WO2013180036A1 - 導電性薄膜積層体の製造方法 - Google Patents

導電性薄膜積層体の製造方法 Download PDF

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WO2013180036A1
WO2013180036A1 PCT/JP2013/064533 JP2013064533W WO2013180036A1 WO 2013180036 A1 WO2013180036 A1 WO 2013180036A1 JP 2013064533 W JP2013064533 W JP 2013064533W WO 2013180036 A1 WO2013180036 A1 WO 2013180036A1
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group
thin film
conductive thin
ring
substrate
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PCT/JP2013/064533
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English (en)
French (fr)
Japanese (ja)
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健史 五十島
優記 大嶋
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三菱化学株式会社
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Priority to JP2014518426A priority Critical patent/JP6432347B2/ja
Priority to KR1020147031960A priority patent/KR102107355B1/ko
Priority to CN201380028499.0A priority patent/CN104365180B/zh
Publication of WO2013180036A1 publication Critical patent/WO2013180036A1/ja

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/20—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the material in which the electroluminescent material is embedded
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • 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
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene

Definitions

  • the present invention relates to a method for producing a conductive thin film laminate, a conductive thin film laminate obtained by the method, an organic electroluminescence element, an organic EL (electroluminescence) display, and organic EL illumination.
  • the wet film-forming method is advantageous in terms of material utilization efficiency, manufacturing cost, and area increase compared to the vacuum deposition method.
  • the wet film forming method it is necessary to dissolve or disperse various materials in a solvent, and it is necessary to remove the solvent when forming a thin film. Therefore, several methods have been proposed for removing the solvent.
  • Patent Documents 1 to 4 describe that heating using electromagnetic waves, particularly infrared rays, is effective. Further, it is considered that heating can increase the density of the thin film and improve the strength and conductivity of the thin film. Furthermore, when a conductive thin film has a crosslinkable group, it crosslinks by heating, becomes insoluble with respect to a solvent, and lamination
  • An object of the present invention is to provide a method for producing a conductive thin film laminate in which the above-mentioned problems are solved. Furthermore, it is an object of the present invention to provide a conductive thin film laminate, particularly an organic electroluminescence device having a low driving voltage, a high luminous efficiency and a long driving life, an organic EL display including the organic EL display, and an organic EL illumination. .
  • the present inventors have found that the present invention can be solved by heating the conductive thin film using infrared rays as a heating means, and the present invention has been completed. It was.
  • the gist of the present invention is the following [1] to [36].
  • a method for producing a conductive thin film laminate including a substrate and a conductive thin film formed on the substrate,
  • the conductive thin film includes a conductive thin film precursor containing a repeating unit represented by the following formula (1) and containing a polymer compound having a crosslinking group, on the substrate or on the substrate.
  • Ar a or Ar b each independently represents an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group having 4 to 60 carbon atoms.
  • R 21 to R 25 each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
  • Ar 41 represents an aromatic hydrocarbon group or substituent which may have a substituent.
  • Ar 6 and Ar 7 each independently represent a divalent aromatic ring group which may have a substituent
  • Ar 8 represents an aromatic which may have a substituent
  • R 8 and R 9 each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted carbon group having 1 to 12 represents an alkoxy ring group or an aromatic ring group which may have a substituent
  • R 8 and R 9 may combine with each other to form a ring
  • p represents an integer of 1 to 5.
  • Ar 31 , Ar 33 , Ar 34 and Ar 35 each independently have a divalent aromatic hydrocarbon ring group or substituent which may have a substituent.
  • Ar 32 represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
  • R 11 represents an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted alkoxy group having 1 to 12 carbon atoms
  • R 12 to R 12 each represents Independently, it may have a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted alkoxy group having 1 to 12 carbon atoms, or a substituent.
  • R 12 and R 13 may combine with each other to form a ring.
  • R 14 and R 15 may combine with each other to form a ring.
  • R 16 and R 17 may be bonded to each other to form a ring.
  • l, m and n each independently represents an integer of 0 to 2.
  • the substrate has a minimum value of infrared transmittance in a wavelength range of 2000 to 3300 nm, The conductivity according to any one of [1] to [6], wherein a product ( ⁇ ) of a wavelength at a minimum value of the infrared transmittance and a peak wavelength of the infrared ray is 2 ⁇ m 2 or more and 16 ⁇ m 2 or less.
  • a method for producing a thin film laminate [8] The method for producing a conductive thin film laminate according to any one of [1] to [7], wherein the minimum value of infrared transmittance of the substrate is 95% or less.
  • the conductive thin film precursor is heated at 150 ° C. or more and 300 ° C. or less when the temperature of the substrate is irradiated with infrared rays, and the holding time in the temperature range is 5 seconds or more and 30 minutes or less.
  • the conductive thin film precursor is heated at a temperature of 150 ° C. or more and 300 ° C.
  • a method for producing a conductive thin film laminate comprising a substrate and a film thickness of the conductive thin film formed on the substrate being 50 nm or more and 1 ⁇ m or less,
  • the conductive thin film includes a conductive thin film precursor containing a repeating unit represented by the following formula (1) and containing a polymer compound having a crosslinking group, on the substrate or on the substrate.
  • a method for producing a conductive thin-film laminate which is formed by coating on the substrate and then crosslinking by heating with infrared rays.
  • Ar a or Ar b each independently represents an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group having 4 to 60 carbon atoms.
  • R 21 to R 25 each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
  • Ar 41 represents an aromatic hydrocarbon group or substituent which may have a substituent.
  • Ar 6 and Ar 7 each independently represent a divalent aromatic ring group which may have a substituent
  • Ar 8 represents an aromatic which may have a substituent
  • R 8 and R 9 each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted carbon group having 1 to 12 represents an alkoxy ring group or an aromatic ring group which may have a substituent
  • R 8 and R 9 may combine with each other to form a ring
  • p represents an integer of 1 to 5.
  • Ar 31 , Ar 33 , Ar 34 and Ar 35 each independently have a divalent aromatic hydrocarbon ring group or substituent which may have a substituent.
  • Ar 32 represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
  • R 11 represents an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted alkoxy group having 1 to 12 carbon atoms
  • R 12 to R 17 each represents Independently, it may have a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted alkoxy group having 1 to 12 carbon atoms, or a substituent.
  • R 12 and R 13 may combine with each other to form a ring.
  • R 14 and R 15 may combine with each other to form a ring.
  • R 16 and R 17 may be bonded to each other to form a ring.
  • l, m and n each independently represents an integer of 0 to 2.
  • the substrate has a minimum value of infrared transmittance in a wavelength range of 2000 to 3300 nm, The conductivity according to any one of [14] to [19], wherein a product ( ⁇ ) of a wavelength at a minimum value of the infrared transmittance and a peak wavelength of the infrared ray is 2 ⁇ m 2 or more and 16 ⁇ m 2 or less.
  • a method for producing a thin film laminate [21] The method for producing a conductive thin film laminate according to any one of [14] to [20], wherein the substrate has a minimum infrared transmittance of 95% or less.
  • a method for producing a conductive thin film laminate including a substrate and a conductive thin film formed on the substrate,
  • the conductive thin film precursor contains a light emitting material
  • a method for producing a conductive thin film laminate comprising maintaining the temperature of the substrate at 70 ° C. or higher and 150 ° C. or lower during infrared irradiation for 5 seconds or longer and 20 minutes or shorter.
  • the conductive thin film precursor is heated at a temperature of 70 ° C. or higher and 150 ° C. or lower when the temperature of the substrate is irradiated with infrared rays, and is maintained at a constant temperature in the temperature range for 20 seconds or longer.
  • a conductive thin film laminate can be obtained by heating in a short time without damaging the conductive thin film.
  • the obtained conductive thin film laminate has high conductivity, and in particular, the organic electroluminescence device is not only a device with high luminous efficiency and low driving voltage, but also a decrease in light emission luminance, voltage increase during constant current driving, Generation of non-light emitting portions (dark spots), short circuit defects, and the like are suppressed.
  • FIG. 1 is a schematic cross-sectional view showing a structural example of an organic electroluminescent element.
  • FIG. 2 is a graph showing the relationship between the initial film thickness and the remaining film ratio of the hole injection layer forming compositions obtained in Example 8 and Comparative Example 6.
  • FIG. 3 is a graph showing the relationship between the heating time and the residual film ratio of the composition for forming a hole injection layer obtained in Example 9.
  • FIG. 4 is a graph showing the relationship between the initial film thickness and the remaining film ratio of the hole injection layer forming compositions obtained in Example 10 and Comparative Example 7.
  • the present invention relates to a method for manufacturing a conductive thin film laminate including a substrate and a conductive thin film formed on the substrate, wherein the conductive thin film has a conductive thin film precursor on the substrate or on the substrate. It is applied on the formed conductive thin film and then heated by infrared rays to be formed.
  • the substrate has a minimum value of infrared transmittance in a wavelength range of 2000 to 3300 nm, and a product ( ⁇ ) of a wavelength at the minimum value of the infrared transmittance and a peak wavelength of the infrared ray is 2 ⁇ m 2 or more and 16 ⁇ m 2 or less. It is.
  • inorganic glass or various resins can be used as the substrate used for the conductive thin film laminate.
  • inorganic glass such as alkali-free glass, blue plate glass, quartz glass, borosilicate glass, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), cellulose acetate propionate, polyethersulfone, polycarbonate, polyimide, polyamide, etc.
  • Resin glass is mentioned.
  • a metal plate, metal foil, etc. can also be used. Inorganic glass is preferred.
  • the thickness of the substrate is usually 0.01 mm or more, preferably 0.1 mm or more, and more preferably 0.2 mm or more. Moreover, it is 10 mm or less normally, Preferably it is 5 mm or less, More preferably, it is 1 mm or less.
  • the substrate can remove the heat of the conductive thin film that has been heated excessively by infrared rays, and the destruction of the conductive thin film can be suppressed. Further, the substrate is heated moderately, and the conductive thin film is heated by the heat. That is, the conductive thin film can be heated appropriately with the thickness of the substrate, and the performance of the conductive thin film can be enhanced.
  • the conductive thin film is disposed and laminated on the substrate.
  • a plurality of conductive thin films may be laminated.
  • the conductive thin film may be any film as long as it has conductivity, but is usually 10 M ⁇ / ⁇ or less, preferably 1 M ⁇ / ⁇ or less, more preferably 1000 ⁇ / ⁇ or less, and particularly preferably 500 ⁇ / ⁇ . It is as follows.
  • the thickness of the conductive thin film is usually 3 nm or more, preferably 5 nm or more, more preferably 8 nm or more, and usually 1 ⁇ m or less, preferably 800 nm or less, more preferably 500 nm or less, and particularly preferably 400 nm or less.
  • An electroconductive thin film precursor means the composition adjusted when forming an electroconductive thin film.
  • the said composition is a composition containing an electroconductive material, and details are mentioned later.
  • the conductive thin film laminate has a structure in which a conductive thin film is disposed and laminated on a substrate.
  • the method for arranging and laminating the conductive thin film on the substrate can be achieved by applying a conductive thin film precursor, for example, a composition containing a conductive material on the substrate, and heating with infrared rays after the coating.
  • a conductive thin film precursor for example, a composition containing a conductive material on the substrate
  • a conductive thin film precursor is coated on the conductive thin film previously formed on the substrate, and heated by infrared rays after coating.
  • the use of infrared rays makes it possible to produce a conductive thin film laminate having the above effects in a short time. Further, as compared with the use of a hot stove or a hot plate, firing can be performed in a short time, and there is an advantage that the influence of gas (oxygen and moisture) in the firing atmosphere and the influence of dust can be minimized.
  • Infrared heating For infrared heating, a halogen heater, a ceramic-coated halogen heater, a ceramic heater, or the like can be used.
  • the halogen heater include Ushio Electric Co., Ltd. (UH-USC, UH-USD, UH-MA1, UH-USF, UH-USP, UH-USPN, and halogen coaters in which these are ceramic coated (black coat)), The product made from Heraeus etc. is mentioned.
  • As a far-infrared heater for example, there is AMK (far-infrared panel type clean heater).
  • the heating method examples include a method in which the infrared heater is installed on the top of the substrate and infrared heating is performed.
  • the infrared transmission of the substrate preferably has a minimum value in the wavelength range of 2000 nm to 3300 nm.
  • the upper limit of the infrared transmittance is usually 95% or less, preferably 90% or less, more preferably 85% or less, still more preferably 80% or less, and particularly preferably 75% or less.
  • the lower limit is usually 5% or more, preferably 10% or more, more preferably 20% or more, and further preferably 25% or more.
  • the substrate is heated appropriately, and the conductive thin film precursor is heated by the heat conduction. That is, the conductive thin film precursor can be heated appropriately with the thickness of the substrate, and the performance of the conductive thin film can be enhanced. In addition, when the conductive thin film precursor is heated too much, it can be a hot bath that releases heat moderately.
  • the lower limit of the peak wavelength of the infrared heater is usually 0.8 ⁇ m or more, preferably 0.9 ⁇ m or more, more preferably 1 ⁇ m or more, and particularly preferably 1.1 ⁇ m or more.
  • the upper limit is 25 ⁇ m or less, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and particularly preferably 3 ⁇ m or less.
  • the conductive thin film precursor can be heated by absorbing infrared rays. Further, the substrate is heated appropriately by the peak wavelength of the infrared heater in this range, and the conductive thin film precursor can be heated with the heat.
  • the organic material absorbs infrared rays from the infrared heater, and the conductive thin film precursor can be heated by infrared induction heating.
  • the infrared transmittance of the substrate has a minimum value of transmittance in the wavelength range of 2000 to 3300 nm, and the wavelength at the minimum value and the peak wavelength of the infrared heater.
  • the lower limit of the product ( ⁇ ) is usually 2 ⁇ m 2 or more, preferably 2.5 ⁇ m 2 or more, more preferably 3 ⁇ m 2 or more.
  • the upper limit thereof is generally, 16 [mu] m 2 or less, preferably 15.5 2 or less, more preferably 15 [mu] m 2 or less.
  • the conductive thin film precursor can be appropriately heated, and the performance of the conductive thin film is improved. be able to.
  • the reason why the product ( ⁇ ) of the wavelength at the minimum value of the infrared transmittance of the substrate and the peak wavelength of the infrared heater is used as a parameter for specifying the invention will be described below.
  • the minimum wavelength in the range of 2000 to 3300 nm in the infrared absorption of the substrate can be appropriately heated without overheating the substrate.
  • the infrared heater for heating the substrate includes a peak wavelength of the infrared heater as a typical value indicating the characteristics.
  • the relationship between the wavelength and the energy is inversely proportional, so that the smaller the value of this parameter ( ⁇ ), the greater the energy that can be obtained from the substrate.
  • the larger the value of the parameter ( ⁇ ) the lower the energy obtained by the substrate.
  • This parameter serves as an index in the present invention.
  • polymer compound of the present invention contains a repeating unit represented by the following formula (1).
  • Ar a and Ar b each independently represents an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group having 4 to 60 carbon atoms.
  • aromatic hydrocarbon ring group examples include a benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, triphenylene ring, chrysene ring, naphthacene ring, perylene ring, coronene ring having one or two free valences.
  • free valence can form bonds with other free valences as described in Organic Chemistry / Biochemical Nomenclature (above) (Revised 2nd edition, Nankodo, 1992). Say things. That is, for example, “a benzene ring having one free valence” refers to a phenyl group, and “a benzene ring having two free valences” refers to a phenylene group.
  • aromatic heterocyclic group examples include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having one or two free valences.
  • the aromatic hydrocarbon ring group or the aromatic heterocyclic group is a condensed ring having one or two free valences
  • the number of the condensed monocycles has high ring stability. In terms of point, it is preferably less, preferably 8 or less, and more preferably 5 or less. On the other hand, the lower limit is two.
  • An aromatic hydrocarbon ring group or an aromatic heterocyclic group is specifically a benzene ring, a thiophene ring, a pyridine ring or the like having one or two free valences from the viewpoint of solubility and heat resistance.
