WO2007060826A1 - Élément électroluminescent organique, dispositif d’affichage et système d’éclairage - Google Patents

Élément électroluminescent organique, dispositif d’affichage et système d’éclairage Download PDF

Info

Publication number
WO2007060826A1
WO2007060826A1 PCT/JP2006/322143 JP2006322143W WO2007060826A1 WO 2007060826 A1 WO2007060826 A1 WO 2007060826A1 JP 2006322143 W JP2006322143 W JP 2006322143W WO 2007060826 A1 WO2007060826 A1 WO 2007060826A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
organic
layer
compound
carbon atoms
Prior art date
Application number
PCT/JP2006/322143
Other languages
English (en)
Japanese (ja)
Inventor
Shuichi Sugita
Hiroshi Kita
Original Assignee
Konica Minolta Holdings, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Holdings, Inc. filed Critical Konica Minolta Holdings, Inc.
Priority to JP2007546392A priority Critical patent/JPWO2007060826A1/ja
Publication of WO2007060826A1 publication Critical patent/WO2007060826A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1048—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum

Definitions

  • Organic electoluminescence device display device and lighting device
  • the present invention relates to an organic electroluminescent mouth luminescence element, and a display device and an illumination device using the organic electroluminescent mouth luminescence element.
  • ELD electoric luminescence display
  • organic EL devices organic electroluminescence devices
  • An organic EL device has a structure in which a light emitting layer containing a compound that emits light is sandwiched between a cathode and an anode.
  • excitons excitons Is a device that emits light using the emission of light (fluorescence / phosphorescence) when this exciton is deactivated, and can emit light at a voltage of several volts to several tens of volts. Therefore, it is a thin-film, completely solid element that has a wide viewing angle and high visibility, and has attracted attention from the viewpoints of space saving and portability.
  • Non-Patent Document 1 organic EL devices that use phosphorescence from excited triplets
  • Non-Patent Document 2 research on materials that exhibit phosphorescence at room temperature has become active.
  • the upper limit of the internal quantum efficiency is 100% when the 0 excited triplet is used, the luminous efficiency is doubled in principle compared to the case of the excited singlet. It has attracted attention because it has almost the same performance as a tube and can be applied to lighting.
  • there have been many compounds are synthesized and studied about the heavy metal complexes such as iridium complexes (e.g., Non-Patent Documents 3 and Patent Document 1.) 0
  • Patent Document 2 JP 2002-100476 A
  • Patent Document 3 JP 2002-117978 A
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2002-299061
  • Non-Patent Document 1 M. A. Baldo et al., Nature, 395 ⁇ , 151–154 (1998)
  • Non-Patent Document 2 M. A. Baldo et al., Nature, 403 ⁇ , 17, 750-753 (2000)
  • Non-Patent Document 3 S. Lamansky et al., J. Am. Chem. Soc., 123 ⁇ , 4304 (2001)
  • the conventional organic-electric-mouth luminescence device is desired to be improved in voltage rise when driven at a low voltage, generation of dark spots, and stability over time at high temperature and high humidity. Yes.
  • further improvement in light emission luminance is desired.
  • the present invention has been made in view of the related problems, and an object of the present invention is to exhibit a favorable light emission luminance, increase in voltage when driven at a constant current, further increase in temperature and humidity with fewer dark spots. It is to provide an organic EL element having high stability with time, a display device using the same, and a lighting device.
  • An organic electroluminescent device having at least one organic layer between an anode and a cathode on a substrate
  • At least one of the organic layers is a light emitting layer containing a phosphorescent compound represented by the following general formula (1), and the organic layer contains 10-pm to 10 3 ppm of an organic solvent. With features Organic-elect luminescence element.
  • R represents a substituent.
  • Z is a group of nonmetallic atoms necessary to form a 5- to 7-membered ring
  • nl represents an integer of 0 to 5.
  • B to B are carbon atom, nitrogen atom and oxygen atom, respectively.
  • M is the element circumference
  • L represents a group of atoms that form a bidentate ligand with X and X.
  • ml represents an integer of 1, 2 or 3
  • m2 represents a force of 0, 1 or 2
  • ml + m2 represents 2 or 3.
  • a display device comprising the organic electoluminescence element according to any one of 1 to 6 above.
  • An illuminating device comprising the organic electoluminescence element according to any one of 1 to 6 above.
  • a display device comprising the illumination device according to 8 and a liquid crystal element as display means.
  • an organic EL device that exhibits good light emission luminance, increases voltage when driven at a constant current, has less dark spots, has higher temperature stability under high temperature and high humidity, and the same is used.
  • a display device and a lighting device could be provided.
  • FIG. 1 is a schematic view showing a layer structure of a transparent gas noria film according to the present invention.
  • FIG. 2 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus of a type that treats a substrate between counter electrodes useful for the present invention.
  • FIG. 3 is a diagram showing a discharge and film forming process of an organic EL element OLED1-1.
  • FIG. 4 is a schematic view showing an example of a display device constituted by an organic EL element cover.
  • FIG. 5 is a schematic diagram of a display unit.
  • the structure defined in any one of claims 1 to 6 exhibits good light emission luminance and voltage increase when driven at a constant current. We were able to provide an organic EL device with less dark spots and high stability over time at high temperatures and high humidity. In addition, a display device and a lighting device provided with the organic EL element could be provided.
  • the present inventors have provided at least one organic layer between the anode and the cathode on the substrate as described in claim 1.
  • the organic layer is a light emitting layer containing the phosphorescent compound represented by the general formula (1), and the organic layer contains an organic solvent. By adjusting it to contain 2 ppm to 10 pm, it exhibits good light emission brightness, voltage rise when driven at constant current, high darkness with fewer dark spots, high temporal stability under high humidity, and organic EL It was found that an element can be obtained.
  • the organic layer according to the present invention is a feature may contain organic solvents 10- 2 ppm ⁇ 10 pm
  • the organic solvent contains 0.1 lppm to: LOOppm
  • the organic solvent according to the present invention is not particularly limited.
  • alcohols methanol, ethanol, etc.
  • carboxylic acid esters ethyl acetate, propyl acetate, etc.
  • nitriles acetonitrile
  • Etc. nitriles
  • ethers isopropyl ether, THF, etc.
  • aromatic hydrocarbons cyclohexylbenzene, toluene, xylene, etc.
  • halogenated alkyls salt methylene, etc.
