インクを得た。
TEGの使用量を3gとし、TEGDMEの使用量を8gとした以外は、比較調製例1-3と同様の方法で有機機能インクを得た。
TEGの使用量を4gとし、TEGDMEの使用量を7gとした以外は、比較調製例1-3と同様の方法で有機機能インクを得た。
TEGの代わりにBEHP(沸点385℃)を用いた以外は、調製例1-4と同様の方法で有機機能インクを得た。
[比較例1-1]
製造例2で作製した隔壁付基板上の長方形の開口部(膜形成領域)に、クラスターテクノロジー(株)製 Inkjet Designerを用いて、比較調製例1-1で調製した有機機能インクを吐出し、得られた塗膜を、その後すぐに、常温で10Pa以下の減圧度(真空度)で15分間減圧乾燥し、次いで常圧で、230℃15分間乾燥して隔壁内に有機機能膜を形成し、有機機能膜付き基板を得た。なお、有機機能膜の開口部中央付近の膜厚が80nmとなるように吐出した。
比較調製例1-1で調製した有機機能インクの代わりに、調製例1-1~1-3,比較調製例1-2で調製した有機機能インクをそれぞれ用いた以外は、比較例1-1と同様の方法で有機機能膜を形成し、有機機能膜付き基板を得た。有機機能膜の開口部中央付近の膜厚が80nmとなるように吐出した。
調製例1-4~1-6,比較調製例1-3~1-4で調製した有機機能インクをそれぞれ用いた以外は、比較例1-1と同様の方法で有機機能膜を形成し、有機機能膜付き基板を得た。なお、得られる有機機能膜の開口部中央付近の膜厚が60nmとなるように吐出した。
比較調製例1-1で調製した有機機能インクの代わりに、比較調製例1-5で調製した有機機能インクを用いた以外は、比較例1-1と同様の方法で有機機能膜を形成し、有機機能膜付き基板を得た。しかし、有機機能膜の凹凸が顕著であり平坦性が著しく悪く、後述するパイルアップ指数を算出するのが困難であった。
なお、パイルアップ指数は、図1に示されるように、隔壁(バンク)幅をAμmとし、隔壁(バンク)中央部の膜厚から+10%の膜厚の範囲をB(μm)とした場合におけるB/A×100(%)として求めた。
Claims (9)
- 基板と、この基板上に開口部を規定する隔壁と、この隔壁内に有機機能膜とを有する有機機能膜付き基板の製造方法であって、
有機機能材料と、トリエチレングリコールを含む溶媒とを含む有機機能インクを前記隔壁内にインクジェット法で塗布する工程と、
減圧することで、前記隔壁内に塗布された有機機能インクから溶媒を除去して有機機能膜を形成する工程と、
を備え、
前記溶媒中のトリエチレングリコールの含有量が、3~17質量%であることを特徴とする有機機能膜付き基板の製造方法。 - 前記減圧することにより溶媒成分を除去した後、加熱する工程を備える請求項1記載の有機機能膜付き基板の製造方法。
- 前記溶媒が、トリエチレングリコールよりも沸点の低いグリコール溶媒を含む請求項1または2記載の有機機能膜付き基板の製造方法。
- 前記溶媒が、トリエチレングリコールよりも沸点の低いグリコールエーテル溶媒を含む請求項1~3のいずれか1項記載の有機機能膜付き基板の製造方法。
- 前記溶媒が、トリエチレングリコール、ジエチレングリコールおよびトリエチレングリコールジメチルエーテルを含む請求項1~4のいずれか1項記載の有機機能膜付き基板の製造方法。
- 前記有機機能材料が、アニリン誘導体である請求項1~5のいずれか1項記載の有機機能膜付き基板の製造方法。
- 請求項1~6の製造方法によって得られた有機機能膜付き基板の上に、さらに有機機能層を作製する工程を含む電子素子の製造方法。
- 基板と、この基板上に開口部を規定する隔壁と、この隔壁内に有機機能膜とを有する有機機能膜付き基板を製造するにあたって、
有機機能材料と、溶媒とを含む有機機能インクを前記隔壁内にインクジェット法で塗布する際に前記有機機能インクが前記隔壁内を這い上がる現象を抑制する這い上がり抑制方法であって、
前記有機機能インクとして、トリエチレングリコールの含有量が3~17質量%である溶媒を用いることを特徴とする這い上がり抑制方法。 - 基板と、この基板上に開口部を規定する隔壁と、この隔壁内に有機機能膜とを有する有機機能膜付き基板を製造する際に、前記隔壁内にインクジェット法で塗布されるインクジェット法用インクであって、
有機機能材料と、トリエチレングリコールを含む溶媒とを含み、この溶媒中のトリエチレングリコールの含有量が、3~17質量%であることを特徴とするインクジェット法用インク。
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JP7334741B2 (ja) | 2023-08-29 |
CN112771995A (zh) | 2021-05-07 |
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