  • Monocyclic ring A condensed ring such as naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring and pyrene ring, and an aromatic hydrocarbon ring in which 2 to 8 aromatic rings such as fluorene ring, biphenyl and terphenyl are connected are preferable.
  • a benzene ring, a fluorene ring, biphenyl, and terphenyl having one or two free valences are more preferable in terms of high solubility and high stability.
  • Examples of the substituent that the aromatic hydrocarbon ring group or aromatic heterocyclic group may have include a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon ring group having 6 to 25 carbon atoms, and a carbon number of 3 Aromatic heterocyclic group having 20 carbon atoms, diarylamino group having 12 to 60 carbon atoms, alkyloxy group having 1 to 20 carbon atoms, (hetero) aryloxy group having 3 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms , A (hetero) arylthio group having 3 to 20 carbon atoms, a cyano group, and the like.
  • a saturated hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon ring group having 6 to 25 carbon atoms are preferable from the viewpoint of solubility and heat resistance.
  • examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, and a hexyl group.
  • methyl group, ethyl group and isopropyl group are preferable, and methyl group and ethyl group are more preferable from the viewpoint of availability of raw materials and low cost.
  • Examples of the monovalent aromatic hydrocarbon ring group having 6 to 25 carbon atoms include a naphthyl group such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group; a phenanthyl group such as a 9-phenanthyl group and a 3-phenanthyl group; Anthryl groups such as anthryl group, 2-anthryl group, and 9-anthryl group; naphthacenyl groups such as 1-naphthacenyl group and 2-naphthacenyl group; 1-chrycenyl group, 2-chrysenyl group, 3-chrysenyl group, 4-chrysenyl group Group, chrycenyl group such as 5-chrycenyl group and 6-chrycenyl group; pyrenyl group such as 1-pyrenyl group; triphenylenyl group such as 1-triphenylenyl group;
  • a phenyl group, a 2-naphthyl group and a 3-biphenyl group are preferable from the viewpoint of stability of the compound, and a phenyl group is particularly preferable from the viewpoint of ease of purification.
  • Examples of the aromatic heterocyclic group having 3 to 20 carbon atoms include thienyl groups such as 2-thienyl group; furyl groups such as 2-furyl group; imidazolyl groups such as 2-imidazolyl group; carbazolyl groups such as 9-carbazolyl group; And a pyridyl group such as a 2-pyridyl group and a triazinyl group such as a 1,3,5-triazin-2-yl group.
  • a carbazolyl group, particularly a 9-carbazolyl group is preferable from the viewpoint of stability.
  • diarylamino group having 12 to 60 carbon atoms examples include diphenylamino group, N-1-naphthyl-N-phenylamino group, N-2-naphthyl-N-phenylamino group, and N-9-phenanthryl-N-phenylamino.
  • a diphenylamino group an N-1-naphthyl-N-phenylamino group, and an N-2-naphthyl-N-phenylamino group are preferable, and a diphenylamino group is particularly preferable from the viewpoint of stability.
  • alkyloxy group having 1 to 20 carbon atoms examples include methoxy group, ethoxy group, isopropyloxy group, cyclohexyloxy group, and octadecyloxy group.
  • Examples of the (hetero) aryloxy group having 3 to 20 carbon atoms include substituents having an aryloxy group such as a phenoxy group, a 1-naphthyloxy group, and a 9-anthranyloxy group, and a heteroaryloxy group such as a 2-thienyloxy group Etc.
  • alkylthio group having 1 to 20 carbon atoms examples include a methylthio group, an ethylthio group, an isopropylthio group, and a cyclohexylthio group.
  • Examples of the (hetero) arylthio group having 3 to 20 carbon atoms include an arylthio group such as a phenylthio group, a 1-naphthylthio group and a 9-anthranylthio group, and a heteroarylthio group such as a 2-thienylthio group.
  • the polymer compound in the present invention has an arylamino structure in which a group other than an aromatic hydrocarbon ring group or an aromatic heterocyclic group is bonded in a repeating unit, other than an aromatic hydrocarbon ring group or an aromatic heterocyclic group
  • the group is preferably an aliphatic hydrocarbon group having 1 to 70 carbon atoms.
  • the aliphatic hydrocarbon group may be linear or cyclic and may be saturated or unsaturated.
  • Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a hexyl group, an octyl group, a cyclohexyl group, and a decyl group. Group, octadecyl group and the like.
  • methyl group, 1,2-ethyl group, 1,3-propyl group, 1,4-butyl group, 1,5-pentyl group and 1,8- Groups having 1 to 10 carbon atoms such as an octyl group are preferred, and groups having 1 to 8 carbon atoms are more preferred.
  • groups having 1 to 3 carbon atoms such as a methyl group, an ethyl group and an isopropyl group are particularly preferable, and groups having 1 to 2 carbon atoms such as a methyl group and an ethyl group are most preferable.
  • the aliphatic hydrocarbon group is preferably a saturated hydrocarbon group from the viewpoint of redox durability.
  • the aliphatic unsaturated hydrocarbon group is preferably an alkenylene group, and specific examples thereof include 1,2-vinylene group, 1,3-propenylene group, 1,2-propenylene group and 1,4-butenylene group. Etc. Among these, a vinylene group is particularly preferable because a conjugate plane is expanded by improving the planarity of the molecule, and the charge is delocalized and the stability of the compound is easily increased.
  • the number of carbon atoms of the unsaturated aliphatic hydrocarbon group is preferably 2 or more from the viewpoint of planarity and charge spread, and is preferably 10 or less, and more preferably 6 or less.
  • the number of carbon atoms contained in the aliphatic hydrocarbon group is preferably large from the viewpoint of increasing the solubility, but on the other hand, it is preferably small from the viewpoint of the stability of the compound and the film density. Specifically, the carbon number is usually 1 or more, preferably 4 or more, more preferably 6 or more, and usually 70 or less, preferably 60 or less, more preferably 36 or less.
  • structures, such as a polymer which has a repeating unit represented by following formula (11), (12), (13), (14), are further more preferable.
  • a polymer having a repeating unit represented by the following formula (11) is synthesized by a reaction that forms an N—Ar bond such as a Buchwald-Hartwig reaction or an Ulmann reaction.
  • Ar 1 to Ar 3 each independently represents an aromatic hydrocarbon ring group or aromatic heterocyclic group as defined above
  • Z represents a divalent group, preferably — It represents a group in which 1 to 24 groups selected from the group consisting of CR 1 R 2 —, —CO—, —O—, —S—, —SO 2 —, —SiR 3 R 4 — are linked.
  • R 1 to R 4 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an aromatic hydrocarbon ring group or an aromatic heterocyclic group as defined above.
  • R 1 and R 2 , R 3 and R 4 may be bonded to each other to form a ring.
  • a represents an integer of 0 to 8. When a is an integer of 2 to 8, Ar 3 and Z may be different from each other.
  • n represents the number of repeating units.
  • Ar 1 to Ar 3 , Z, and a have the same definitions as in the formula (11).
  • b represents an integer of 0 to 8.
  • X 1 represents a sulfonate group such as a halogen atom or a trifluoromethanesulfonyloxy group (CF 3 SO 2 O—).
  • the monomers represented by the formulas (M1-1) to (M1-3) may be used independently or in combination of two or more, preferably 10 or less.
  • a polymer having a repeating unit represented by the following formula (12) is synthesized by a reaction that forms an Ar—Ar bond, such as a Yamamoto reaction, a Negishi reaction, a Migita-Kosugi-Stile reaction, or a Suzuki-Miyaura reaction.
  • Ar 1 to Ar 3 , Z, a, b, X 1 , and n are formula (11), formula (M1-1) to It has the same definition as in formula (M1-3).
  • G represents a zinc atom having a substituent such as BrZn- in the case of a Negishi reaction, or a substituent such as (CH 3 ) 3 Sn- in the case of a Migita-Kosugi-Stile reaction.
  • a polymer having a repeating unit represented by the following formula (13) is synthesized by a reaction that forms an O—Ar bond or an S—Ar bond.
  • Ar 1 to Ar 3 , Z, a, b, X 1 , and n are formula (11), formula (M1-1) to It has the same definition as in formula (M1-3).
  • Q 1 represents an oxygen atom or a sulfur atom.
  • Ar 1 to Ar 3 , Z, a, b, Q 1 , and X 1 are present in two or more, they are different from each other. May be.
  • a polymer having a repeating unit represented by the following formula (14) is synthesized by a reaction that forms an ester bond or an amide bond.
  • Ar 1 to Ar 3 , Z, a, b, and n are formula (11), formula (M1-1) to formula (M1). -3) Same definition as in In Formula (14), Formula (M4-1), and Formula (M4-2), Q 2 represents a carbonyl group or a sulfonyl group, and Q 3 represents an oxygen atom, a sulfur atom, or a —NR 5 — group (R 5 represents a hydrogen atom, an alkyl group which may have a substituent, an aromatic hydrocarbon ring group or an aromatic heterocyclic group as defined above, and X 2 represents a halogen atom. In Formula (14), Formula (M4-1), and Formula (M4-2), when Ar 1 to Ar 3 , Z, a, b, Q 2 , and Q 3 are present in two or more, they are different from each other. May be.
  • a polymer having a repeating unit represented by the formula (11) and the formula (12) is preferable, and a polymer having a repeating unit represented by the formula (11) is preferable. More preferable in terms of hole transportability and durability.
  • a is preferably 0 from the viewpoint of excellent hole injection / transport properties.
  • a is preferably 1 or 2, and more preferably 1, in terms of wide band gap and excellent hole transportability.
  • Z is preferably —CR 1 R 2 — because it is excellent in durability.
  • PEDOT / PSS Advanced Mater., 2000, 12 volumes, 481 pages
  • emeraldine hydrochloride J. Chem., 1990, Vol. 94, p. 7716
  • the polymer compound according to the present invention preferably has an insolubilizing group.
  • the insolubilizing group is preferably a crosslinkable group or a dissociating group.
  • the insolubilizing group is preferably a crosslinkable group because it is chemically bonded three-dimensionally.
  • the polymer compound according to the present invention preferably has a crosslinkable group.
  • the crosslinkable group refers to a group that reacts with the same or different groups of other molecules located nearby by irradiation with heat and / or active energy rays to form a new chemical bond.
  • these crosslinkable groups can be used for crosslinking to insolubilize the conductive thin film. Thereby, a functional thin film can be further laminated
  • the crosslinkable group is selected from the following ⁇ crosslinkable group group T> for ease of bonding. ⁇ Crosslinkable group T>
  • R 21 to R 25 each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
  • Ar 41 represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
  • the benzocyclobutene ring may have a substituent.
  • a cyclic ether group such as an epoxy group and an oxetane group, and a cationically polymerizable group such as a vinyl ether group are preferable in terms of high reactivity and easy crosslinking to an organic solvent.
  • an oxetane group is particularly preferable from the viewpoint that the rate of cationic polymerization can be easily controlled, and a vinyl ether group is preferable from the viewpoint that a hydroxyl group that may cause deterioration of the device during the cationic polymerization is hardly generated.
  • an arylvinylcarbonyl group such as a cinnamoyl group or a group that undergoes a cycloaddition reaction such as a benzocyclobutene ring is preferable in terms of further improving the electrochemical stability, and the structure stability after crosslinking is high.
  • a benzocyclobutene ring is particularly preferred.
  • the crosslinkable group may be directly bonded to an aromatic hydrocarbon group or an aromatic heterocyclic group in the molecule, and —O— group, —C ( ⁇ O) —
  • Specific examples of the crosslinkable group via these divalent groups, that is, a group containing a crosslinkable group are as shown in ⁇ Group group T ′ containing a crosslinkable group> below, but the present invention is not limited thereto. It is not something.
  • ⁇ Group T ′ containing crosslinkable group> are as shown in ⁇ Group group T ′ containing a crosslinkable group> below, but the present invention is not limited thereto. It is not something.
  • the polymer compound in the present invention preferably contains a repeating unit consisting of the following formula (2).
  • p represents an integer of 0 to 3
  • Ar 21 and Ar 22 each independently have a direct bond, an aromatic hydrocarbon group which may have a substituent, or a substituent.
  • Each of Ar 23 to Ar 25 independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
  • T 2 represents a crosslinkable group.
  • the aromatic hydrocarbon group that may have a substituent that can be used for Ar 21 , Ar 22, and Ar 24 , or the aromatic heterocyclic group that may have a substituent is the above-mentioned Ar a . It is the same as the structure represented.
  • T 2 is selected from the aforementioned crosslinkable group T and T ′.
  • T 2 is particularly preferably a group containing a group represented by the following formula (3).
  • the benzocyclobutene ring in formula (3) may have a substituent.
  • the substituents may be bonded to each other to form a ring.
  • the substituent that Ar 21 to Ar 25 may have is the same as the substituent that the aromatic hydrocarbon group or aromatic heterocyclic group represented by the aforementioned Ar a or Ar b may have. is there.
  • the polymer compound in the present invention preferably includes a partial structure consisting of the following formula (4).
  • Ar 6 and Ar 7 each independently represent a divalent aromatic ring group which may have a substituent
  • Ar 8 represents an aromatic ring which may have a substituent
  • R 8 and R 9 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted carbon group having 1 to 12 carbon atoms.
  • R 8 and R 9 may be bonded to each other to form a ring.
  • p represents an integer of 1 to 5.
  • the polymer compound in the present invention preferably includes a partial structure consisting of the following formula (6).
  • Ar 31 , Ar 33 , Ar 34 and Ar 35 may each independently have a divalent aromatic hydrocarbon ring group or substituent which may have a substituent.
  • Ar 32 represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
  • R 11 represents an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted alkoxy group having 1 to 12 carbon atoms
  • R 12 to R 17 each represents Independently, it may have a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted alkoxy group having 1 to 12 carbon atoms, or a substituent.
  • R 12 and R 13 may combine with each other to form a ring.
  • R 14 and R 15 may combine with each other to form a ring.
  • R 16 and R 17 may be bonded to each other to form a ring.
  • l, m and n each independently represents an integer of 0 to 2.
  • the divalent aromatic hydrocarbon group which may have a substituent which can be used for Ar 31 , Ar 33 , Ar 34 , Ar 35 and Ar 6 , Ar 7 can be used for the aforementioned Ar a. It is the same as a divalent aromatic hydrocarbon group.
  • the aromatic hydrocarbon group which may have a substituent which can be used for Ar 32 and Ar 8 is the same as the aromatic hydrocarbon group which can be used for Ar b described above.
  • R 12 to R 17 and R 8 and R 9 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent.
  • An aromatic group that may be present, may be bonded to each other to form a ring.
  • R 11 , R 12 to R 17, and R 8 and R 9 are preferably an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms from the viewpoint of solubility. Groups are more preferred.
  • the substituent which Ar 31 , Ar 33 , Ar 34 , Ar 35 , Ar 6 , Ar 7 , R 12 to R 17 , R 8 , R 9 may have is represented by the aforementioned Ar a or Ar b.
  • the substituent which the aromatic hydrocarbon group or aromatic heterocyclic group which may have, or the said crosslinkable group is mentioned.
  • the weight average molecular weight (Mw) of the polymer compound in the present invention is usually 3,000,000 or less, preferably 1,000,000 or less, more preferably 500,000 or less, and usually 2,000 or more, preferably Is 3,000 or more, more preferably 5,000 or more.
  • the number average molecular weight (Mn) of the polymer compound is usually 3,000 or more, preferably 6,000 or more, and usually 1,000,000 or less, preferably 500,000 or less. If the weight average molecular weight or number average molecular weight is below the lower limit of this range, the insolubility of the crosslinked layer in the organic solvent may be reduced, and lamination may not be possible, and the glass transition temperature may be reduced and heat resistance may be impaired. There is sex. If the upper limit of this range is exceeded, there is a possibility that a flat film cannot be obtained without dissolving in the organic solvent even before crosslinking.
  • the dispersity (Mw / Mn) of the polymer compound in the present invention is usually 3.5 or less, preferably 2.5 or less, more preferably 2.0 or less. If the degree of dispersion of the polymer compound exceeds the upper limit of this range, purification may be difficult, solubility in organic solvents may be reduced, and charge transport capability may be reduced.