  • saturated hydrocarbons heptane, etc.
  • carboxylic acid esters preferred are: carboxylic acid esters, nitriles, ethers, aromatic hydrocarbons, alkyl halides, and saturated hydrocarbons, and more preferably carboxylic acid esters. , Ethers and aromatic hydrocarbons.
  • the boiling point of the organic solvent used in the present invention is preferably 200 ° C or less, more preferably 150 ° C or less.
  • the volatile organic solvent contained in the organic layer according to the present invention can be measured by gas chromatography (GC) mass spectrometry (MS) equipped with a purge & trap sampler.
  • GC gas chromatography
  • MS mass spectrometry
  • PT-GCZMS Specifically, a 10cm x 10cm square organic EL device was fabricated, and the residual solvent was adsorbed in the gas recovery chamber and the organic gas adsorption tube (TENAX GR), and PT-GCZMS measurement was performed. It was.
  • the solvent concentration was determined from a calibration curve prepared using a reference sample with a known concentration.
  • the organic layer according to the present invention has at least one light emitting layer, and the light emitting layer is characterized by containing the phosphorescent compound represented by the general formula (1).
  • the phosphorescent compound represented by the general formula (1) will be described.
  • examples of the substituent represented by R include an alkyl group (for example,
  • aromatic hydrocarbon ring group aromatic carbocyclic group, aryl group, etc., for example, Phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenyl group), aromatic Group heterocyclic group (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, virazolyl group, pyrazol group, triazolyl group (for example, 1, 2, 4 triazole-1-y
  • acyl group for example, acetyl group, ethylcarbonyl group, propylcarbon group, pentylcarbonyl group, cyclohexylcarboxyl group.
  • octylcarbol group 2-ethylhexylcarbol group, dodecylcarpol group, phenolcarol group, naphthylcarbol group, pyridylcarbol group, etc.
  • acyloxy group for example, acetylyloxy group
  • Ethylcarbonyloxy group butylcarbonyloxy group
  • octylcarbonyloxy group dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.
  • amide group for example, methylcarbolamino group, ethylcarbo- group) Luamino group, dimethyl carbolumino group, propyl carbolumino group, pentyl carbolumino group, cyclohexyl Carboxylamino group, 2-ethylhexylcarbolamino group, octylcarbolamino group, dodecylcarbolamino group
  • Sylsulfuric group dodecylsulfuric group, phenylsulfuric group, naphthylsulfuric group, 2-pyridylsulfiferic group, etc.
  • alkylsulfuric group for example, methinolesnorehoninole group, Ethinolesnole-nole group, butinolesnolehoninole group, cyclohexenolesnoleol group, 2-ethylhexylsulfol group, dodecylsulfol group, etc.
  • arylsulfol group or heteroarylsulfol group for example, a phenylsulfol group, a naphthylsulfol group, a 2-pyridylsulfol group, etc.
  • an amino group for example, amino Group, Echirua amino group, Jimechiruamino group, Buchirua
  • an alkyl group or an aryl group is preferable, and an unsubstituted alkyl group or an aryl group is more preferable.
  • Z represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring.
  • the 5- to 7-membered ring formed by Z include a benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, pyrrole ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring, and thiazole ring. It is done. Of these, a benzene ring is preferred.
  • B to B are each a carbon atom, a nitrogen atom, an oxygen atom or sulfur.
  • a monocyclic ring is preferred as the aromatic nitrogen-containing heterocycle formed by these five atoms. Examples thereof include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an oxadiazole ring, and a thiadiazole ring.
  • a pyrazole ring and an imidazole ring are preferable, and an imidazole ring is more preferable.
  • substituents are unsubstituted alkyl groups and unsubstituted aryl groups.
  • L represents an atomic group that forms a bidentate ligand with X and X.
  • bidentate ligand represented by 1 1 2 1 L -X for example, substituted or unsubstituted
  • Examples thereof include phenyl pyridine, vinyl virazole, phenol imidazole, phenol triazole, phenol tetrazole, virazol ball, picolinic acid, and acetylacetone.
  • these groups may be further substituted with the above substituents.
  • ml represents an integer of 1, 2 or 3
  • m2 represents a force representing an integer of 0, 1 or 2 ml + m2 is
  • m2 is preferably 0.
  • the metal represented by M (including the field of metal ions) is an element.
  • Transition metal elements from Group 8 to Group 10 of the periodic table are used. However, iridium and platinum are preferred, and iridium is more preferred.
  • the phosphorescent compound represented by the general formula (1) of the present invention may have a polymerizable group or a reactive group! .
  • the host compound preferably contained in the light emitting layer according to the present invention will be described.
  • the host compound used in the present invention includes, for example, a force rubazole derivative, a carboline derivative, a diaza force rubazole derivative (here, diaza force rubazole has at least one carbon atom constituting a carboline ring.
  • Triazole derivatives Triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, phenanthoracin derivatives, oxazoles Derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, organometallic compounds, arylene methane derivatives, and the like.
  • R to R each represents a substituent.
  • nl and n2 represent an integer of 0 to 3.
  • Z and Z represent an aromatic heterocyclic group or an aromatic hydrocarbon ring group, and Z represents 2 Represents a valent linking group or a simple bond.
  • L is a divalent linking group or a simple bond
  • R represents a substituent. ni l is 0
  • a and A are the above general
  • n21 and n22 are 0
  • A represents a group represented by the general formula (a).
  • L represents a divalent linking group.
  • R 1 and R 2 represent a substituent.
  • n31 and n32 are 0
  • Y represents an oxygen atom, an ion atom, an imino group, a sulfinyl group, an alkylsulfonyl group or an arylsulfonyl group.
  • a and A represent a compound represented by the above general formula (a)
  • Examples of the substituent represented by 1 4 11 23 24 31 32 include alkyl groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms. methyl group, Echiru group, i so - propyl, tert- butyl group, n- Okuchiru group, n- decyl group, Kisadeshi to n- group, a cyclopropyl group, a cyclopentyl group, cyclohexyl group and the like cyclohexylene.
  • Alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as vinyl group, aryl group, 2-butur group, 3-pentene
  • An alkyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as a propargyl group, 3— Pentynyl group, etc.), aromatic hydrocarbon ring group (Also known as an aromatic hydrocarbon group or aryl group, preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
  • amino group, methylamino group, etc. A dimethylamino group, a jetylamino group, a dibenzylamino group, etc.