  • the dispersity is ideally 1.0. Usually, this weight average molecular weight is determined by SEC (size exclusion chromatography) measurement.
  • the elution time is shorter for higher molecular weight components and the elution time is longer for lower molecular weight components, but using the calibration curve calculated from the elution time of polystyrene (standard sample) with a known molecular weight, the elution time of the sample is changed to the molecular weight.
  • the weight average molecular weight is calculated by conversion.
  • the conductive thin film precursor is prepared by mixing a conductive thin film forming material such as the above-described polymer compound and other components as necessary with a solvent that can be dissolved or dispersed.
  • the solvent contained in the conductive thin film precursor is not particularly limited, but the polymer compound is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1.0%. It is a solvent that dissolves by weight% or more.
  • the boiling point of the solvent is usually 110 ° C. or higher, preferably 140 ° C. or higher, more preferably 180 ° C. or higher, particularly preferably 200 ° C. or higher, usually 400 ° C. or lower, and preferably 300 ° C. or lower. If the boiling point of the solvent is too low, the drying speed is too high and the film quality may be deteriorated. Further, if the boiling point of the solvent is too high, it is necessary to increase the temperature of the drying step, which may adversely affect other layers and the substrate.
  • the solvent contained in the conductive thin film precursor is not particularly limited as long as it satisfies the above required characteristics, and includes ester solvents, aromatic hydrocarbon solvents, ether solvents, halogen-containing organic solvents, amide solvents, and the like.
  • An ester solvent, an aromatic hydrocarbon solvent, and an ether solvent are preferable because of high solubility and less adverse effects of the residual solvent.
  • ester solvents include aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate, and n-butyl lactate, and phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and benzoic acid. and aromatic esters such as n-butyl.
  • aromatic hydrocarbon solvent examples include toluene, xylene, methicylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, and methylnaphthalene.
  • ether solvents include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA), 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, and anisole.
  • ether solvents such as aromatic ethers such as phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole and 2,4-dimethylanisole.
  • halogen-containing organic solvent examples include 1,2-dichloroethane, chlorobenzene and o-dichlorobenzene.
  • amide solvent examples include N, N-dimethylformamide and N, N-dimethylacetamide. In addition to these, dimethyl sulfoxide and the like can also be used. These solvents may be used alone or in combination of two or more in any combination and ratio.
  • the amount of the solvent contained in the conductive thin film precursor is usually 10% by weight or more, preferably 50% by weight or more, more preferably 60% by weight or more, particularly preferably 80% by weight or more, and usually 99.99. % By weight or less.
  • the amount of the conductive thin film forming material contained in the conductive thin film precursor is preferably larger in terms of increasing the viscosity of the composition, but is preferably smaller in terms of solubility.
  • the amount of the conductive thin film forming material included for forming the conductive thin film is usually 0.01% by weight or more, preferably 0.1% by weight or more, More preferably, it is at least 50% by weight, and on the other hand, it is usually at most 50% by weight, preferably at most 40% by weight, more preferably at most 20% by weight.
  • the conductive thin film forming composition may contain two or more conductive thin film forming materials, and in that case, the total of the two or more types is preferably within the above range.
  • the lower limit of the substrate temperature in infrared irradiation is usually 150 ° C. or higher, preferably 160 ° C. or higher, more preferably 170 ° C. or higher, and further preferably 180 ° C. or higher.
  • the upper limit is 300 degrees C or less normally, Preferably it is 290 degrees C or less, More preferably, it is 280 degrees C or less, More preferably, it is 270 degrees C or less.
  • the conductive thin film is not heated more than necessary, and if the conductive thin film is a material that is difficult to be heated by infrared rays, heat is applied from the substrate to the conductive thin film. Can do. Furthermore, within the above range, when the conductive thin film is formed by coating, the solvent can be removed, the density in the layer can be further increased, and the adhesion between the layers can be further increased. The characteristics of the conductive thin film can be improved.
  • the lower limit of the holding time in the above temperature range is usually 5 seconds or longer, preferably 20 seconds or longer, more preferably 30 seconds or longer.
  • the upper limit is usually 30 minutes or less, preferably 25 minutes or less, more preferably 20 minutes or less.
  • the polymer compound according to the present invention when a conductive thin film is formed by coating, when the polymer compound according to the present invention has a crosslinkable group, it can be crosslinked and insolubilized by the crosslinkable group. preferable.
  • the lower limit of the time for which the temperature of the substrate in infrared irradiation is held at a constant temperature in the temperature range of 150 ° C. or more and 300 ° C. or less is usually 20 seconds or more, preferably 30 seconds or more, more preferably. 1 minute or more.
  • the upper limit is usually 15 minutes or less, preferably 8 minutes or less, more preferably 5 minutes or less.
  • the lower limit of the heating rate of the substrate in the conductive thin film laminate is usually 10 ° C./min or more, preferably 20 ° C./min or more, more preferably 30 ° C./min or more.
  • the upper limit is usually 250 ° C./min or less, preferably 200 ° C./min or less, more preferably 150 ° C./min or less. Further, this temperature rise rate is measured in 30 seconds. By setting it as this temperature increase rate range, while suppressing the rapid contraction of an electroconductive thin film, an electroconductive thin film can be heated effectively and productivity can be raised.
  • the infrared transmittance of the substrate has a minimum value of the transmittance in the wavelength range of 2000 to 3300 nm, and the product ( ⁇ ) of the wavelength at the minimum value and the peak wavelength of the infrared heater indicates that the temperature of the substrate is 150 ° C. or higher.
  • the value ( ⁇ / t) divided by the holding time (t) in the above satisfies the relationship of the following formula (7).
  • the lower limit of alpha / t is usually 0.002 .mu.m 2 / s or more, preferably 0.005 .mu.m 2 / s or more, more preferably 0.01 [mu] m 2 / s or more, even more preferably at 0.02 [mu] m 2 / s or more .
  • the upper limit is usually 0.2 ⁇ m 2 / s or less, preferably 0.1 ⁇ m 2 / s or less, more preferably 0.05 ⁇ m 2 / s or less, and further preferably 0.04 ⁇ m 2 / s or less.
  • the substrate can remove the heat of the conductive thin film that has been heated by infrared rays, and the breakdown of the conductive thin film can be suppressed.
  • the substrate is heated appropriately and the thin film is heated with the heat. That is, when ⁇ / t is in this range, the conductive thin film can be appropriately heated, and the performance of the conductive thin film can be improved.
  • the parameter ⁇ / t will be described below.
  • the parameter ⁇ is inversely proportional to the ease with which the substrate is heated. That is, when ⁇ is small, the substrate is easily heated. To heat the conductive thin film, the holding time t can be short, and when ⁇ is large, the substrate is difficult to be heated and the time t is long. Therefore, by dividing ⁇ by t, an appropriate heating condition can be set in manufacturing the conductive thin film laminate according to the present invention, and the range is as described above.
  • a thick film is a film whose thickness is usually 50 nm or more, preferably 60 nm or more, more preferably 100 nm or more, further preferably 120 nm or more, usually 1 ⁇ m or less, preferably 800 nm or less, more preferably 600 nm or less. Thickness.
  • the hole transporting material on the substrate or the transparent electrode is restrained from insolubilization such as a crosslinking reaction because the molecular motion is restricted by the adsorption of molecules on the surface.
  • the film thickness of the conductive thin film is 50 nm or more, sufficient molecular motion can be achieved, the collision probability between the crosslinking groups can be increased, and the crosslinking reaction can proceed.
  • the thickness of the conductive thin film is 50 nm or more, the heat generated by infrared induction heating will contribute to the promotion of the crosslinking reaction of the polymer compound without the heat being taken away by the substrate due to heat transfer. Can do.
  • Another advantage of making the conductive thin film thicker is to increase the coverage of foreign matter that becomes a leak source. Furthermore, it is possible to increase the degree of freedom in optical design of the organic electroluminescent element based on light interference.
  • the film thickness of the conductive thin film is 1 ⁇ m or less, the time for drying the solvent can be shortened, and the amount of the polymer compound used can be limited, thereby reducing the cost.
  • the lower limit value of the substrate temperature in infrared heating is usually 70 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 ° C. or higher, more preferably 140 ° C. or higher. It is.
  • the upper limit is 300 degrees C or less normally, Preferably it is 290 degrees C or less, More preferably, it is 280 degrees C or less, More preferably, it is 270 degrees C or less.
  • the conductive thin film cannot be heated more than necessary, and if it is a material that is difficult to be heated by infrared rays, heat can be applied from the substrate to the conductive thin film. Furthermore, within the above range, when a conductive thin film is formed by coating, the solvent can be removed, the density in the layer can be increased, and the adhesion between the layers can be further improved. The characteristics of the conductive thin film can be improved.
  • the lower limit of the holding time in the above temperature range is usually 5 seconds or longer, preferably 20 seconds or longer, more preferably 30 seconds or longer.
  • the upper limit is usually 30 minutes or less, preferably 25 minutes or less, more preferably 20 minutes or less.
  • the polymer compound according to the present invention when a conductive thin film is formed by coating, when the polymer compound according to the present invention has a crosslinkable group, it can be crosslinked and insolubilized by the crosslinkable group. preferable.
  • the time during which the temperature of the substrate is maintained at a constant temperature in the temperature range of 70 ° C. or more and 300 ° C. or less is usually 20 seconds or more, preferably 30 seconds or more, more preferably 1 minute. That's it.
  • the upper limit is usually 15 minutes or less, preferably 8 minutes or less, more preferably 5 minutes or less.
  • the lower limit of the heating rate of the substrate is usually 10 ° C./min or more, preferably 20 ° C./min or more, more preferably 30 ° C./min or more.
  • the upper limit is usually 250 ° C./min or less, preferably 200 ° C./min or less, more preferably 150 ° C./min or less. Further, this temperature rise rate is measured in 30 seconds. By setting it as this temperature increase rate range, an electroconductive thin film can be heated effectively, without reducing an electroconductive thin film rapidly, and productivity can be raised.
  • the infrared transmittance of the substrate has a minimum value of the transmittance in a wavelength range of 2000 to 3300 nm, and the product ( ⁇ ) of the wavelength at the minimum value and the peak wavelength of the infrared heater is the time (t divided by the) ( ⁇ / t), the lower limit is usually 0.002 .mu.m 2 / s or more, preferably 0.005 .mu.m 2 / s or more, more preferably 0.01 [mu] m 2 / s or higher, more preferably 0.02 ⁇ m 2 / s or more.
  • the upper limit is usually 0.2 ⁇ m 2 / s or less, preferably 0.15 ⁇ m 2 / s or less, more preferably 0.10 ⁇ m 2 / s or less, and further preferably 0.08 ⁇ m 2 / s or less.
  • the substrate can remove the heat of the conductive thin film that has been heated by infrared rays, and the breakdown of the conductive thin film can be suppressed.
  • the substrate is appropriately heated and heats the conductive thin film with the heat. That is, when ⁇ / t is in this range, the conductive thin film can be appropriately heated, and the performance of the conductive thin film can be improved.
  • Examples of the method for applying the conductive thin film precursor composition in the present invention include spin coating, dip coating, die coating, bar coating, blade coating, roll coating, spray coating, capillary coating, and inkjet. Methods such as a printing method, a nozzle printing method, a screen printing method, a gravure printing method, and a flexographic printing method can be employed.
  • the temperature at the time of film formation is preferably 10 ° C. or higher, and preferably 50 ° C. or lower from the viewpoint that film defects due to crystals generated in the composition are less likely to occur.
  • the relative humidity at the time of film formation is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.01 ppm or more and usually 80% or less.
  • the coating film may be dried by heating, drying under reduced pressure, or the like to obtain a dry film.
  • the heating means include a hot plate and a clean oven.
  • a dry film can be obtained by heating the substrate on which the coating film is formed on a hot plate or by heating in an oven.
  • a dried film can be obtained by putting the substrate on which the coating film is formed into a pressure reducing device and reducing the pressure. Since the surface of the conductive thin film after infrared heating becomes flatter, it is preferable to dry the coating film before the step of heating with infrared radiation according to the present invention to form a dry film.
  • a conductive thin film laminate can be manufactured without applying excessive heat to the conductive thin film.
  • a polymer material usually forms a string (coil) in a solution.
  • a slightly shrunk shape is obtained.
  • the thread will spread and become in a random state where they are intertwined.
  • the heating time is shortened, it is considered that such a thread-thread state is maintained.
  • a method for discriminating the structure can be selected as appropriate, but measurement by fine angle X-ray scattering (GI-SAXS) is preferable for measuring the structure of the thin film layer.
  • This structure is usually 1 to 50 nm, preferably 2 to 40 nm, more preferably 3 to 30 nm. If it is outside this range, there is a possibility that a sufficient conductive path cannot be obtained.
  • the conductive thin film containing the polymer compound formed as described above is preferably provided as a hole injection layer or a hole transport layer in the organic electroluminescence device described later.
  • an organic electroluminescent element will be described as a suitable example of the conductive thin film laminate.
  • FIG. 1 is a schematic cross-sectional view showing a structural example suitable for an organic electroluminescent device.
  • reference numeral 1 is a substrate
  • reference numeral 2 is an anode
  • reference numeral 3 is a hole injection layer
  • reference numeral 4 is a hole transport layer.
  • 5 represents a light emitting layer
  • 6 represents a hole blocking layer
  • 7 represents an electron transport layer
  • 8 represents an electron injection layer
  • 9 represents a cathode.
  • layers corresponding to the conductive thin film layer of the present invention are denoted by reference numerals 3 to 8. At least one of these conductive thin film layers is preferably formed by a wet film formation method, and further, the layer is formed by infrared heating. Next, the light emitting layer will be described as a conductive thin film.
  • the light emitting layer is formed by applying a light emitting layer composition containing a light emitting material and a solvent and baking.
  • Luminescent material A known material can be used as the light emitting material.
  • a fluorescent material or a phosphorescent material may be used. Details will be described later.
  • the light emitting layer composition contains at least a light emitting material and a solvent.
  • a solvent the same solvent as the solvent contained in the composition for forming an electroconductive thin film described above can be used.
  • the light emitting material contained in the composition is usually contained in an amount of 0.01% by weight or more, preferably 0.05% by weight or more, and more preferably 0.1% by weight or more. Further, the light emitting material is usually contained in an amount of 35% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less. In addition, when using together 2 or more types of luminescent material, it is preferable that these total content is included in the said range.
  • the boiling point of the solvent is usually 75 ° C. or higher, preferably 100 ° C. or higher, more preferably 110 ° C. or higher, more preferably 120 ° C. or higher, and usually 350 ° C. or lower, preferably 280 ° C. or lower, more preferably 275 ° C. or lower. More preferably, it is 260 ° C. or lower. If it is more than this lower limit, there is no possibility that the coating film becomes non-uniform due to drying of the coating film before heating and firing of the light emitting layer. Moreover, if it is below this upper limit, a solvent can fully be removed and the desired characteristic of an organic electroluminescent layer can be acquired. Further, the solvent can be removed in a short time, and the productivity is improved.
  • the coating method of the light emitting layer composition the above-described coating method of the conductive thin film forming composition can be used.
  • the light emitting layer composition applied as described above is fired by infrared heating.
  • the lower limit temperature of the substrate is usually 70 ° C. or higher, preferably 75 ° C. or higher, more preferably 80 ° C. or higher
  • the upper limit temperature is usually 150 ° C. or lower, preferably 140 ° C. or lower, more preferably. Is 130 ° C. or lower. Within this temperature range, usually 5 seconds or more, preferably 10 seconds or more, more preferably 20 seconds or more, particularly preferably 30 seconds or more, usually 20 minutes or less, preferably 15 minutes or less, more preferably 10 minutes or less, even more preferably. Hold for 8 minutes or less.
  • the temperature and the holding time are not less than the lower limit value, a sufficiently dense film can be formed, and when the light emitting layer composition is applied to the previously formed hole injection layer or hole transport layer, Desirable device characteristics can be realized without sufficiently evaporating the solvent and remaining of the solvent. Further, if the temperature and the holding time are not more than the upper limit values, there is no possibility of destroying the light emitting layer due to absorption of infrared rays, so that the device characteristics can be maintained.
  • the time during which the temperature of the substrate is kept constant in the above temperature range is usually 20 seconds or longer, preferably 30 seconds or longer, more preferably 1 minute or longer, and usually 10 minutes or shorter, preferably 8 Min or less, more preferably 5 min or less.
  • desired characteristics can be exhibited without forming a metastable state.
  • the light emitting layer is formed from a mixture of a host, a dopant, and the like, if the light emitting layer is kept at a steady temperature for a long time, the light emitting layer component causes phase separation or the roughness of the surface structure increases in the film. This is because there is a fear.
  • constant temperature refers to a state in which the temperature is maintained within a range of ⁇ 5 ° C.
  • the heating rate of the substrate is usually 10 ° C./min or more, preferably 20 ° C./min or more, more preferably 30 ° C./min or more, usually 50 ° C./min or less, preferably 200 ° C./min or less, more Preferably it is 150 degrees C / min or less.
  • the heating rate is lower than the above, the light emitting layer is not destroyed without a rapid temperature rise.
  • the temperature increase rate is measured for 30 seconds.
  • a light emitting layer contains a host and a dopant, and the quantity ratio needs to be precisely controlled.
  • the wet film forming method is an effective method in that since the ink containing the light emitting material and the solvent is preliminarily weighed and precisely adjusted, there is no change in the quantity ratio and the variation of elements can be suppressed. Further, in the vapor deposition method, the material once input into the vapor deposition source of the film forming apparatus is continuously heated for a long time, and as the apparatus becomes larger, the time increases, and the problem of material deterioration becomes obvious.
  • the heating can be a useful method in that the heating time can be shortened by heating using the infrared rays of the present invention.
  • infrared rays as a heating means, firing can be performed in a relatively short time compared to using a hot stove or a hot plate. Therefore, the influence of gas in the firing atmosphere such as oxygen and moisture and the influence of dust are minimized.
  • Another advantage is that it can be limited.
  • At least one organic layer is fired by infrared rays at a temperature higher than the firing temperature of the light emitting layer.
  • heating of the light emitting layer may cause degassing from the hole injection layer or the hole transport layer, which may contaminate the light emitting layer.
  • the hole injection layer or hole transport layer is heated by a method other than infrared rays, a skin layer is formed on the surface, and residual solvent may be trapped in the hole injection layer or hole transport layer. is there. This is because molecular vibration due to infrared heating occurs, and the residual solvent is easily removed, and the skin layer is difficult to form due to molecular vibration, or even if formed, the solvent is easy to remove.
  • infrared heating In infrared heating, the type of heater that can be used, the minimum value of infrared transmission of the substrate, the infrared transmittance, the peak wavelength of the infrared heater and the minimum value of the infrared transmission of the substrate and the product of the peak wavelength of the infrared Peter ( ⁇ ) is This is the same as the infrared heating of the conductive thin film described above. Further, the infrared transmittance of the substrate has a minimum value of transmittance in the wavelength range of 2000 to 3300 nm, and the product ( ⁇ ) of the wavelength at the minimum value and the peak wavelength of the infrared heater is 70 ° C.
  • the value ( ⁇ / t) divided by the holding time (t) at 150 ° C. or lower satisfies the relationship of the following formula (8).
  • the lower limit of alpha / t is usually 0.003 .mu.m 2 / s or more, preferably, 0.004 m 2 / s or more, more preferably 0.005 .mu.m 2 / s or more, more preferably, 0.008 .mu.m 2 / s or more It is.
  • the upper limit is usually 0.5 ⁇ m 2 / s or less, preferably 0.4 ⁇ m 2 / s or less, more preferably 0.3 ⁇ m 2 / s or less, and particularly preferably 0.2 ⁇ m 2 / s or less.
  • the substrate removes the heat of the light emitting layer that has been heated by infrared rays, and the destruction of the light emitting layer can be suppressed. Further, even when the light emitting layer is weakly heated by infrared rays, the substrate is appropriately heated, and the light emitting layer is heated with the heat. That is, when ⁇ / t is in this range, the light emitting layer can be appropriately heated, and the performance of the organic electroluminescent element can be improved.
  • the solvent When heating with infrared rays, if the amount is below the above upper limit value, there is no possibility of destroying the light-emitting layer, which is a thin film, because the solvent is rapidly evaporated or boiled by infrared electromagnetic induction heating. When it is at least this lower limit, the solvent can be sufficiently removed, and the desired characteristics of the organic electroluminescent layer can be obtained. Further, the solvent can be removed in a short time, and the productivity is improved.
  • the film thickness of the light emitting layer is usually 3 nm or more, preferably 5 nm or more, and usually 300 nm or less, preferably 100 nm or less.
  • fluorescent light-emitting material blue fluorescent dye
  • examples of the fluorescent light-emitting material blue fluorescent dye that emits blue light include naphthalene, chrysene, perylene, pyrene, anthracene, coumarin, p-bis (2-phenylethenyl) benzene, and derivatives thereof.
  • fluorescent dyes that give green light emission include quinacridone derivatives, coumarin derivatives, and aluminum complexes such as Al (C 9 H 6 NO) 3 .
  • fluorescent light emitting material yellow fluorescent dye
  • red fluorescent dyes fluorescent dyes
  • DCM dicyanomethyrene
  • red fluorescent dyes red fluorescent dyes
  • DCM dicyanomethyrene
  • rhodamine derivatives examples thereof include benzothioxanthene derivatives and azabenzothioxanthene.
  • phosphorescent materials include tris (2-phenylpyridine) iridium, tris (2-phenylpyridine) ruthenium, tris (2-phenylpyridine) palladium, bis (2-phenylpyridine) platinum, tris (2- Phenylpyridine) osmium, tris (2-phenylpyridine) rhenium, octaethyl platinum porphyrin, octaphenyl platinum porphyrin, octaethyl palladium porphyrin, octaphenyl palladium porphyrin, and the like.
  • Polymeric light-emitting materials include poly (9,9-dioctylfluorene-2,7-diyl), poly [(9,9-dioctylfluorene-2,7-diyl) -co- (4,4′- (N- (4-sec-butylphenyl)) diphenylamine)], poly [(9,9-dioctylfluorene-2,7-diyl) -co- (1,4-benzo-2 ⁇ 2,1'-3 ⁇ -Triazole)] and polyphenylene vinylene materials such as poly [2-methoxy-5- (2-hexylhexyloxy) -1,4-phenylene vinylene].
  • the above-described polymer compound can be used as a light-emitting material.
  • the molecular weight of the compound used as the light emitting material is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 10,000 or less, preferably 5000 or less, more preferably 4000 or less, still more preferably 3000 or less, and usually 100 or more, Preferably it is 200 or more, More preferably, it is 300 or more, More preferably, it is the range of 400 or more. If the molecular weight of the luminescent material is too small, the heat resistance will be significantly reduced, gas will be generated, the film quality will deteriorate when the film is formed, or the morphology of the organic electroluminescent element will change due to migration, etc. Sometimes come. On the other hand, if the molecular weight of the luminescent material is too large, it tends to be difficult to purify the organic compound, or it may take time to dissolve in the solvent.
  • any 1 type may be used for the luminescent material mentioned above, and 2 or more types may be used together by arbitrary combinations and a ratio.
  • a phosphorescent material is preferred.
  • the phosphorescent material for example, a long-period type periodic table (hereinafter, unless otherwise specified, the term “periodic table” refers to a long-period type periodic table) selected from Group 7 to 11 A Werner complex or an organometallic complex compound containing a metal as a central metal.
  • a metal complex compound having Ir which is a heavy element, is more preferable because it has excellent heat resistance.
  • the phosphorescent organometallic complex of the phosphorescent material is preferably a compound represented by the following formula (III) or formula (IV).
  • M represents a metal
  • q represents a valence of the metal
  • L and L ′ represent a bidentate ligand
  • j represents a number of 0, 1 or 2.
  • the plurality of L or the plurality of L ′ may be the same or different.
  • M 7 represents a metal
  • T represents a carbon atom or a nitrogen atom.
  • R 92 to R 95 each independently represents a substituent. However, when T is a nitrogen atom, R 7 No 94 and R 95 )
  • M is a metal selected from Groups 7 to 11 of the periodic table, and preferably includes ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, gold, and the like. Is iridium or platinum, and is most preferably iridium from the viewpoint of high stability and high luminous efficiency.
  • bidentate ligand L represents a ligand having the following partial structure.
  • ring A1 represents an aromatic ring group which may have a substituent.
  • the aromatic ring group in the present invention may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • the aromatic hydrocarbon ring group include a 5- or 6-membered monocyclic ring or a 2-5 condensed ring having one free valence.
  • aromatic hydrocarbon ring group examples include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene having one free valence. Ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.
  • aromatic heterocyclic group examples include a 5- or 6-membered monocyclic ring or a 2-4 condensed ring having one free valence.
  • a furan ring a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, and a pyrroloimidazole ring having one free valence.
  • ring A2 represents a nitrogen-containing aromatic heterocyclic group which may have a substituent.
  • the nitrogen-containing aromatic heterocyclic group include a 5- or 6-membered monocyclic ring or a 2-4 condensed ring having one free valence.
  • Specific examples include a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, and a fluropyrrole having one free valence.
  • each of ring A1 and ring A2 may have include a halogen atom; an alkyl group; an alkenyl group; an alkoxycarbonyl group; an alkoxy group; an aralkyl group; an aryloxy group; a dialkylamino group; Carbazolyl group; acyl group; haloalkyl group; cyano group; aromatic hydrocarbon ring group and the like.
  • ring A1 is a nitrogen-containing aromatic heterocyclic group and ring A2 may have an aromatic hydrocarbon ring group as a substituent.
  • bidentate ligand L ′ represents a ligand having the following partial structure. However, in the following formulae, “Ph” represents a phenyl group.
  • L ′ the following ligands are preferable from the viewpoint of stability of the complex.
  • More preferable examples of the compound represented by the formula (III) include compounds represented by the following formulas (IIIa), (IIIb), and (IIIc).
  • M 4 represents the same metal as M
  • w represents the valence of the metal
  • ring A1 represents an aromatic hydrocarbon ring group which may have a substituent.
  • Ring A2 represents an optionally substituted nitrogen-containing aromatic heterocyclic group, and when there are a plurality of rings A1 or A2, the plurality of rings A1 or A2 are the same or different. May be.
  • M 5 represents the same metal as M
  • w-1 represents the valence of the metal
  • ring A1 represents an aromatic ring group which may have a substituent.
  • Ring A2 represents a nitrogen-containing aromatic heterocyclic group which may have a substituent, and when there are a plurality of rings A1 or A2, the plurality of rings A1 or A2 may be the same or different. May be.
  • M 6 represents the same metal as M, w represents the valence of the metal, j represents 0, 1 or 2, and ring A1 and ring A1 ′ each represent Independently, it represents an optionally substituted aromatic ring group, and ring A2 and ring A2 ′ each independently represent a nitrogen-containing aromatic heterocyclic group optionally having a substituent.
  • the plurality of rings A1, ring A1 ′, ring A2 or ring A2 ′ may be the same or different.
  • aromatic group of ring A1 and ring A1 ′ include phenyl group, biphenyl group, naphthyl group, anthryl group, thienyl group, furyl group, benzothienyl group, benzofuryl group.
  • aromatic group of ring A1 and ring A1 ′ include phenyl group, biphenyl group, naphthyl group, anthryl group, thienyl group, furyl group, benzothienyl group, benzofuryl group.
  • preferred examples of the nitrogen-containing aromatic heterocyclic group for ring A2 and ring A2 ′ include pyridyl group, pyrimidyl group, pyrazyl group, triazyl group, benzothiazole group, benzoxazole group. Benzoimidazole group, quinolyl group, isoquinolyl group, quinoxalyl group, phenanthridyl group and the like.
  • the aromatic group of ring A1 and ring A1 ′ and the nitrogen-containing aromatic heterocyclic group of ring A2 and ring A2 ′ may have a halogen atom;
  • a diarylamino group having 8 to 24 carbon atoms, a 5- or 6-membered monocyclic ring or an aromatic hydrocarbon ring group or carbazolyl group which is a 2 to 4 condensed ring further has a substituent at the aryl moiety constituting the group.
  • the substituent may be substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aralkyl group having 1 to 24 carbon atoms, or an alkyl group having 1 to 12 carbon atoms.
  • substituents may be connected to each other to form a ring.
  • a substituent of the ring A1 and a substituent of the ring A2 are bonded, or a substituent of the ring A1 ′ and a substituent of the ring A2 ′ are bonded.
  • a condensed ring may be formed. Examples of such a condensed ring include a 7,8-benzoquinoline group.
  • substituent for ring A1, ring A1 ′, ring A2 and ring A2 ′ more preferably, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aralkyl group having 1 to 24 carbon atoms.
  • An aromatic hydrocarbon ring group, a cyano group, a halogen atom, a haloalkyl group, a diarylamino group or a carbazolyl group which is a 5- or 6-membered monocyclic ring or a condensed ring having 2 to 4 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • the substituent may be substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aralkyl group having 1 to 24 carbon atoms, or an alkyl group having 1 to 12 carbon atoms.
  • an aromatic hydrocarbon ring group which is a 6-membered monocyclic ring or a 2-4 condensed ring.
  • M 4 to M 6 in the formulas (IIIa) to (IIIc) are the same as M.
  • organometallic complexes represented by the above formulas (III) and (IIIa) to (IIIc) are shown below, but are not limited to the following compounds.
  • a 2-arylpyridine-based ligand that is, 2-arylpyridine, which has an optional substituent.
  • bonded and what an arbitrary group condensed to this is preferable.
  • the compounds described in International Publication No. 2005/019373 can also be used as the light emitting material.
  • M 7 represents a metal. Specific examples include the metals described above as the metal selected from Groups 7 to 11 of the periodic table. M 7 is preferably ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum or gold, and particularly preferably a divalent metal such as platinum or palladium.
  • R 92 and R 93 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, a cyano group, an amino group, an acyl group, an alkoxycarbonyl group, a carboxyl group, An alkoxy group, an alkylamino group, an aralkylamino group, a haloalkyl group, a hydroxyl group, an aryloxy group, and an aromatic ring group are represented.
  • R 94 and R 95 each independently represent the same substituent as those listed as R 92 and R 93 .
  • R 94 and R 95 are absent.
  • R 92 to R 95 may further have a substituent.
  • a substituent there is no restriction
  • any two or more groups of R 92 to R 95 may be connected to each other to form a ring.
  • Specific examples (T-1, T-10 to T-15) of the organometallic complex represented by the formula (IV) are shown below, but are not limited to the following examples. In the chemical formulas below, “Me” represents a methyl group, and “Et” represents an ethyl group.
  • One of these light emitting materials may be used alone, or two or more of these light emitting materials may be used in any combination and ratio.
  • five or more types of charge transport materials are included in the light emitting layer.
  • luminescent materials are included in the light emitting layer.
  • the molecular weight of the luminescent material in the present invention is arbitrary as long as the effects of the present invention are not significantly impaired.
  • the molecular weight of the luminescent material in the present invention is preferably 10,000 or less, more preferably 5000 or less, still more preferably 4000 or less, and particularly preferably 3000 or less.
  • the molecular weight of the light emitting material in the present invention is usually 100 or more, preferably 200 or more, more preferably 300 or more, and still more preferably 400 or more.
  • the molecular weight of the luminescent material is high due to its high glass transition temperature, melting point, decomposition temperature, etc., excellent heat resistance of the luminescent layer material and the formed luminescent layer, and gas generation, recrystallization and molecular migration. It is preferable that the film quality is low and the impurity concentration is not increased due to thermal decomposition of the material.
  • the molecular weight of the light-emitting material is preferably small in that the organic compound can be easily purified and easily dissolved in a solvent.