  • an alkoxy group preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
  • An acyloxy group preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to carbon atoms: L0, and examples thereof include an acetoxy group and a benzoyloxy group).
  • An acylamino group preferably having 2 to 20 carbon atoms, more preferably Preferably, it has 2 to 16 carbon atoms, particularly preferably 2 to carbon atoms: LO, and examples thereof include acetylamino groups and benzoylamino groups.
  • An alkoxycarbolumino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include a methoxycarbolamino group).
  • Aryloxy-carboamino groups (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenylcarbocarboamino groups and the like.
  • a sulfo-lumino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfo-lumino group and a benzenesulfo-lumino group.
  • a sulfamoyl group (preferably having a carbon number of 0 to 20, more preferably a carbon number of 0 to 16, particularly preferably a carbon number of 0 to 12, such as sulfamoyl group, methylsulfamoy Group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.), rubamoyl group (preferably 1-20 carbon atoms, more preferably 1-16 carbon atoms, particularly preferably 1-12 carbon atoms).
  • a strong rubamoyl group a methylcarbamoyl group, a jet carbamoyl group, a phenylcarbamoyl group, etc.
  • an alkylthio group preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, Particularly preferably, it has 1 to 12 carbon atoms, and examples thereof include a methylthio group, an ethylthio group, etc.
  • an arylthio group preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably carbon atoms).
  • a phenylthio group an alkylsulfonyl group or an arylsulfonyl group (preferably having a carbon number of 1 to 20, more preferably carbon.
  • 1 to 16 particularly preferably 1 to 12 carbon atoms such as mesyl group and tosyl group
  • sulfyl group preferably 1 to 20 carbon atoms, more preferably 1 carbon atom
  • ureido group preferably 1 to 20 carbon atoms, more preferably 1 carbon atom
  • phosphoric acid amide group preferably having 1 to 20 carbon atoms, and more).
  • the sulfo group is C1-C16, Most preferably, it is C1-C12, for example, a jetyl phosphoric acid amide group, a phenylphosphoric acid amide group, etc. are mentioned. ), Hydroxy group, mercapto group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), cyan group, sulfo group, carbo group Xyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (including hetero atoms such as nitrogen atom, oxygen atom, sulfur atom, selenium atom, preferably 1 to 30 and more preferably those having 1 to 20 carbon atoms, such as imidazolyl, pyridyl, furyl group, piperidyl group, morpholino group, etc.). These substituents may be further substituted. If possible, connect them to
  • an alkyl group and an aryl group are preferred.
  • hydrocarbon groups such as a alkylene group, an alkylene group, an alkylene group, and an arylene group
  • those containing a hetero atom eg, a heteroarylene group
  • thiophene-2, 5 A divalent linking group derived from a compound having an aromatic heterocycle such as a diyl group or a pyrazine-2,3-diyl group, or oxygen Or a chalcogen atom such as sulfur.
  • it may be a group that meets and links heteroatoms such as an alkylimino group, a dialkylsilane diyl group, or a diarylgermandyl group.
  • a force capable of using either a low molecular compound or a high molecular compound is preferable, and a high molecular compound is particularly preferable.
  • the polymer compound is a compound obtained by polymerizing a compound having at least one polymerizable group (polymerizable compound).
  • the polymerizable group include a vinyl group, an epoxy group, an oxetane group, a isocyanate group, Examples include thioisocyanate groups. Of these, preferred is a vinyl group.
  • the compounds represented by the above general formulas (2) to (5) have these polymerizable groups in the molecule!
  • a polymer formed by using a monomer at any position is preferred.
  • a bond may be formed after the organic EL element is fabricated!
  • energy such as heat (light 'light' ultrasonic waves, etc.) or to add a polymerization initiator, acid catalyst or base catalyst to cause the reaction.
  • the reaction may be caused by a current supplied at the time of driving the light emitting device, generated light or heat. Two or more polymerizable compounds may be polymerized to form a copolymer.
  • the polymer formed by polymerization preferably has a weight average molecular weight of 5000 to 100,000, more preferably 5000 to 200,000. As a result, the luminous brightness and dark spots are further improved.
  • the weight average molecular weight according to the present invention can be measured by a commercially available GPC (gel permeation chromatography) measuring apparatus.
  • GPC gel permeation chromatography
  • radical polymerization initiator examples include 2,2'-azobisbutyoxy-tolyl, 2,2'-azobiscyclohexanecarbonitryl, 1,1'-azobis (cyclohexane-1 carbotolyl), 2, 2 '— Azobis (2-methylbutyryl-tolyl), 2, 2 ′ — Azobis (2, 4-dimethyl valerine-tolyl), 2, 2' — Azobis (4-methoxy-1,4-dimethyl valerine-tolyl) Ril), 4, 4'-azobis (4-cyananovaleric acid), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis (2-methylpropionamidoxime), 2, 2'-azobis (2-(2--imi) 1-yl) propane), 2,2'-azobis (2,4,4 trimethylpentane) and other initiators, benzoyl peroxide, tert-butyl peroxide, tert-butyl hydroperu Development of pera
  • disulfide initiators such as tetraethylthiilamdisulfide, -troxyl initiators such as 2,2,6,6-tetramethylbiperidine 1-oxyl, 4,4'-di-tert-butyl-2 Living radical polymerization initiators such as, 2'-bipyridine copper complex-trichloromethyl acetate complex can also be used.
  • Acid catalysts include activated clays, clays such as acid clays, mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as ⁇ -toluenesulfonic acid and trifluoroacetic acid, aluminum chloride, ferric chloride, chloride Lewis acids such as stannic, titanium trichloride, titanium tetrachloride, boron trifluoride, hydrogen fluoride, boron trifluoride, aluminum bromide, gallium chloride, gallium bromide, solid acids such as Various materials such as zeolite, silica, alumina, silica'alumina, cation exchange resin, and heteropolyacid (for example, phosphotungstic acid, phosphomolybdic acid, key tungstic acid, and chemolybdenic acid) can be used.
  • clays such as acid clays, mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as ⁇ -toluenesulfonic acid and trifluoro
  • Examples of the basic catalyst used in the present invention include Li CO, Na CO, and K CO.