  • the light emitting layer preferably contains a host material such as a hole transport material or an electron transport material in addition to the above light emitting material.
  • a host material such as a hole transport material or an electron transport material in addition to the above light emitting material.
  • low molecular weight hole transport materials include two or more tertiary amines represented by 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl. Starbursts such as aromatic diamines in which the above condensed aromatic rings are substituted with nitrogen atoms (Japanese Patent Laid-Open No. 5-234811), 4,4 ′, 4 ′′ -tris (1-naphthylphenylamino) triphenylamine, etc.
  • Aromatic amine compounds having a structure Journal of Luminescence, 1997, Vol. 72-74, pp. 985
  • aromatic amine compounds consisting of tetramers of triphenylamine (Chemical Communications, 1996, pp. 2175) 2,2 ′, 7,7′-tetrakis- (diphenylamino) -9,9′-spirobifluorene B Compound (Synthetic Metals, 1997 years, Vol.91, pp.209), and the like.
  • low molecular weight electron transport materials examples include 2,5-bis (1-naphthyl) -1,3,4-oxadiazole (BND) and 2,5-bis (6 ′-(2 ′, 2 "-bipyridyl))-1,1-dimethyl-3,4-diphenylsilole (PyPySPyPy), bathophenanthroline (BPhen), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) , Bathocuproin), 2- (4-biphenylyl) -5- (p-tertiarybutylphenyl) -1,3,4-oxadiazole (tBu-PBD) and 4,4′-bis (9-carbazole) -Biphenyl (CBP), 9,10-di- (2-naphthyl) anthracene (ADN) and the like.
  • BND 2,5-bis (1-naphthyl)
  • the Hetero structure represents any of the following structural formulas (A-1), (A-2) and (A-3), and Xa 1 , Xa 2 , Ya 1 , Ya 2 , Za 1 and Za 2 are each independently an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or an aromatic complex having 3 to 30 carbon atoms which may have a substituent.
  • Xa 3 , Ya 3 and Za 3 each independently represent a hydrogen atom, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or a substituent. Represents an aromatic heterocyclic group having 3 to 30 carbon atoms.
  • Xe 1 , Xe 2 , Ye 1 , Ye 2 , Ze 1 and Ze 2 are each independently an aromatic hydrocarbon having 6 to 30 carbon atoms which may have a substituent.
  • Xe 3 , Ye 3 and Ze 3 may each independently have a hydrogen atom or a substituent. It represents a good aromatic hydrocarbon group having 6 to 30 carbon atoms or an optionally substituted aromatic heterocyclic group having 3 to 30 carbon atoms.
  • Xa 1 , Xa 2 , Ya 1 , Ya 2 , Za 1 and Za 2 , Xe 1 , Xe 2 , Ye 1 , Ye 2 , Ze 1 and Ze 2 in the general formula (E) are Each independently represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 30 carbon atoms which may have a substituent. To express. Among these, from the viewpoint of stability of the compound, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent is preferable.
  • aromatic hydrocarbon ring forming the aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent a 6-membered monocyclic ring or a 2 to 5 condensed ring is preferable.
  • Specific examples include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, and fluoranthene ring.
  • a benzene ring is preferable from the viewpoint of stability and solubility of the compound.
  • At least one of Xa 1 , Xa 2 , Ya 1 , Ya 2 , Za 1 and Za 2 is preferably 1,2-phenylene group or 1,3-phenylene group. , 3-phenylene group, and any one of Xa 1 , Xa 2 , any one of Ya 1 , Ya 2 , or any one of Za 1 , Za 2 is more preferable.
  • a 1,2-phenylene group or a 1,3-phenylene group is particularly preferred, and a 1,3-phenylene group is most preferred.
  • the stericity of the molecular structure is increased, the solubility in a solvent is increased, and the energy gap of the molecule is increased due to non-conjugated bonds.
  • the excited triplet energy is increased, it is preferable as a HOST material of a phosphorescent material.
  • a 1,3-phenylene group is more preferable from the viewpoint of stability of the compound and ease of synthesis.
  • At least one of Xe 1 , Xe 2 , Ye 1 , Ye 2 , Ze 1 and Ze 2 in the general formula (E) is a 1,2-phenylene group or a 1,3-phenylene group.
  • it is more preferably a 1,3-phenylene group, and further any one of Xe 1 and Xe 2 , one of Ye 1 and Ye 2 , or one of Ze 1 and Ze 2 ,
  • aromatic heterocyclic ring forming an aromatic heterocyclic group having 3 to 30 carbon atoms which may have a substituent
  • a 5- or 6-membered monocyclic ring, or a 2 to 5 condensed ring thereof is preferable.
  • a carbazole ring, a dibenzofuran ring and a dibenzothiophene ring are preferable from the viewpoint of high stability and charge transportability of the compound, and a pyridine ring, a pyrimidine ring and a triazine ring are preferable from the viewpoint of high electron transportability. is there.
  • Xa 3 , Ya 3 and Za 3 in the general formula (A), and Xe 3 , Ye 3 and Ze 3 in the general formula (E) each independently have a hydrogen atom or a substituent.
  • an aromatic hydrocarbon group having 6 to 30 carbon atoms or an aromatic heterocyclic group having 3 to 30 carbon atoms which may have a substituent As the aromatic hydrocarbon ring forming the aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a 6-membered monocyclic ring or a 2 to 5 condensed ring is preferable. Specific examples thereof include the same rings as those mentioned above as examples of Xa 1 in the general formula (A). Among these, from the viewpoint of stability of the compound, a benzene ring, a naphthalene ring or a phenanthrene ring is preferable.
  • the aromatic heterocyclic ring that forms an optionally substituted aromatic heterocyclic group having 3 to 30 carbon atoms is preferably a 5- or 6-membered monocyclic ring, or a 2 to 5 condensed ring thereof.
  • the same ring as mentioned above as an example of Xa 1 in the general formula (A) can be mentioned.
  • a carbazole ring, dibenzofuran ring or dibenzothiophene ring is preferable from the viewpoint of high stability and charge transportability of the compound.
  • the three substituents of Hetero structure in formula (A), -Xa 1 -Xa 2 -Xa 3, -Ya 1 -Ya 2 -Ya 3, and, -Za 1 -Za 2 -Za 3 is They may be the same or different. It is preferable that at least one of them is different from the viewpoint of reducing the target property of the compound and increasing the solubility in a solvent.
  • the three substituents of N in the general formula (E), -Xe 1 -Xe 2 -Xe 3 , -Ye 1 -Ye 2 -Ye 3 , and -Ze 1 -Ze 2 -Ze 3 are the same. Or different. It is preferable that at least one of them is different from the viewpoint of reducing the target property of the compound and increasing the solubility in a solvent.
  • Examples of the substituent that the aromatic hydrocarbon group or the aromatic heterocyclic group may have include a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 25 carbon atoms, and 3 to 20 carbon atoms.
  • a saturated hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 25 carbon atoms are preferable from the viewpoint of solubility and heat resistance.
  • examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, and a hexyl group.
  • methyl group, ethyl group and isopropyl group are preferable, and methyl group and ethyl group are more preferable from the viewpoint of availability of raw materials and low cost.
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 25 carbon atoms include a naphthyl group such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group; a phenanthyl group such as a 9-phenanthyl group and a 3-phenanthyl group; Anthryl group such as anthryl group, 2-anthryl group and 9-anthryl group; naphthacenyl group such as 1-naphthacenyl group and 2-naphthacenyl group; 1-chrycenyl group, 2-chrysenyl group, 3-chrysenyl group and 4-chrysenyl group Chrysenyl groups such as 1-pyrenyl group; Triphenylenyl groups such as 1-triphenylenyl group; Coronenyl groups such as 1-coronenyl group; 4-biphenyl group, 3-biphenyl A group
  • a phenyl group, a 2-naphthyl group and a 3-biphenyl group are preferable from the viewpoint of stability of the compound, and a phenyl group is particularly preferable from the viewpoint of ease of purification.
  • Examples of the aromatic heterocyclic group having 3 to 20 carbon atoms include thienyl groups such as 2-thienyl group; furyl groups such as 2-furyl group; imidazolyl groups such as 2-imidazolyl group; carbazolyl groups such as 9-carbazolyl group; And a pyridyl group such as a 2-pyridyl group and a triazinyl group such as a 1,3,5-triazin-2-yl group.
  • a carbazolyl group, particularly a 9-carbazolyl group is preferable from the viewpoint of stability.
  • diarylamino group having 12 to 60 carbon atoms examples include diphenylamino group, N-1-naphthyl-N-phenylamino group, N-2-naphthyl-N-phenylamino group, and N-9-phenanthryl-N-phenylamino.
  • a diphenylamino group an N-1-naphthyl-N-phenylamino group, and an N-2-naphthyl-N-phenylamino group are preferable, and a diphenylamino group is particularly preferable from the viewpoint of stability.
  • alkyloxy group having 1 to 20 carbon atoms examples include methoxy group, ethoxy group, isopropyloxy group, cyclohexyloxy group, and octadecyloxy group.
  • Examples of the (hetero) aryloxy group having 3 to 20 carbon atoms include substituents having an aryloxy group such as a phenoxy group, a 1-naphthyloxy group, and a 9-anthranyloxy group, and a heteroaryloxy group such as a 2-thienyloxy group Etc.
  • alkylthio group having 1 to 20 carbon atoms examples include a methylthio group, an ethylthio group, an isopropylthio group, and a cyclohexylthio group.
  • Examples of the (hetero) arylthio group having 3 to 20 carbon atoms include an arylthio group such as a phenylthio group, a 1-naphthylthio group and a 9-anthranylthio group, and a heteroarylthio group such as a 2-thienylthio group.
  • the light emitting layer has been described above, but other configurations will be described below.
  • the aforementioned substrate can be used.
  • inorganic glass is preferable.
  • the anode plays a role of hole injection into a layer on the light emitting layer side (such as a hole injection layer or a light emitting layer).
  • This anode is usually made of metal such as aluminum, gold, silver, nickel, palladium, platinum, metal oxide such as oxide of indium and / or tin, metal halide such as copper iodide, carbon black, or poly It is composed of conductive polymers such as (3-methylthiophene), polypyrrole and polyaniline.
  • the anode is often formed by a sputtering method, a vacuum deposition method, or the like.
  • fine metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, conductive polymer fine powder, etc.
  • it is dispersed in an appropriate binder resin solution and placed on the substrate.
  • An anode can also be formed by coating.
  • a conductive polymer a thin film can be directly formed on a substrate by electrolytic polymerization, and an anode can be formed by applying a conductive polymer on the substrate (Applied Physics Letters, 1992, Vol. 60, pp. 2711).
  • the anode can be formed by stacking different materials.
  • the thickness of the anode varies depending on the required transparency. When transparency is required, it is desirable that the visible light transmittance is usually 60% or more, preferably 80% or more. In this case, the thickness is usually 5 nm or more, preferably 10 nm or more, Usually, it is 1000 nm or less, preferably 500 nm or less. If it may be opaque, the anode may be the same as the substrate. Furthermore, it is also possible to laminate different conductive materials on the anode. In addition, the surface of the anode is treated with ultraviolet (UV) / ozone, oxygen plasma, or argon plasma for the purpose of removing impurities adhering to the anode and adjusting the ionization potential to improve the hole injection property. Is preferred.
  • UV ultraviolet
  • the hole injection layer is a layer that injects and transports holes from the anode toward the light emitting layer.
  • the material forming the hole injection layer is preferably a material having a high hole transport capability and capable of efficiently transporting the injected holes. Therefore, it is preferable that the ionization potential is small, the transparency to visible light is high, the hole mobility is large, the stability is excellent, and impurities that become traps are not easily generated during manufacture or use. In many cases, it is preferable that the light emission from the light emitting layer is not quenched or the exciplex is formed with the light emitting layer to reduce efficiency.
  • materials conventionally used as a constituent material for the hole injection layer can be used.
  • materials conventionally used as a constituent material for the hole injection layer can be used.
  • polyvinylcarbazole derivatives polyarylamine derivatives, polyvinyltriphenylamine derivatives, polyfluorene derivatives, polyarylene derivatives, polyarylene ether sulfone derivatives containing tetraphenylbenzidine, polyarylene vinylene derivatives, polysiloxane derivatives, polythiophene derivatives And poly (p-phenylene vinylene) derivatives.
  • These may be any of alternating copolymer compounds, random polymer compounds, block polymer compounds, and graft copolymer compounds. Further, it may be a polymer having a branched main chain and three or more terminal portions, or a so-called dendrimer. Of these, polyarylamine derivatives and polyarylene derivatives are preferred because of their high hole transport ability.
  • the polyarylamine derivative preferably contains a repeating unit consisting of the following formula (2).
  • T 2 represents a group, and T 2 is selected from the above-mentioned crosslinkable group T and T ′, and a group including a group represented by the following formula (3) is particularly preferable.
  • the benzocyclobutene ring in formula (3) may have a substituent.
  • the substituents may be bonded to each other to form a ring.
  • the hole injection layer is more preferably a conductive thin film in the present invention.
  • a hole transporting compound constituting the hole injection layer and, if necessary, other components are mixed with an appropriate solvent to form a film forming composition.
  • a composition for forming a charge transport layer of a hole injection layer is prepared and used.
  • the content of the hole transporting compound in the composition for forming a hole injection layer is usually 0.1% by weight or more, preferably 0.5% by weight or more, usually 50% by weight or less, preferably 20% by weight or less.
  • the hole injection layer forming composition may contain two or more types of hole transporting compounds, and in that case, the total of two or more types is preferably within the above range.
  • the composition for forming a hole injection layer according to the present invention usually contains a solvent.
  • the solvent contained in the composition for forming a hole injection layer according to the present invention is not particularly limited, but the hole transporting compound is usually 0.1% by weight, preferably 0.5% by weight. %, More preferably 1.0% by weight or more.
  • the range and specific examples of the boiling point of the solvent are the same as those of the solvent that can be used for the composition containing the conductive thin film forming material in the present invention.
  • the hole injection layer preferably contains an electron accepting compound because the conductivity of the hole injection layer can be improved by oxidation of the hole transporting compound.
  • an electron accepting compound a compound having an oxidizing power and the ability to accept one electron from the above-described hole-transporting compound is preferable, and specifically, a compound having an electron affinity of 4 eV or more is preferable. More preferably, the compound is 5 eV or more.
  • electron-accepting compounds include triarylboron compounds, metal halides, Lewis acids, organic acids, onium salts, salts of arylamines and metal halides, and salts of arylamines and Lewis acids.
  • examples thereof include one or more compounds selected from the group. Specifically, an onium salt substituted with an organic group such as triphenylsulfonium tetrafluoroborate; iron (III) chloride (Japanese Unexamined Patent Publication No.
  • a high-valent inorganic compound such as ammonium peroxodisulfate
  • a cyano compound such as tetracyanoethylene
  • an aromatic boron compound such as tris (pendafluorophenyl) borane
  • an ionic compound described in International Publication No. 2005/089024
  • a fullerene derivative And iodine
  • an onium salt substituted with an organic group, an inorganic compound having a high valence, and the like are preferable in terms of having strong oxidizing power.
  • an onium salt substituted with an organic group, a cyano compound, an aromatic boron compound, and the like are preferable from the viewpoint of high solubility in an organic solvent and easy formation of a film by a wet film formation method.
  • Specific examples of the onium salt, cyano compound or aromatic boron compound substituted with an organic group suitable as an electron-accepting compound include those described in WO 2005/089024, and preferred examples thereof are also the same. .
  • n1 in the following general formula (I-1), n2 in the following general formula (I-2), and n3 in the following general formula (I-3) are each independently a counter anion Z n1 to Z n3.
  • - is any positive integer corresponding to the valency.
  • the values of n1 to n3 are not particularly limited, but all are preferably 1 or 2, and most preferably 1.
  • an electron-accepting compound may be used individually by 1 type, or may be used 2 or more types by arbitrary combinations and a ratio.
  • the content of the electron-accepting compound in the composition for forming a hole injection layer is usually 0.01% by weight or more, preferably 0.05% by weight or more, usually 20% by weight or less, preferably 10% by weight or less.
  • 2 or more types of electron-accepting compounds may be contained, In that case, it is preferable that the sum total of 2 or more types becomes said range.
  • the hole injection layer preferably contains a cation radical compound in terms of enhancing the hole injecting property from the anode and enhancing the hole transporting property.
  • a cation radical compound an ionic compound composed of a cation radical which is a chemical species obtained by removing one electron from a hole transporting compound and a counter anion is preferable.
  • the cation radical is derived from a hole transporting polymer compound, the cation radical has a structure in which one electron is removed from the repeating unit of the polymer compound.
  • the cation radical is preferably a chemical species obtained by removing one electron from the compound described above as the hole transporting compound from the viewpoints of amorphousness, visible light transmittance, heat resistance, solubility, and the like.
  • the cation radical compound can be generated by mixing the hole transporting compound and the electron accepting compound. That is, by mixing the hole transporting compound and the electron accepting compound, electron transfer occurs from the hole transporting compound to the electron accepting compound, and the cation radical and the counter anion of the hole transporting compound A cation ion compound consisting of
  • Oxidative polymerization here refers to oxidation of a monomer chemically or electrochemically with peroxodisulfate in an acidic solution.
  • the monomer is polymerized by oxidation, and a cation radical that is removed from the polymer repeating unit by using an anion derived from an acidic solution as a counter anion is removed.
  • the hole injection layer is formed by a wet film forming method, it can be applied and dried in the same manner as the method for applying the composition for forming a conductive thin film in the present invention. Drying may be performed twice or more.
  • the hole injection layer is a conductive thin film according to the present invention, it has the aforementioned infrared heating step.
  • the thickness of the hole injection layer is usually 1 nm or more, preferably 5 nm or more, and usually 1000 nm or less, preferably 500 nm or less.
  • the hole transport layer in the present invention is a layer that is provided on the hole injection layer and transports holes carried from the hole injection layer to the light emitting layer.
  • the material for forming the hole transport layer is preferably a material having high hole transportability and capable of efficiently transporting injected holes. Therefore, it is preferable that the ionization potential is small, the transparency to visible light is high, the hole mobility is large, the stability is excellent, and impurities that become traps are not easily generated during manufacture or use. In many cases, since it is in contact with the light emitting layer, it is preferable not to quench the light emitted from the light emitting layer or to reduce the efficiency by forming an exciplex with the light emitting layer.
  • Such a material for forming the hole transport layer may be a compound including the structure described in the above section [Hole Injection Layer], but in terms of excellent charge transport ability and solubility in an organic solvent, It is preferable that it is a high molecular compound containing the repeating unit represented by following formula (5).
  • q represents an integer of 0 to 3
  • Ar 11 and Ar 12 each independently have an aromatic hydrocarbon group which may have a substituent, or a substituent.
  • Ar 13 to Ar 15 each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic which may have a substituent.
  • neither Ar 11 nor Ar 12 is a direct bond.
  • Ar 11 and Ar 12 are each independently a direct bond, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocycle which may have a substituent.
  • Each of Ar 13 to Ar 15 independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
  • a group derived from a 6-membered monocyclic ring or a 2-5 condensed ring such as a ring, a fluoranthene ring, and a fluorene ring.
  • Examples of the aromatic heterocyclic group which may have a substituent include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring.
  • Ar 11 to Ar 15 are each independently from a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a thiophene ring, a pyridine ring, and a fluorene ring from the viewpoint of solubility in a solvent and heat resistance.
  • Ar 11 to Ar 15 a divalent group in which one or two or more rings selected from the above group are directly bonded or connected by a —CH ⁇ CH— group is preferable, and a biphenylene group and a terphenylene group are also preferable. Is more preferable.
  • the substituent that the aromatic hydrocarbon group and the aromatic heterocyclic group in Ar 11 to Ar 15 may have in addition to the insolubilizing group described later is not particularly limited. For example, the following [Substituent group Z] 1 type (s) or 2 or more types selected from are mentioned.
  • Substituent group Z Preferably an alkyl group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms such as a methyl group or an ethyl group; preferably an alkenyl group having 2 to 24 carbon atoms, such as a vinyl group, more preferably 2 to 12 carbon atoms.
  • an alkynyl group having 2 to 24 carbon atoms more preferably 2 to 12 carbon atoms such as an ethynyl group; preferably an alkoxy group having 1 to 24 carbon atoms, such as a methoxy group or an ethoxy group, more preferably an alkoxy having 1 to 12 carbon atoms;
  • the molecular weight of the substituent that the aromatic hydrocarbon group and aromatic heterocyclic group in Ar 11 to Ar 15 may have in addition to the insolubilizing group described below is preferably 500 or less, including substituted groups, and is preferably 250 or less. Is more preferable.
  • the substituents that the aromatic hydrocarbon group and aromatic heterocyclic group in Ar 11 to Ar 15 may have are each independently an alkyl group having 1 to 12 carbon atoms and a carbon number. 1 to 12 alkoxy groups are preferred.
  • q represents an integer of 0 to 3.
  • q is usually 0 or more, usually 3 or less, preferably 2 or less. When q is 2 or less, synthesis of a monomer as a raw material is easier.
  • the polymer compound for forming the hole transport layer in the present invention is preferably a polymer compound containing one or more repeating units represented by the formula (5).
  • the polymer compound for forming the hole transport layer in the present invention has two or more types of repeating units, examples thereof include random copolymers, alternating copolymers, block copolymers, and graft copolymers.
  • a random copolymer is preferable from the viewpoint of solubility in a solvent.
  • An alternating copolymer is preferable in that the charge transport ability is further enhanced.
  • the polymer compound for forming the hole transport layer in the present invention preferably has a crosslinkable group selected from the above crosslinkable group groups T and T ′.
  • the crosslinkable group is preferably a benzocyclobutene ring represented by the formula (3).
  • the polymer compound for forming the hole transport layer in the present invention may have a dissociation group.
  • the dissociating group refers to a group that dissociates from a bonded aromatic hydrocarbon ring at 70 ° C. or more and is soluble in a solvent.
  • being soluble in a solvent means that the compound is dissolved in toluene at 0.1% by weight or more at room temperature in a state before reacting by irradiation with heat and / or active energy rays.
  • the solubility in toluene is preferably 0.5% by weight or more, more preferably 1% by weight or more. Having such a dissociating group is preferable from the viewpoint of excellent charge transport ability after the dissociation reaction.
  • Such a dissociating group is preferably a group that thermally dissociates without forming a polar group on the aromatic hydrocarbon ring side, and more preferably a group that dissociates thermally by a reverse Diels-Alder reaction. Furthermore, it is preferably a group that thermally dissociates at 100 ° C. or higher, and is preferably a group that thermally dissociates at 300 ° C. or lower. Specific examples of the dissociating group are as follows, but the present invention is not limited thereto. A specific example in the case where the dissociating group is a divalent group is as shown in ⁇ Divalent dissociating group group A> below. ⁇ Divalent dissociation group A>
  • the hole transport layer is more preferably the conductive thin film in the present invention.
  • the hole transport layer is formed by a wet film formation method.
  • the wet film forming method is not limited as long as the effects of the present invention are not significantly impaired, but the solvent, additive, drying method, and coating method in the hole transport layer forming composition are, for example, ⁇ hole injection layer forming composition It can be used in the same manner as described in the item>.
  • the thickness of the hole transport layer is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less.
  • a hole blocking layer may be provided between the light emitting layer and an electron injection layer described later.
  • the hole blocking layer is a layer stacked on the light emitting layer so as to be in contact with the cathode side interface of the light emitting layer.
  • the hole blocking layer has a role of blocking holes moving from the anode from reaching the cathode and a role of efficiently transporting electrons injected from the cathode toward the light emitting layer.
  • the physical properties required for the material constituting the hole blocking layer include high electron mobility, low hole mobility, large energy gap (difference between HOMO and LUMO), and excited triplet level (T1). It is expensive.
  • Examples of the hole blocking layer material satisfying such conditions include bis (2-methyl-8-quinolinolato) (phenolato) aluminum, bis (2-methyl-8-quinolinolato) (triphenylsilanolato) aluminum, and the like.
  • Mixed ligand complexes of, such as metal complexes such as bis (2-methyl-8-quinolato) aluminum- ⁇ -oxo-bis- (2-methyl-8-quinolinato) aluminum binuclear metal complexes, distyryl biphenyl derivatives, etc.
  • Triazole derivatives such as styryl compounds (Japanese Patent Laid-Open No.
  • a hole-blocking layer there is no restriction
  • the thickness of the hole blocking layer is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less.
  • the electron transport layer is provided between the light emitting layer and the electron injection layer for the purpose of further improving the current efficiency of the device.
  • the electron transport layer is formed of a compound capable of efficiently transporting electrons injected from the cathode between the electrodes to which an electric field is applied in the direction of the light emitting layer.
  • the electron transporting compound used in the electron transporting layer is a compound that has high electron injection efficiency from the cathode or the electron injection layer and has high electron mobility and can efficiently transport injected electrons. It is necessary.
  • Metal complexes such as aluminum complexes of 8-hydroxyquinoline (Japanese Unexamined Patent Publication No. 59-194393), metal complexes of 10-hydroxybenzo [h] quinoline, oxadiazole derivatives Distyrylbiphenyl derivatives, silole derivatives, 3- or 5-hydroxyflavone metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, trisbenzimidazolylbenzene (US Pat. No.
  • the lower limit of the thickness of the electron transport layer is usually 1 nm, preferably about 5 nm, and the upper limit is usually 300 nm, preferably about 100 nm.
  • the electron transport layer is formed by laminating on the hole blocking layer by a wet film formation method or a vacuum deposition method in the same manner as described above. Usually, a vacuum deposition method is used.
  • the electron injection layer plays a role of efficiently injecting electrons injected from the cathode into the electron transport layer or the light emitting layer.
  • the material for forming the electron injection layer is preferably a metal having a low work function. Examples include alkali metals such as sodium and cesium, and alkaline earth metals such as barium and calcium.
  • the film thickness is usually preferably from 0.1 nm to 5 nm.
  • organic electron transport materials represented by metal complexes such as nitrogen-containing heterocyclic compounds such as bathophenanthroline and aluminum complexes of 8-hydroxyquinoline described later are doped with alkali metals such as sodium, potassium, cesium, lithium and rubidium.
  • alkali metals such as sodium, potassium, cesium, lithium and rubidium.
  • the electron injection layer is formed by laminating on the light emitting layer or the hole blocking layer thereon by a wet film formation method or a vacuum deposition method. Details of the wet film forming method are the same as those of the hole injection layer and the light emitting layer.
  • the vacuum vapor deposition method the vapor deposition source is put into a crucible or a metal boat installed in the vacuum vessel, and the inside of the vacuum vessel is evacuated to about 10 ⁇ 4 Pa with an appropriate vacuum pump, and then the crucible or metal The boat is heated and evaporated to form an electron injection layer on the light emitting layer, hole blocking layer or electron transport layer on the substrate placed facing the crucible or metal boat.
  • the alkali metal as the electron injection layer is deposited by using an alkali metal dispenser in which nichrome is filled with an alkali metal chromate and a reducing agent. By heating the dispenser in a vacuum container, the alkali metal chromate is reduced and the alkali metal is evaporated.
  • the organic electron transport material and alkali metal are co-evaporated, the organic electron transport material is put in a crucible installed in a vacuum vessel, and the inside of the vacuum vessel is evacuated to about 10 ⁇ 4 Pa with an appropriate vacuum pump.
  • Each crucible and dispenser are simultaneously heated and evaporated to form an electron injection layer on the substrate placed facing the crucible and dispenser. At this time, co-evaporation is uniformly performed in the film thickness direction of the electron injection layer, but there may be a concentration distribution in the film thickness direction.
  • the cathode plays a role of injecting electrons into a layer on the light emitting layer side (such as an electron injection layer or a light emitting layer).
  • a metal having a low work function is preferable, and tin, magnesium, indium, calcium, aluminum, A suitable metal such as silver or an alloy thereof is used.
  • Specific examples include low work function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy.
  • the thickness of the cathode is usually the same as that of the anode.
  • a metal layer having a high work function and stable to the atmosphere because the stability of the device is increased.
  • metals such as aluminum, silver, copper, nickel, chromium, gold, platinum are used.
  • the organic electroluminescent element in the present invention may have another configuration without departing from the gist thereof.
  • an arbitrary layer may be provided between the anode and the cathode in addition to the layers described above, and an arbitrary layer may be omitted.
  • the structure opposite to that described above, that is, a cathode, an electron injection layer, a light emitting layer, a hole injection layer, and an anode can be laminated in this order on the substrate. It is also possible to provide the organic electroluminescent element of the present invention between two sheets of substrates. Furthermore, a structure in which a plurality of layers are stacked (a structure in which a plurality of light emitting units are stacked) may be employed. In that case, instead of the interfacial layer (between the light emitting units) (when the anode is ITO and the cathode is Al, the two layers), for example, V 2 O 5 is used as the charge generation layer (CGL). This is more preferable from the viewpoint of current efficiency and driving voltage.
  • the present invention can be applied to any of organic electroluminescent elements, a single element, an element having a structure arranged in an array, and a structure in which an anode and a cathode are arranged in an XY matrix.
  • Organic EL Display and Organic EL Lighting in the present invention use the organic electroluminescent element in the present invention as described above.
  • the organic EL display and the organic EL display according to the present invention can be obtained by the method described in “Organic EL Display” (Ohm, August 20, 2004, written by Shizushi Tokito, Chiba Adachi, and Hideyuki Murata). EL illumination can be formed.
  • the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and the present invention can be arbitrarily modified and implemented without departing from the gist thereof.
  • Example 1 A 0.7 mm-thick inorganic glass substrate (non-alkali glass) was used as the substrate.
  • This inorganic glass substrate had a minimum value of infrared transmittance at a wavelength of 2.8 ⁇ m, and the infrared transmittance was 39.6%.
  • an indium tin oxide (ITO) transparent conductive film deposited to a thickness of 70 nm is subjected to normal photolithography technology and hydrochloric acid etching.
  • An anode was formed by patterning into a stripe having a width of 2 mm.
  • ITO indium tin oxide
  • the patterned ITO substrate is cleaned in the order of ultrasonic cleaning with an aqueous surfactant solution, water cleaning with ultrapure water, ultrasonic cleaning with ultrapure water, and water cleaning with ultrapure water, followed by drying with compressed air, and finally UV irradiation. Ozone cleaning was performed.
  • 4-isopropyl-4 represented by the following structural formula (A1)
  • a composition for forming a hole injection layer was prepared using 20 parts by weight of '-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate and ethyl benzoate as a solvent (2.5% by weight). Filtration was performed using a 2 ⁇ m PTFE (polytetrafluoroethylene) membrane filter to prepare a coating composition.
  • This coating composition was spin coated on the substrate.
  • the spin coat was rotated at 4000 rpm and the film was formed for 30 seconds.
  • the solvent was dried on a hot plate at 80 ° C. for 30 seconds. Thereafter, the periphery of the glass substrate was wiped off with toluene. The film thickness at this time was about 35 nm.
  • the substrate was heated from 30 ° C. to 230 ° C. using a halogen heater (USHIO Inc .; heater peak wavelength 1.2 ⁇ m) as electromagnetic wave heating.
  • a halogen heater USHIO Inc .; heater peak wavelength 1.2 ⁇ m
  • the product ⁇ of the wavelength at the minimum absorption value in the range of 2000 nm to 3300 nm and the peak wavelength of the halogen heater was 3.4 ⁇ m 2 .
  • the substrate temperature was measured using an infrared camera (manufactured by NEC Avio Infrared Technology Co., Ltd.), and the exposed part of the glass substrate (around the glass substrate wiped with toluene) was measured.
  • the heating time was 3 minutes.
  • the temperature rising rate was 140 ° C./min for the initial 30 seconds.
  • the time to reach 150 ° C. was 1 minute after the start. That is, the main firing temperature condition was 2 minutes at 150 ° C. or higher.