  • Li metal carbonate alkaline earth metal carbonate such as BaCO, CaCO, Li 0, Na 0, K O
  • Alkali metal oxides such as 3 3 2 2 2, alkaline earth metal oxides such as BaO and CaO, alkali metals such as Na and K, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or Examples thereof include alkoxides such as sodium, potassium, rubidium and cesium.
  • the present invention is not limited to these.
  • the host compound according to the present invention may be a polymer formed by polymerizing the polymerizable compound, which may be used alone.
  • the layer structure of the organic electoluminescence device (organic EL device) according to the present invention will be described.
  • the organic EL device of the present invention has an electrode (cathode and anode) and at least one organic layer on a substrate, and at least one of the organic layers contains a phosphorescent compound. It is.
  • the light emitting layer according to the present invention is a layer that emits light when an electric current is applied to an electrode having a cathode and an anodic force. This refers to a layer containing a compound that emits light.
  • the organic layer according to the present invention is sandwiched between a cathode and an anode, which may have a hole transport layer, an electron transport layer, a cathode buffer layer, a cathode buffer layer, etc. in addition to the light emitting layer, if necessary. Take the structure. Specific examples include the structures shown below.
  • the light emitting layer is formed by a coating method, but the other layers are vapor deposition methods, It may be formed by any coating method.
  • the coating method spin coating, dip coating, roll coating, bar coating, flexographic printing, screen printing, offset printing, and ink jetting are used, and an inkjet method is preferable.
  • the organic layer is preferably 2 layers or more, more preferably 3 layers or more.
  • the light emitting layer of the organic EL device of the present invention contains a phosphorescent compound represented by the above general formula (1), and examples of the host compound include the above general formulas (2), (3), (4 And a compound selected from the group consisting of compounds (5) and (5).
  • the phosphorescent compound according to the present invention is a compound in which luminescence with an excited triplet force is observed, and is a compound that emits phosphorescence at room temperature (25 ° C). A compound having a rate of 0.01 or more at 25 ° C.
  • the phosphorescence quantum yield is preferably 0.1 or more.
  • the phosphorescent quantum yield can be measured by the method described in the fourth edition of Experimental Chemistry Course 7, Spectroscopy II, page 398 (1992 edition, Maruzen). Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence quantum compound used in the present invention can achieve the above phosphorescence quantum yield in any solvent. If you do.
  • the host compound is a compound having a phosphorescence quantum yield of phosphorescence emission of less than 0.01 at room temperature (25 ° C) among the compounds contained in the light emitting layer. Defined as a compound.
  • a plurality of host compounds may be used in combination. By using multiple types of host compounds, it is possible to adjust the movement of electric charge, and the organic EL device can be made highly efficient. In addition, by using a plurality of phosphorescent compounds, it is possible to mix different light emission, thereby obtaining an arbitrary emission color. White light emission is possible by adjusting the type of phosphorescent compound and the amount of doping, and it can also be applied to lighting and knocklights.
  • the host compound according to the present invention may be used in combination with a conventionally known compound.
  • the host compound has a hole transporting ability and an electron transporting ability, and prevents the emission of light from being increased in wavelength.
  • a compound having a Tg (glass transition temperature) is preferred.
  • the host compound has one of hole injection or transport and electron barrier properties. For example, a force rubazole derivative, a carboline derivative, a diaza force rubazole derivative, a triazole derivative, an oxadiazole derivative.
  • Imidazole derivatives polyarylalkane derivatives, pyrazoline derivatives and pyrazophane derivatives, fluorenedamine derivatives, arylamine derivatives, phanantorin derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, organometallics Compounds, arylmethane derivatives, etc.
  • a force rubazole derivative a carboline derivative, or a diaza force rubazole derivative.
  • a conventionally known phosphorescent compound or a fluorescent compound (also referred to as a fluorescent compound) may be used in combination.
  • phosphorescent compounds that can be used in combination are shown below, but are not limited thereto.
  • these compounds can be synthesized by, for example, the method described in Inorg. Chem. 40 ⁇ , 1704-1711.
  • these compounds may or may not have a polymerizable group or a reactive group.
  • the fluorescent compound used in the present invention is a compound that, by containing a fluorescent compound, can emit fluorescent light having a maximum emission wavelength different from the case where it does not contain, preferably in a solution state.
  • the fluorescence quantum yield is high.
  • the fluorescence quantum yield is preferably 10% or more, particularly preferably 30% or more.
  • Specific fluorescent compounds include, for example, coumarin dyes, anthracene dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes.
  • fluorescence quantum yield here can be measured by the method described on page 362 (1992 edition, Maruzen) of Spectroscopy II, 4th edition, Experimental Chemistry Course 7.
  • the film thickness of the light emitting layer thus formed can be appropriately selected according to the situation where there is no limit. It is preferable to adjust the film thickness to a range of ⁇ 5 ⁇ m.
  • the hole injection layer and hole transport layer used in the present invention have a function of transmitting holes injected from the anode to the light emitting layer.
  • the hole injection layer and hole transport layer are formed of an anode and a light emitting layer. By interposing them, many holes are injected into the light emitting layer with a lower electric field, and electrons injected into the light emitting layer from the cathode, the electron injection layer, or the electron transport layer are injected into the light emitting layer and the hole.
  • An electron barrier existing at the interface of the layer or the hole transport layer is accumulated at the interface in the light emitting layer, and the light emitting efficiency is improved.
  • hole injection material and hole transport material has a property of transmitting the holes injected from the anode to the light emitting layer.
  • hole injection material and hole transport material Conventionally, in photoconductive materials, those conventionally used as hole charge injecting and transporting materials, and known materials used in hole injection layers and hole transporting layers of EL devices are not particularly limited. Any one can be selected and used.
  • the hole injecting material and the hole transporting material have either hole injection or transport and electron barrier properties, and may be either organic or inorganic.
  • Examples of the hole injection material and hole transport material include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazophan derivatives, furan diamine derivatives, arylamine derivatives, and amino-substituted chalcone derivatives.
  • Oxazole derivatives styrylanthracene derivatives, fluorenone derivatives, hydrazole derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, or conductive polymer oligomers, particularly thiophene oligomers.
  • aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N' —tetraphenyl 4,4 ′ — diaminophenol; N , N ′ —Diphenyl N, N ′ —Bis (3-methylphenol) 1 [1, 1 ′ —Biphenyl] 4,4 ′ —Diamine (TPD); 2, 2—Bis ( 4-di-p-tolylaminophenol) propane; 1, 1-bis (4-di-p —Tolylaminophenyl) cyclohexane; N, N, N ′, N ′ —tetra-l-tril-l, 4,4′-diaminobiphenyl; 1, 1 bis (4-di-l-r-tri-laminophenyl) 4 phenyl cyclo Hexane; Bis (4-dimethylamino-2-methylphenol) phenylmethane; Bis (4-dimethylamino-2-
  • inorganic compounds such as ⁇ -type Si and p-type SiC can also be used as the hole injection material and the hole transport material.
  • the above hole injection material and hole transport material are formed into a thin film by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. Can be formed.
  • the thicknesses of the hole injection layer and the hole transport layer are not particularly limited, but are preferably adjusted to a range of 5 nm to 5 ⁇ m @.
  • the hole injection layer and the hole transport layer may be a single layer structure of one or more of the above materials, or may be a laminated structure including a plurality of layers having the same composition or different compositions.
  • the electron transport layer according to the present invention is not particularly limited as long as it has a function of transmitting electrons injected from the cathode to the light emitting layer. Can be used.
  • electron transport materials examples include: -to-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, and heterocyclic rings such as naphthalene perylene. Examples thereof include tetracarboxylic anhydride, carbodiimide, fluorenylidenemethane derivative, anthraquinodimethane and anthrone derivative, oxadiazole derivative, and organometallic complex.
  • thiadiazole derivatives in which the oxygen atom of the oxaziazole ring is substituted with a sulfur atom, and quinoxaline derivatives having a quinoxaline ring known as an electron withdrawing group can also be used as the electron transporting material.
  • quinoxaline derivatives having a quinoxaline ring known as an electron withdrawing group can also be used as the electron transporting material.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • [0123] or 8 Metal complexes of quinolinol derivatives for example, tris (8 quinolinol) aluminum (Alq), tris (5,7-dichloro-1-8-quinolinol) aluminum, tris (5,7-dibromone 8
  • the central metal of these metal complexes is quinolinol) aluminum, tris (2methyl 8-quinolinol) aluminum, tris (5-methyl 8-quinolinol) aluminum, bis (8-quinolinol) zinc (Zn q), etc.
  • Metal complexes replacing In, Mg, Cu, Ca, Sn, Ga or Pb can also be used as electron transport materials.
  • metal-free or metal phthalocyanine and those having a terminal substituted with an alkyl group or a sulfonic acid group can be preferably used as an electron transporting material.
  • the distyrylvirazine derivative exemplified as the material for the light-emitting layer can also be used as an electron transport material, and, like the hole injection layer and the hole transport layer, n-type mono-Si, n-type—such as SiC A semiconductor can also be used as an electron transport material.
  • the thickness of the electron transport layer is not particularly limited, but is preferably adjusted to a range of 5 ⁇ to 5 / ⁇ m.
  • the electron transport layer may have a single layer structure that is one or two or more of these electron transport materials, or may have a laminated structure that includes a plurality of layers having the same composition or different compositions.
  • a buffer layer may exist between the anode and the light emitting layer or hole injection layer and between the cathode and the light emitting layer or electron injection layer.
  • the nofer layer is a layer provided between the electrode and the organic layer in order to lower the driving voltage and improve the luminous efficiency. “The organic EL element and its industrial front line (November 30, 1998) 2) Chapter 2 “Electrode Materials” (pages 123 to 166) of “Nuichi” Co., Ltd.), and has an anode buffer layer and a cathode buffer layer.
  • anode buffer layer The details of the anode buffer layer are also described in JP-A-9-45479, JP-A-9260062, JP-A-8-288069 and the like.
  • copper phthalocyanine is described in detail.
  • cathode buffer layer The details of the cathode buffer layer are also described in JP-A-6-325871, JP-A-917574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc.
  • a single layer buffer For example, a single layer buffer.
  • the thickness of the buffer layer is preferably in the range of 0.1 nm to LOOnm, although it depends on the material desired to be a very thin film.
  • layers having other functions may be laminated as required.
  • the electrode of the organic EL element consists of a cathode and an anode.
  • an electrode material made of a metal, an alloy, an electrically conductive compound or a mixture thereof having a high work function (4 eV or more) is preferably used.
  • Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as Cul, indium tin oxide (ITO), SnO, and ZnO.
  • the anode may be formed by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or pattern accuracy is not required. If not (about 100 m or more), a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. In the case where light emission is extracted from this anode, it is desirable that the transmittance be greater than 10%, or the sheet resistance as the anode is preferably several hundred ⁇ / mouth or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1 ⁇ m, preferably 10 nm to 200 nm.
  • the cathode those having a small work function! / E (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof are preferably used.
  • an electron injecting metal referred to as an electron injecting metal
  • an alloy referred to as an electrically conductive compound
  • a mixture thereof are preferably used.
  • electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium Z copper mixture, magnesium Z silver mixture, magnesium z aluminum mixture, magnesium Z indium mixture, aluminum Z aluminum oxide.
  • a mixture of an electron injectable metal and a second metal which is a stable metal having a larger work function value than this, for example, magnesium Z Silver mixture, magnesium Z aluminum mixture, magnesium Z indium mixture, aluminum Z acid aluminum (Al o) mixture, lithium
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as the cathode is preferably several hundred ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 1 ⁇ m, preferably 50 nm to 200 nm.
  • the anode or the cathode of the organic EL element is transparent or translucent, it is advantageous because the light emission efficiency is improved.
  • the organic EL device of the present invention is preferably formed on a substrate (hereinafter also referred to as a substrate, a substrate, a support, a film, etc.).
  • Examples of the base material that can be used in the organic EL device of the present invention include glass and plastic.
  • the type is not particularly limited, and is not particularly limited as long as it is transparent.
  • Examples of the substrate preferably used include glass, quartz, and a transparent film.
  • the base material is a transparent film capable of giving flexibility to the organic EL element.
  • a homopolymer or copolymer such as ethylene, polypropylene, or butene, or a polyolefin (PO) resin such as a copolymer, or an amorphous polyolefin resin such as a cyclic polyolefin (APO).
  • PO polyolefin
  • APO amorphous polyolefin resin
  • a rosin composition comprising an acrylate compound having a radical-reactive unsaturated compound, or a mercapto compound having a thiol group and the acrylate resin compound.
  • a photocurable resin such as a resin composition prepared by dissolving an oligomer such as epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, etc. in a polyfunctional acrylate monomer, and a mixture thereof. Etc. can also be used.