  • the temperature was constantly rising and was not maintained at a constant temperature.
  • the value ( ⁇ / t) obtained by dividing ⁇ by the time t during which the substrate was held at a temperature of 150 ° C. or higher was 0.028 ⁇ m 2 / s.
  • the above steps were performed in the atmosphere. Thereby, a hole injection layer was obtained.
  • This hole transport layer coating solution was spin-coated under nitrogen on the previously prepared hole injection layer, and deposited at a spin coating speed of 2100 rpm for 120 seconds.
  • the solvent was dried for 30 seconds on a hot plate at 230 ° C.
  • the film thickness at this time was 10 nm, and then the periphery of the substrate was wiped off with toluene.
  • a halogen heater was used under the same conditions to obtain a hole transport layer.
  • ⁇ Light emitting layer> The compounds represented by the following formulas, H1, H2, and D1, were mixed at 25 parts by weight, 75 parts by weight, and 15 parts by weight, respectively, using cyclohexylbenzene as a solvent to give 5.75 wt%, and emitted light.
  • a layer coating solution was prepared. This light emitting layer coating solution was spin-coated under nitrogen on the previously prepared hole transport layer. The film was formed for 120 seconds at a spin coating speed of 1800 rpm. Thereafter, the periphery of the substrate was wiped off with toluene. After film formation, it was heated at 120 ° C. for 20 minutes with a hot plate. The film thickness at this time was 60 nm. Thus, a light emitting layer was obtained.
  • HB1 a compound represented by the following formula
  • a 2 mm wide stripe-shaped shadow mask as a cathode evaporation mask is brought into close contact with the anode ITO stripe so as to be perpendicular to the anode, and lithium fluoride (LiF) is used as an electron injection layer by vacuum evaporation.
  • the film was laminated to a thickness of 5 nm.
  • a sealing process was performed by the method described below.
  • a photocurable resin 30Y-437 manufactured by ThreeBond
  • a moisture getter sheet manufactured by Dynic
  • substrate which completed cathode formation was bonded together so that the vapor-deposited surface might oppose a desiccant sheet.
  • coated was irradiated with ultraviolet light, and resin was hardened.
  • an organic electroluminescent element 1 having a light emitting area portion having a size of 2 mm ⁇ 2 mm was obtained.
  • Example 2 Organic electroluminescent element 2 was obtained in the same manner as in Example 1 except that the hole injection layer and the hole transport layer were baked for 6 minutes. In this firing, the heating rate was 140 ° C./min from the start of heating to 30 seconds, and the time to reach 150 ° C. was 1 minute after the start. Thereafter, the temperature was further increased to 267 in 3 minutes. That is, the time of 150 ° C. or more was 5 minutes depending on the main firing temperature condition. ⁇ / t was 0.011 ⁇ m 2 / s.
  • Example 1 The organic electroluminescent element A was obtained in the same manner as in Example 1 except that the hole injection layer and the hole transport layer were fired using a hot air heating furnace (furnace temperature 230 ° C.).
  • the peak wavelength of infrared rays in a hot-air heating furnace (230 ° C.) was obtained by the following Wien equation and was 5.76 ⁇ m.
  • Vienna formula: peak wavelength 2897 / T (* T is absolute temperature)
  • the product of the infrared transmission minimum value and the infrared peak wavelength in the wavelength range of 2000 to 3300 nm of the substrate was 16.1 ⁇ m 2 .
  • the temperature of the substrate reached only 123 ° C.
  • Example 2 An organic electroluminescent element B was obtained in the same manner as in Example 1 except that the hole injection layer and the hole transport layer were baked for 40 minutes. In this firing, the heating rate was 140 ° C./min from the start of heating to 30 seconds, and the time to reach 150 ° C. was 1 minute after the start. Thereafter, the temperature was further raised to 280 ° C. in 12 minutes. The temperature was kept at that temperature for another 27 minutes. Depending on the main firing temperature conditions, the time of 150 ° C. or higher was 39 minutes. ⁇ / t was 0.0014 ⁇ m 2 / s.
  • Example 3 An organic electroluminescent element C was obtained in the same manner as in Example 1 except that the firing time of the hole injection layer and the hole transport layer was 30 seconds. In this baking, the temperature of the substrate reached only 100 ° C.
  • Example 3 The hole injection layer and hole transport layer were fired in the same manner as in Example 1 except that a ceramic-coated infrared heater (manufactured by Ushio Inc .: heater peak wavelength 2.5 ⁇ m) was used. A light emitting device 3 was obtained. Under the firing conditions using this heater, the time to reach 150 ° C. was 50 seconds after the start of heating. Then, it became 230 degreeC in 2 minutes and 10 seconds. The product of the minimum value of infrared transmission in the wavelength range of 2000 to 3300 nm of the substrate and the peak wavelength of the ceramic-coated infrared heater was 7.0 ⁇ m 2 . ⁇ / t was 0.026 ⁇ m 2 / s.
  • a ceramic-coated infrared heater manufactured by Ushio Inc .: heater peak wavelength 2.5 ⁇ m
  • Example 4 An organic electroluminescent device 4 was obtained in the same manner as in Example 1 except that PEDOT / PSS was used for the hole injection layer. PEDOT / PSS (manufactured by Aldrich) was adjusted to 0.65 wt% using water as a solvent and spin-coated. The film was formed for 30 seconds at a spin coating speed of 1000 rpm.
  • Example 4 The organic electroluminescence device D was fabricated in the same manner as in Example 4 except that the hole injection layer and the hole transport layer were fired using a hot air heating furnace (furnace temperature 230 ° C.) that was not electromagnetic heating. Obtained. In addition, the temperature of the substrate reached only 123 ° C.
  • Example 5 An organic electroluminescent element E was obtained in the same manner as in Example 4 except that the hole injection layer and the hole transport layer were baked for 40 minutes. In this firing, the rate of temperature increase was 67 ° C./min from the start of heating to 3 minutes, and the time to reach 150 ° C. was 50 seconds after the start. Thereafter, the temperature was further raised to 280 ° C. in 12 minutes. The temperature was kept at that temperature for another 25 minutes. Depending on the main firing temperature condition, the time of 150 ° C. or higher was 39 minutes and 10 seconds. ⁇ / t was 0.0014 ⁇ m 2 / s.
  • Example 5 The hole injection layer was fired in the same manner as in Example 3 except that the firing time was 3 minutes using a far-infrared ceramic heater (manufactured by NGK, Inc .: heater peak wavelength 5.2 ⁇ m), and organic electroluminescence was produced. Element 5 was obtained.
  • the time for the substrate temperature to reach 150 ° C. was 120 seconds after the start. Depending on the main firing temperature condition, the time t of 150 ° C. or higher was 60 seconds.
  • the product ⁇ of the minimum value of infrared transmission in the wavelength range of 2000 to 3300 nm of the substrate and the peak wavelength of this far-infrared ceramic heater was 14.6 ⁇ m 2 .
  • ⁇ / t was 0.24 ⁇ m 2 / s.
  • Example 6 An organic electroluminescent layer laminate element 6 was obtained in the same manner as in Example 3 except that the firing time of the hole injection layer was 6 minutes and the firing time of the hole transport layer was 6 minutes. At this time, the time for the substrate temperature to reach 150 ° C. was 50 seconds after the start of heating. Thereafter, the temperature reached 270 ° C. in 5 minutes and 10 seconds. ⁇ / t was 0.023 ⁇ m 2 / s.
  • Example 7 The hole transport layer was fired in the same manner as in Example 5 except that the firing time was 20 minutes with a far-infrared ceramic heater (manufactured by NGK: heater peak wavelength 5.2 ⁇ m), and organic electroluminescence was produced. Element 7 was obtained. The time for the substrate temperature to reach 150 ° C. was 120 seconds after the start. Depending on the main firing temperature condition, the time t of 150 ° C. or higher was 18 minutes. ⁇ / t was 0.013 ⁇ m 2 / s.
  • Table 12 shows the results of measuring the driving voltage and current efficiency at 2500 cd / m 2 in Examples 1 to 7 and Comparative Examples 1 to 5.
  • Example 1 the driving voltage is low, the current efficiency is high, and the performance as an organic electroluminescence device is high.
  • the drive voltage is high and the current efficiency is low.
  • Comparative Example 2 and Comparative Example 5 the drive voltage is high.
  • Comparative Example 3 the current efficiency is low.
  • Example 8 A 0.7 mm thick inorganic glass substrate was used as the substrate.
  • This inorganic glass substrate had a minimum value of infrared transmittance at a wavelength of 2.8 ⁇ m, and the infrared transmittance was 68.84%.
  • an indium tin oxide (ITO) transparent conductive film was deposited to a thickness of 70 nm.
  • This ITO substrate is cleaned in the order of ultrasonic cleaning with an aqueous surfactant solution, water cleaning with ultra pure water, ultrasonic cleaning with ultra pure water, and water cleaning with ultra pure water, followed by drying with compressed air, and finally UV ozone cleaning. Went.
  • ITO indium tin oxide
  • a composition for forming a hole injection layer was prepared by using 15 ′ parts by weight of 4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate and ethyl benzoate as a solvent (5.50% by weight and 2.75% by weight). %).
  • This coating composition was spin coated on the substrate.
  • the rotation speed of the spin coat was changed from 3000 rpm to 700 rpm.
  • the rotation time was 30 seconds.
  • a halogen heater (USHIO INC .; heater peak wavelength: 1.2 ⁇ m) was used for infrared heating of the substrate.
  • the product ⁇ of the wavelength at the minimum absorption value in the range of 2000 nm to 3300 nm and the peak wavelength of the halogen heater was 3.4 ⁇ m 2 .
  • the infrared irradiation time was 1 minute. It became 70 degreeC or more in 10 seconds after infrared irradiation.
  • the maximum temperature reached by the substrate was 160 ° C.
  • the temperature rising rate at this time was 180 ° C./min in the initial 30 seconds.
  • the time t during which the substrate was 70 ° C. or higher was 50 seconds.
  • ⁇ / t was 0.067 ⁇ m 2 / sec.
  • the above steps were performed in the atmosphere.
  • the obtained initial film thickness was 52 nm to 345 nm.
  • Example 6 Film formation, firing, and residual film ratio measurement were performed in the same manner as in Example 8 except that only 2.75% by weight of the composition for hole injection layer was used and the rotation speed of spin coating was changed from 4500 rpm to 1500 rpm. went.
  • the initial film thicknesses were 21.4 nm, 34.4 nm, and 40.4 nm. The obtained results are shown in FIG. As a result, it was found that the residual film rate was low and the hole transporting material layer was not insolubilized.
  • Example 9 The film formation, baking, and remaining in the same manner as in Example 8 except that the rotation speed of the spin coating was 1400 rpm, the baking method was a hot air furnace (furnace temperature 230 ° C.), and the baking time was 3 minutes to 60 minutes. The film ratio was measured. The initial film thickness was 150 nm. The result is shown in FIG. It was insolubilized with a remaining film rate of 100% by heating for 45 minutes.
  • Example 11 As the halogen heater, a ceramic-coated halogen heater (USHIO INC .; heater peak wavelength 2.5 ⁇ m) was used, the firing time was 2.5 minutes, the concentration of the composition for the hole transport layer was 5.50 wt%, and the spin The experiment was performed in the same manner as in Example 10 except that the number of revolutions of the coat was 1400 rpm. The obtained initial film thickness was 200 nm. The remaining film rate was 100%. At this time, the product ⁇ of the wavelength at the minimum absorption value in the range of 2000 nm to 3300 nm of the substrate and the peak wavelength of the halogen heater was 7.0 ⁇ m 2 . It became 70 degreeC or more in 10 seconds after infrared irradiation. The maximum temperature reached by the substrate was 230 ° C. The rate of temperature increase at this time was 192 ° C./min for the initial 30 seconds. ⁇ / t was 0.050 ⁇ m 2 / sec.
  • Example 8 The experiment was performed in the same manner as in Example 11 except that the concentration of the composition for the hole transport layer was 2.75% and the rotation speed of the spin coat was 4500 rpm. The initial film thickness was 21 nm. As a result, the remaining film rate was 0% and the hole transporting material layer was not dissolved.
  • Example 12 the organic electroluminescent element 8 was obtained similarly to Example 1 except having changed the baking conditions of the positive hole injection layer, the positive hole transport layer, and the light emitting layer as follows.
  • ⁇ Hole injection layer, hole transport layer: Firing was performed in a hot air oven at 230 ° C. for 1 hour.
  • ⁇ Light emitting layer For firing the light emitting layer, a halogen heater (USHIO INC .; heater peak wavelength: 1.2 ⁇ m) was used, and the temperature was raised from 30 ° C. to 95 ° C. in 1.5 minutes.
  • an exposed part of the glass substrate was measured using an infrared camera (manufactured by NEC Avio Infrared Technology).
  • the heating rate was 50 ° C./min for the initial 30 seconds.
  • the temperature reached 70 ° C. after 48 seconds. That is, the time of 70 ° C. or higher was 42 seconds. During this time, the temperature was constantly rising and was not maintained at a constant temperature.
  • the firing step was performed in the atmosphere.
  • the film thickness at this time was 60 nm. In this way, the light emitting layer laminated body 1 was obtained.
  • the product of the peak wavelength of the infrared heater at this time and the wavelength at the minimum value of transmittance at a wavelength of 2000 nm to 3300 nm of the glass substrate was 3.4 ⁇ m 2 .
  • ⁇ / t was 0.080 ⁇ m 2 / s.
  • Example 13 An organic electroluminescent element 9 was produced in the same manner as in Example 12 except that the firing condition of the light emitting layer was fired from 30 ° C. to 110 ° C. for 5 minutes. The temperature rising rate in firing the light emitting layer was 90 ° C./min for the initial 30 seconds. The temperature reached 70 ° C. in 27 seconds after heating. That is, the time over 70 ° C. was 4 minutes 33 seconds. The temperature reached 110 ° C. 3 minutes after the heating, and then the temperature was kept constant until the end of firing. ⁇ / t was 0.012 ⁇ m 2 / s.
  • Example 14 An organic electroluminescent element 10 was produced in the same manner as in Example 13 except that a ceramic-coated halogen heater (USHIO Inc .: heater peak wavelength: 2.5 ⁇ m) was used as the light-emitting layer firing condition.
  • a ceramic-coated halogen heater USHIO Inc .: heater peak wavelength: 2.5 ⁇ m
  • the temperature rising rate in firing the light emitting layer was 80 ° C./min for the initial 30 seconds.
  • the temperature reached 70 ° C. 30 seconds after the heating. That is, the time t of 70 ° C. or higher was 1 minute.
  • the substrate temperature reached 110 ° C. in 1 minute 30 seconds from the start of heating.
  • the product ⁇ of the peak wavelength of the infrared heater and the wavelength at the minimum transmittance of the glass substrate at wavelengths of 2000 nm to 3300 nm was 7.0 ⁇ m 2 .
  • ⁇ / t was 0.12 ⁇ m 2 / s.
  • Example 15 An organic electroluminescent element 11 was obtained in the same manner as in Example 14 except that the following points were changed. ⁇ Baking of hole injection layer and hole transport layer> Firing of the hole injection layer and the hole transport layer was performed using a ceramic-coated halogen heater (USHIO INC .: heater peak wavelength 2.5 ⁇ m). The baking conditions were 30 ° C. to 230 ° C. for 3 minutes, respectively. The time for the substrate to reach 150 ° C. was 50 seconds after the start of heating. Then, it became 230 degreeC in 2 minutes and 10 seconds.
  • a ceramic-coated halogen heater USHIO INC .: heater peak wavelength 2.5 ⁇ m
  • the product ⁇ of the minimum value of infrared transmission in the wavelength range of 2000 to 3300 nm of the substrate and the peak wavelength of the ceramic-coated infrared heater was 7.0 ⁇ m 2 .
  • ⁇ / t was 0.026 ⁇ m 2 / s.
  • the organic electroluminescent elements 8 to 11 obtained in Examples 12 to 15 showed higher current efficiency than the organic electroluminescent laminates F and G obtained in Comparative Examples 9 and 10.
  • Example 16 An organic electroluminescent element 12 was obtained in the same manner as in Example 14 except that the following were used as the substrate and the formation conditions of the hole injection layer, the hole transport layer, and the light emitting layer were changed as follows.
  • a 0.7 mm thick inorganic glass substrate was used as the substrate. This inorganic glass substrate had a minimum value of infrared transmittance at a wavelength of 2.8 ⁇ m, and the infrared transmittance was 68.84%.
  • ITO indium tin oxide
  • This ITO substrate is cleaned in the order of ultrasonic cleaning with an aqueous surfactant solution, water cleaning with ultra pure water, ultrasonic cleaning with ultra pure water, and water cleaning with ultra pure water, followed by drying with compressed air, and finally UV ozone cleaning. Went.
  • ⁇ Hole injection layer> A 2.5 wt% hole injection layer using 100 parts by weight of the polymer compound represented by the following formula (P4), 20 parts by weight of the compound represented by the formula (A1), and ethyl benzoate as a solvent. A forming composition was prepared.
  • This coating composition was spin coated on the substrate.
  • the spin coat was rotated at 1500 rpm and the film was formed for 30 seconds.
  • the solvent was dried on a hot plate at 80 ° C. for 30 seconds. Thereafter, the periphery of the glass substrate was wiped off with toluene.
  • a ceramic-coated infrared heater (USHIO Inc .: heater peak wavelength: 2.5 ⁇ m) was used for firing the hole injection layer.
  • the product ⁇ of the wavelength at the minimum absorption value in the range of 2000 nm to 3300 nm and the peak wavelength of the infrared heater was 7.0 ⁇ m 2 .
  • the infrared irradiation time was 7 minutes. The time to reach 70 ° C.
  • the film thickness was 50 nm.
  • a 2.5 wt% hole transport layer coating solution was prepared using cyclohexylbenzene as a solvent for the polymer material represented by the following formula (P5).
  • This hole transport layer coating solution was spin-coated under nitrogen on the previously prepared hole injection layer. The film was formed for 100 seconds at a spin coating speed of 1500 rpm. Thereafter, the solvent was dried on a hot plate at 230 ° C. for 30 seconds. Thereafter, the periphery of the substrate was wiped off with toluene. Firing was performed using the same infrared heater as the hole injection layer. The infrared irradiation time was 6 minutes. The time to reach 150 ° C. was 50 seconds after the infrared irradiation.
  • the time above 150 ° C. was 5 minutes and 10 seconds.
  • the maximum temperature reached by the substrate was 270 ° C.
  • ⁇ / t was 0.023 ⁇ m 2 / sec.
  • the above steps were performed in the atmosphere.
  • the film thickness was 37 nm.
  • ⁇ Light emitting layer> The compounds represented by the following formulas, H3, H4, and D2, were adjusted to 4.0 wt% using 25 parts by weight, 75 parts by weight, and 10 parts by weight, respectively, using cyclohexylbenzene as a solvent.
  • a layer coating solution was prepared. This light emitting layer coating solution was spin-coated under nitrogen on the previously prepared hole transport layer. The film was formed in 120 seconds at a spin coating speed of 2500 rpm. Thereafter, the periphery of the substrate was wiped off with toluene. The light emitting layer was heated under the atmosphere using the same infrared heater as the hole injection layer. The heating time was 60 seconds.
  • the temperature rising rate in firing the light emitting layer was 80 ° C./min for the initial 30 seconds. It reached 70 ° C. 30 seconds after heating, and the time t over 70 ° C. was 30 seconds. During this time, the temperature was constantly rising and was not maintained at a constant temperature. The temperature of the substrate reached 100 ° C. in 60 seconds from the start of heating. The film thickness of the light emitting layer was 54 nm.
  • the product ⁇ of the peak wavelength of the infrared heater at this time and the wavelength at the minimum transmittance of the glass substrate at wavelengths of 2000 nm to 3300 nm was 7.0 ⁇ m 2 .
  • ⁇ / t was 0.23 ⁇ m 2 / s.
  • Example 17 An organic electroluminescent element 13 was produced in the same manner as in Example 16 except that the firing conditions of the light emitting layer were changed to the following conditions.
  • the infrared irradiation time to the light emitting layer was 7 minutes.
  • the temperature rising rate in firing the light emitting layer was 80 ° C./min for the initial 30 seconds.
  • the temperature of the substrate reached 120 ° C. in 3 minutes from the start of heating, and then heated at a constant temperature at 120 ° C. ⁇ / t was 0.018 ⁇ m 2 / s.
  • Example 18 An organic electroluminescent element 14 was obtained in the same manner as in Example 16 except that the formation conditions of the hole injection layer and the hole transport layer were changed as follows. ⁇ Hole injection layer> 3.5 wt% hole injection layer using 100 parts by weight of the polymer compound represented by the following formula (P6), 15 parts by weight of the compound represented by the formula (A1), and using ethyl benzoate as a solvent. A forming composition was prepared.
  • This coating composition was spin coated on the substrate.
  • the spin coat was rotated at 1500 rpm and the film was formed for 30 seconds.
  • the solvent was dried on a hot plate at 80 ° C. for 30 seconds. Thereafter, the periphery of the glass substrate was wiped off with toluene. Firing was performed using the same infrared heater as in Example 16.
  • the infrared irradiation time was 10 minutes.
  • the time to reach 70 ° C. was 10 seconds after infrared irradiation, and the time to reach 150 ° C. was 50 seconds after infrared irradiation. Therefore, the time above 150 ° C. was 9 minutes and 10 seconds.
  • the maximum temperature reached by the substrate was 270 ° C. ⁇ / t was 0.013 ⁇ m 2 / sec.
  • the above steps were performed in the atmosphere.
  • the film thickness was 50 nm.
  • a 2.5 wt% hole transport layer coating solution was prepared using cyclohexylbenzene as a solvent for the polymer material represented by the formula (P5).
  • This hole transport layer coating solution was spin-coated under nitrogen on the previously prepared hole injection layer. The film was formed for 100 seconds at a spin coating speed of 1500 rpm. Thereafter, the solvent was dried on a hot plate at 230 ° C. for 30 seconds. Thereafter, the periphery of the substrate was wiped off with toluene. Firing was performed using the same infrared heater as in Example 16. The infrared irradiation time was 10 minutes. The time to reach 150 ° C. was 50 seconds after the infrared irradiation.
  • the time above 150 ° C. was 9 minutes and 10 seconds.
  • the maximum temperature reached by the substrate was 270 ° C.
  • ⁇ / t was 0.013 ⁇ m 2 / sec.
  • the above steps were performed in the atmosphere.
  • the film thickness was 37 nm.
  • Example 19 An organic electroluminescent device 15 was produced in the same manner as in Example 16 except that the composition for forming the light emitting layer was changed as follows. ⁇ Light emitting layer> A light emitting layer was formed in the same manner as in Example 16 except that 25 parts by weight, 75 parts by weight, and 10 parts by weight of each of the compounds represented by the following formulas, H5, H6, and D3 were used as a solvent. did.
  • Example 20 The formation of the hole injection layer and the hole transport layer was the same as that of Example 18, and the formation of the light emitting layer was the same as that of Example 19 to fabricate the organic electroluminescent element 16.
  • Example 21 An organic electroluminescent device 17 was produced in the same manner as in Example 20 except that the firing conditions of the light emitting layer were changed as follows.
  • the infrared irradiation time to the light emitting layer was 7 minutes.
  • the temperature rising rate in firing the light emitting layer was 80 ° C./min for the initial 30 seconds.
  • ⁇ / t was 0.018 ⁇ m 2 / s.
  • Example 12 When the formation conditions of the hole injection layer of Example 16 were changed as follows, the hole injection layer was not insolubilized and an organic electroluminescence device could not be produced.
  • ⁇ Hole injection layer> A 2.5 wt% hole injection layer using 100 parts by weight of the polymer compound represented by the formula (P4), 20 parts by weight of the compound represented by the formula (A1), and ethyl benzoate as a solvent.
  • a forming composition is prepared. This coating composition is spin-coated on the substrate. The spin coat is rotated at 1500 rpm and the film is formed for 30 seconds. After spin coating, the solvent is dried on a hot plate at 80 ° C. for 30 seconds. Then, the baking method of a positive hole injection layer is made to heat for 10 minutes with a 230 degreeC hot-air dryer.
  • Example 13 When the formation conditions of the hole injection layer of Example 18 were changed as follows, the hole injection layer was not insolubilized and an organic electroluminescence device could not be produced.
  • ⁇ Hole injection layer> A 3.5 wt% hole injection layer using 100 parts by weight of the polymer compound represented by the formula (P6), 20 parts by weight of the compound represented by the formula (A1), and ethyl benzoate as a solvent.
  • a forming composition is prepared. This coating composition is spin-coated on the substrate. The spin coat is rotated at 1500 rpm and the film is formed for 30 seconds. After spin coating, the solvent is dried on a hot plate at 80 ° C. for 30 seconds. Then, the baking method of a positive hole injection layer is made to heat for 10 minutes with a 230 degreeC hot-air dryer.
  • This coating composition is spin-coated on the substrate.
  • the spin coat is rotated at 1500 rpm and the film is formed for 100 seconds. Thereafter, the solvent is dried on a hot plate at 230 ° C. for 30 seconds. Then, the baking method of a positive hole injection layer is made to heat for 10 minutes with a 230 degreeC hot-air dryer.
  • Table 14 summarizes the characteristics of the devices obtained in the above examples.
  • the voltage and current efficiencies are the voltage relative value and the current efficiency relative value obtained by dividing the organic electroluminescent element 12 and the organic electroluminescent element 15 by the voltage (V) and current efficiency (cd / A) at 10 mA / cm 2 . It showed in.
  • the layers can be laminated and applied by baking for a short time, and the baking is performed by a hot air drying furnace or a hot plate.
  • the baking is performed by a hot air drying furnace or a hot plate.
  • Example 22 An organic electroluminescent element 18 was obtained in the same manner as in Example 3 except that the formation conditions of the hole injection layer, the hole transport layer, and the light emitting layer were changed as follows.
  • ⁇ Hole injection layer> Using a polymer compound represented by the following formula (P7) as 100 parts by weight, a compound represented by the formula (A1) as 15 parts by weight, and using ethyl benzoate as a solvent, a 3.0% by weight hole injection layer A forming composition was prepared.
  • This coating composition was spin coated on the substrate.
  • the spin coat was rotated at 3500 rpm and the film was formed for 30 seconds.
  • the solvent was dried on a hot plate at 80 ° C. for 30 seconds. Thereafter, the periphery of the glass substrate was wiped off with toluene.
  • a ceramic-coated infrared heater (USHIO Inc .: heater peak wavelength: 2.5 ⁇ m) was used for firing the hole injection layer.
  • the infrared irradiation time was 6 minutes.
  • the time to reach 70 ° C. was 10 seconds after infrared irradiation, and the time to reach 150 ° C. was 50 seconds after infrared irradiation. Therefore, the time above 150 ° C. was 5 minutes and 10 seconds.
  • the maximum temperature reached by the substrate was 270 ° C. ⁇ / t was 0.023 ⁇ m 2 / sec.
  • the above steps were performed in the atmosphere.
  • the film thickness was 50 nm.
  • This hole transport layer coating solution was spin-coated under nitrogen on the previously prepared hole injection layer.
  • the film was formed for 100 seconds at a spin coating speed of 1500 rpm. Thereafter, the solvent was dried on a hot plate at 230 ° C. for 30 seconds. Thereafter, the periphery of the substrate was wiped off with toluene. Firing was performed using the same infrared heater as that used for forming the hole injection layer.
  • the infrared irradiation time was 6 minutes.
  • the time to reach 150 ° C. was 50 seconds after the infrared irradiation. Therefore, the time above 150 ° C. was 5 minutes and 50 seconds.
  • the maximum temperature reached by the substrate was 270 ° C. ⁇ / t was 0.023 ⁇ m 2 / sec.
  • the above steps were performed in the atmosphere.
  • the film thickness was 40 nm.
  • This light emitting layer coating solution was spin-coated under nitrogen on the previously prepared hole transport layer. The film was formed in 120 seconds at a spin coating speed of 2400 rpm. Thereafter, the periphery of the substrate was wiped off with toluene. After film formation, it was heated at 120 ° C. for 20 minutes with a hot plate under nitrogen. The film thickness at this time was 50 nm.
  • Example 23 An organic electroluminescent element 19 was obtained in the same manner as in Example 22 except that the formation conditions of the hole injection layer were changed as follows.
  • a halogen heater manufactured by Ushio Inc .; heater peak wavelength 1.2 ⁇ m
  • the irradiation time of infrared rays was set to 15 minutes.
  • the time to reach 70 ° C. was 10 seconds after infrared irradiation, and the time to reach 150 ° C. was 50 seconds after infrared irradiation. Therefore, the time above 150 ° C. was 14 minutes and 10 seconds.
  • the maximum temperature reached by the substrate was 270 ° C. ⁇ / t was 0.0040 ⁇ m 2 / sec.
  • Example 24 An organic electroluminescent device 20 was obtained in the same manner as in Example 23 except that the formation conditions of the hole injection layer and the hole transport layer were changed as follows. ⁇ Hole injection layer> The infrared irradiation time was 10 minutes. The time to reach 70 ° C. was 10 seconds after infrared irradiation, and the time to reach 150 ° C. was 50 seconds after infrared irradiation. Therefore, the time above 150 ° C. was 9 minutes and 10 seconds. The maximum temperature reached by the substrate was 270 ° C. ⁇ / t was 0.0061 ⁇ m 2 / sec.
  • ⁇ Hole transport layer> Using a polymer material represented by the following formula (P9) as a solvent, cyclohexylbenzene was used to prepare a 3.0 wt% hole transport layer coating solution. This hole transport layer coating solution was spin-coated under nitrogen on the previously prepared hole injection layer. The film was formed for 100 seconds at a spin coating speed of 1500 rpm. Thereafter, the solvent was dried on a hot plate at 230 ° C. for 30 seconds. Thereafter, the periphery of the substrate was wiped off with toluene. Firing was performed using the same halogen heater as the hole injection layer. The infrared irradiation time was 6 minutes. The time to reach 150 ° C.
  • P9 cyclohexylbenzene
  • the film thickness was 40 nm.
  • Example 25 An organic electroluminescent element 21 was obtained in the same manner as in Example 24 except that the formation conditions of the hole injection layer were changed as follows. ⁇ Hole injection layer> 100 wt parts of the polymer compound represented by the following formula (P10), 15 wt parts of the compound represented by the formula (A1), and ethyl benzoate as a solvent, a 3.0 wt% hole injection layer A forming composition was prepared.
  • This coating composition was spin coated on the substrate.
  • the spin coat was rotated at 3500 rpm and the film was formed for 30 seconds.
  • the solvent was dried on a hot plate at 80 ° C. for 30 seconds. Thereafter, the periphery of the glass substrate was wiped off with toluene. Firing of the hole injection layer was performed using the same infrared heater as in Example 22.
  • the infrared irradiation time was 6 minutes.
  • the time to reach 70 ° C. was 10 seconds after infrared irradiation, and the time to reach 150 ° C. was 50 seconds after infrared irradiation. Therefore, the time above 150 ° C. was 5 minutes and 10 seconds.
  • the maximum temperature reached by the substrate was 270 ° C. ⁇ / t was 0.023 ⁇ m 2 / sec.
  • the above steps were performed in the atmosphere.
  • the film thickness was 50 nm.
  • Table 15 summarizes the characteristics of the devices obtained in the above examples.
  • the voltage and current efficiency are shown as a voltage relative value and a current efficiency relative value divided by the voltage (V) and current efficiency (cd / A) at 2500 cd / m 2 of the organic electroluminescent element 18.
  • each layer can be laminated and coated by baking for a short time, which cannot be achieved by baking in a hot air drying furnace or a hot plate.
  • a short tact time can be achieved, and an organic electroluminescence device can be produced at low cost.

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