  • ZE NEX ZEONOR (manufactured by ZEON CORPORATION), ARTON (manufactured by GSJ), amorphous cyclopolyolefin resin film, Pure Ace of polycarbonate film (manufactured by Teijin), cellulose triacetate film Co-katak KC4UX, KC8UX (Co-power Commercial products such as Minoltaput Co., Ltd.) can be preferably used.
  • the base material according to the present invention using the above-described resin or the like may be an unstretched film or a stretched film.
  • the substrate according to the present invention can be produced by a conventionally known general method.
  • an unstretched substrate that is substantially amorphous and not oriented can be produced by melting the resin as a material with an extruder, extruding it with an annular die or T-die, and quenching it.
  • an unstretched base material is subjected to a known method such as -axial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc.
  • a stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis).
  • the draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.
  • surface treatment such as corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, etc. is performed before forming the deposited film. May be.
  • an anchor coat agent layer may be formed on the surface of the substrate according to the present invention for the purpose of improving the adhesion to the deposited film.
  • the anchor coating agent used in this anchor coating agent layer includes polyester resin, isocyanate resin, urethane resin, acrylic resin, ethyl butyl alcohol resin, bur modified resin, epoxy resin, modified resin. Styrene resin, modified silicone resin, alkyl titanate, etc. can be used alone or in combination. Conventionally known additives can be added to these anchor coating agents.
  • the anchor coating agent is coated on the substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and the solvent, diluent, etc. are removed by drying to remove the anchor coating. can do.
  • the coating amount of the anchor coat agent is preferably about 0.1 lg / m 2 to 5 g / m 2 (dry state).
  • the substrate is conveniently a long product rolled up.
  • the thickness of the base material varies depending on the use of the film obtained, it cannot be specified unconditionally.
  • the film is used for packaging, it is 3 ⁇ ! ⁇ 40 It is preferably 0 / zm, particularly in the range of 6 ⁇ m to 30 ⁇ m.
  • the film thickness of the substrate used in the present invention is preferably 10 m to 200 ⁇ m, more preferably 50 ⁇ m to 100 ⁇ m.
  • the organic EL element of the present invention may be used as a kind of lamp such as an illumination or exposure light source, a projection device that projects an image, or a type that directly recognizes a still image or a moving image. It may be used as a display device (display).
  • the drive method may be either a simple matrix (passive matrix) method or an active matrix method.
  • a full color display device can be produced by using two or more kinds of the organic EL elements of the present invention having different emission colors.
  • the organic EL device of the present invention performs prism-like or lens-like processing on the surface of the substrate, or attaches a prism sheet or lens sheet to the surface of the substrate. May be.
  • the organic EL device of the present invention may have a low refractive index layer between the electrode and the substrate.
  • the low refractive index layer include air mouth gel, porous silica, magnesium fluoride, and fluorine-based polymer.
  • the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.
  • the thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave exuded by evanescent enters the substrate.
  • the organic EL device of the present invention may have a diffraction grating in any layer or in a medium (in a transparent substrate or a transparent electrode). It is desirable that the diffraction grating to be introduced has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in one direction, only light traveling in a specific direction is diffracted. The light extraction efficiency is improved Absent. However, by making the refractive index distribution a two-dimensional distribution, the light traveling in all directions is diffracted, and the light extraction efficiency increases.
  • the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.
  • the period of the diffraction grating is preferably about 1Z2 to 3 times the wavelength of light in the medium.
  • the arrangement of the diffraction gratings is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a Herman lattice.
  • the substrate according to the present invention preferably has a gas noria layer. This has the effect of further improving the stability over time in dark spots and at high temperatures and high humidity.
  • the gas nolia layer according to the present invention is not particularly limited as long as it is a layer that blocks permeation of oxygen and water vapor. It is preferred that the oxygen permeability is 0.005 mlZm 2 Z days or less at 23 ° C. and 0% RH.
  • the water vapor permeability measured according to the JIS K7129 B method is preferably 0.1 lgZm 2 Z days or less.
  • Specific examples of the material constituting the gas barrier layer according to the present invention include silicon oxide, acid aluminum, acid silicon nitride, acid aluminum nitride, magnesium oxide, zinc oxide, and oxide, which are preferably inorganic oxides. Examples thereof include indium and oxide tin.
  • the thickness of the gas nolia layer in the present invention varies depending on the type and configuration of the material used, and the force selected as appropriate is 5 ⁇ ! It is preferable to be within a range of ⁇ 2000 nm. This is because when the thickness of the gas noria layer is smaller than the above range, a uniform film cannot be obtained, and it is difficult to obtain noria properties for the gas. If the thickness of the gas noria layer is larger than the above range, it is difficult to maintain the flexibility of the gas noria film, and the gas barrier film cracks due to external factors such as bending and pulling after film formation. This is because there is a risk of occurrence.
  • the gas nore layer according to the present invention comprises a raw material described later using a spray method, a spin coating method, a sputtering method, an ion assist method, a plasma CVD method described later, a plasma under atmospheric pressure or a pressure near atmospheric pressure described later. It can be formed by applying a CVD method or the like.
  • FIG. 1 is an example showing the configuration of a substrate having a gas barrier layer according to the present invention.
  • the structure and density of the substrate having the gas nolia layer according to the present invention will be described.
  • the gas nolia layer 21 according to the present invention has a structure in which layers having different densities are laminated on a base material 22, and an adhesive film 23, a ceramic film 24, and a protective film 25 are laminated.
  • Fig. 1 shows an example in which three layers are stacked. The density distribution in each layer is uniform, and the density of the ceramic film is set higher than the densities of the adhesion film and the protective film positioned above and below the ceramic film. It should be noted that in FIG. 1, each layer is shown as one layer. If necessary, each layer may have two or more layers.
  • a spray method As a method for forming an adhesion film, a ceramic film and a protective film on a substrate, a spray method, a spin coating method, a sputtering method, an ion assist method, a plasma CVD method, atmospheric pressure or a pressure near atmospheric pressure is used. It can be formed by applying a plasma CVD method or the like.
  • a polyethylene naphthalate film having a thickness of 100 ⁇ m (Teijin's DuPont film, hereinafter abbreviated as PEN) (base material 1) is subjected to the following atmospheric pressure plasma discharge treatment equipment and discharge conditions.
  • PEN Teijin's DuPont film, hereinafter abbreviated as PEN
  • a substrate 1 having a gas barrier layer with the profile configuration shown in Fig. 1 was produced.
  • a set of a roll electrode covered with a dielectric and a plurality of rectangular tube electrodes was prepared as follows.
  • the roll electrode serving as the first electrode is coated with a high-density, high-adhesion alumina sprayed film by atmospheric plasma on a titanium alloy T64 jacket roll metal base material that has cooling means using cooling water.
  • the roll diameter was 1000 mm.
  • the square electrode of the second electrode is a hollow square tube type titanium alloy T64 covered with lmm of the same dielectric material as the above under the same conditions, and is opposed to the opposing square tube type fixed electrode group. did.
  • the first electrode roll rotating electrode
  • the second electrode square tube fixed electrode group
  • the roll rotating electrode is rotated by the drive.
  • a thin film was formed.
  • the first layer adheresion layer
  • the next 6 are used for the second layer (ceramic layer).
  • the following two were used for film formation of the third layer (protective layer), and three layers were laminated in one pass by setting each condition.
  • Plasma discharge was performed under the following conditions to form an adhesion layer having a thickness of about 50 nm.
  • Thin-film forming gas Hexamethinoresinsiloxane (vaporized by mixing with nitrogen gas in a vaporizer manufactured by Lintec) 0.5% by volume
  • Additive gas Oxygen gas 5.0 volume 0/0
  • the density of the formed first layer was 1.90 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by Mac Science Co., Ltd. described above.
  • Plasma discharge was performed under the following conditions to form a ceramic layer having a thickness of about 30 nm.
  • Thin-film forming gas hexamethinoresisiloxane (vaporized by mixing with nitrogen gas using a vaporizer manufactured by Lintec) 0.1% by volume
  • Additive gas Oxygen gas 5.0 volume 0/0
  • the density of the formed second layer was 2.20 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by MacScience.
  • Plasma discharge was performed under the following conditions to form a protective layer having a thickness of about 200 nm.
  • Discharge gas nitrogen gas 93.0 volume 0/0
  • Thin-film forming gas Hexamethinoresinsiloxane (vaporized by mixing with nitrogen gas in a Lintec vaporizer) 2.0 vol%
  • Additive gas Oxygen gas 5.0 volume 0/0
  • the density of the third layer (protective layer) formed was 1.95 as a result of measurement by the X-ray reflectivity method using MXP21 manufactured by Mac Science Co., Ltd. described above.
  • the organic EL element OL EDI-1 of the present invention was produced using an ink jet recording method as shown in FIG.
  • the process will be described with reference to FIG.
  • a fluid D3 containing a polymer of the following exemplary compound A28 and ethyl acetate is discharged onto the light emitting layer 112, and the conditions are 100 ° C and 60 minutes.
  • an electron transport layer 113 having a thickness of 50 nm was formed.
  • an aluminum layer 114 (cathode) having a thickness of 200 nm was formed on the electron transport layer 113 by vapor deposition.
  • the organic solvent content in the hole transport layer 111, the light emitting layer 112, and the electron transport layer 113 was adjusted as shown in Table 1. Further, a base material 115 having a gas nolia layer was pasted thereon to produce an organic EL element OLED1-1.
  • Example Reaction Compound A15 1.34 g (2.5 mmol), 2,2'-azobis (isobutyronitryl) (AIBN) O. 010 g (0.06 lmmol) and 30 ml of butyl acetate were placed in a reaction vessel, and the nitrogen was replaced. Thereafter, the mixture was reacted at 80 ° C for 10 hours. After the reaction, it was poured into acetone for reprecipitation, and the polymer was recovered by filtration. Purified by adding the recovered polymer chloroform solution into methanol and reprecipitating it twice, and after recovery, vacuum-dried to give the desired Exemplified Compound A15 polymer 1.20 g Got as.
  • the weight average molecular weight of the obtained polymer was 10,000 in terms of polystyrene (according to GPC (gel permeation chromatography) measurement using HFIP (hexafluoroisopropanol) as an eluent).
  • the organic EL element OL ED 1-2-1 is the same as the manufacturing method of the organic EL element OLED1-1 except that the material of each layer is changed to the material shown in Table 1. — 13 was made.
  • A37 As a hole transport layer with a thickness of 50 nm on a glass substrate having an indium tin oxide transparent electrode (ITO electrode) according to a conventional method, A31 as a light emitting layer, phosphorescent compound 1-60 (mass) The ratio 100: 5) is deposited with a thickness of 50 nm, and then A34 is deposited with a thickness of 50 nm as an electron transport layer. Formed. Furthermore, the organic EL elements OLED1-14 and 1-15 were fabricated by laminating the base material 1 having a gas noria layer.
  • ITO electrode indium tin oxide transparent electrode
  • the materials of each layer are changed to the materials shown in Table 1 below, and the organic EL element is replaced with a glass substrate having an indium tin oxide transparent electrode (ITO electrode).
  • ITO electrode indium tin oxide transparent electrode
  • Table 1 shows the organic solvent contents of the organic layers of organic ELOLED1-1 to 1-16. The measurement method was the method described above.
  • Luminance was expressed as a relative value when OLED1-11 is set to 100.
  • the emission luminance was measured using CS-1000 (manufactured by Co-Camino Norta Sensing).
  • the initial voltage and the voltage after 150 hours were measured.
  • the relative value of the voltage after 100 hours with respect to the initial voltage was defined as the voltage increase rate.
  • the organic EL device was stored for one month at 60 ° C and 70% Rh. cd / m 2 ) was measured. The stability over time was expressed as a relative value with respect to the measured emission luminance before storage.
  • FIG. 5 shows only a schematic diagram of the display portion A of the produced full-color display device. That is, a plurality of scanning lines 5 and data lines 6 are included on the same substrate.
  • It has a wiring section and a plurality of juxtaposed pixels 3 (light emission color is a red area pixel, a green area pixel, a blue area pixel, etc.), and the scanning line 5 and the plurality of data lines 6 of the wiring section are Each of them is made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are not shown).
  • the plurality of pixels 3 are driven by an active matrix system in which an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor are provided, and scanning from a scanning line 5 When a signal is applied, it receives an image data signal from the data line 6 and emits light according to the received image data. In this way, full-color display is possible by appropriately juxtaposing the red, green, and blue pixels.
  • each of the organic EL elements emitting blue light, green light and red light produced in Example 2 was covered with a glass case to obtain a lighting device.
  • An organic EL element OLED4-1 was produced in the same manner as in the production of the organic EL element OLED1-1 of Example 1, except that the materials and film thicknesses shown in Table 3 were changed. In Table 3, “%” represents mass ratio (%).
  • Electron transport layer A 35 50 [0200] The drying conditions were adjusted so that the solvent content of the organic layer was 25 ppm. Next, aluminum having a thickness of 200 nm was deposited thereon. For sealing, the substrate 1 was attached in the same manner as the organic EL element OLED1-1.
  • the produced organic EL element OLED4-1 was provided with a glass case with a reflective coating on the non-light-emitting surface side in the same manner as in Example 3 to provide an illumination device.
  • the obtained illuminating device was able to be used as a thin illuminating device that emits white light with high luminous efficiency and long emission life.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un élément EL organique, qui présente une bonne luminosité, ne provoque pas de hausse de tension significative ni de points sombres pendant le fonctionnement à courant constant, et présente une stabilité temporelle élevée dans des conditions de température élevée et de forte humidité, et un dispositif d'affichage et un système d'éclairage l'utilisant. L’élément électroluminescent organique est caractérisé en ce qu’au moins l’une de couches organiques constituant l’élément est une couche luminescente contenant un composé phosphorescent représenté par la formule générale (1) et en ce que la couche organique contient 10-2 ppm à 103 ppm d’un solvant organique.
PCT/JP2006/322143 2005-11-24 2006-11-07 Élément électroluminescent organique, dispositif d’affichage et système d’éclairage WO2007060826A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007546392A JPWO2007060826A1 (ja) 2005-11-24 2006-11-07 有機エレクトロルミネッセンス素子、表示装置及び照明装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-338411 2005-11-24
JP2005338411 2005-11-24

Publications (1)

Publication Number Publication Date
WO2007060826A1 true WO2007060826A1 (fr) 2007-05-31

Family

ID=38067062

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/322143 WO2007060826A1 (fr) 2005-11-24 2006-11-07 Élément électroluminescent organique, dispositif d’affichage et système d’éclairage

Country Status (2)

Country Link
JP (2) JPWO2007060826A1 (fr)
WO (1) WO2007060826A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009025286A1 (fr) * 2007-08-21 2009-02-26 Konica Minolta Holdings, Inc. Dispositif d'éclairage
US8859110B2 (en) 2008-06-20 2014-10-14 Basf Se Cyclic phosphazene compounds and use thereof in organic light emitting diodes
JP2015214566A (ja) * 2011-12-23 2015-12-03 株式会社半導体エネルギー研究所 イリジウム錯体

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2014141821A1 (ja) * 2013-03-12 2017-02-16 コニカミノルタ株式会社 電子デバイス及び電子デバイスの製造方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002038142A (ja) * 2000-05-19 2002-02-06 Sumitomo Chem Co Ltd 高分子蛍光体およびそれを用いた高分子発光素子
JP2002100476A (ja) * 2000-07-17 2002-04-05 Fuji Photo Film Co Ltd 発光素子及びアゾール化合物
JP2002117978A (ja) * 2000-07-17 2002-04-19 Fuji Photo Film Co Ltd 発光素子及びイリジウム錯体
JP2003109758A (ja) * 2001-09-27 2003-04-11 Konica Corp 有機エレクトロルミネッセンス素子
JP2004001429A (ja) * 2002-04-01 2004-01-08 Konica Minolta Holdings Inc 基板及びその基板を有する有機エレクトロルミネッセンス素子
JP2004103401A (ja) * 2002-09-10 2004-04-02 Konica Minolta Holdings Inc 素子および該素子の製造方法
JP2005203339A (ja) * 2003-12-16 2005-07-28 Matsushita Electric Ind Co Ltd 有機エレクトロルミネッセント素子およびその製造方法
JP2005263900A (ja) * 2004-03-17 2005-09-29 Dainippon Printing Co Ltd マレイミド系重合体

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5352951A (en) * 1991-06-03 1994-10-04 Bkl, Inc. Electroluminescent device
US20020031602A1 (en) * 2000-06-20 2002-03-14 Chi Zhang Thermal treatment of solution-processed organic electroactive layer in organic electronic device
DE10153445A1 (de) * 2001-10-30 2003-05-22 Covion Organic Semiconductors Trocknungsverfahren
JP2003217842A (ja) * 2002-01-23 2003-07-31 Dainippon Printing Co Ltd エレクトロルミネッセント素子の製造方法
JP2003229256A (ja) * 2002-02-04 2003-08-15 Seiko Epson Corp 有機ｅｌ装置の製造方法及び有機ｅｌ装置用インク組成物
JP2004063976A (ja) * 2002-07-31 2004-02-26 Mitsubishi Chemicals Corp 電界効果トランジスタ
JP2005310799A (ja) * 2002-10-03 2005-11-04 Seiko Epson Corp 表示パネル及びその表示パネルを備えた電子機器並びに表示パネルの製造方法
JP4427947B2 (ja) * 2002-11-18 2010-03-10 コニカミノルタホールディングス株式会社 有機エレクトロルミネッセンス素子及び表示装置
JP4374197B2 (ja) * 2003-02-18 2009-12-02 大日本印刷株式会社 機能性素子の製造方法およびその製造装置
JP2004259529A (ja) * 2003-02-25 2004-09-16 Fuji Photo Film Co Ltd 有機電界発光素子
JP4293808B2 (ja) * 2003-03-17 2009-07-08 シャープ株式会社 有機ｅｌ装置の製造方法
JP2004303491A (ja) * 2003-03-28 2004-10-28 Tdk Corp 有機ｅｌ素子及びその製造方法、並びに有機ｅｌディスプレイ
JP4198654B2 (ja) * 2003-08-07 2008-12-17 三星エスディアイ株式会社 イリジウム化合物及びそれを採用した有機電界発光素子
DE10338550A1 (de) * 2003-08-19 2005-03-31 Basf Ag Übergangsmetallkomplexe mit Carbenliganden als Emitter für organische Licht-emittierende Dioden (OLEDs)
JP4506166B2 (ja) * 2003-12-12 2010-07-21 コニカミノルタホールディングス株式会社 有機エレクトロルミネッセンス素子用単量体、有機エレクトロルミネッセンス素子用重合体、有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP4661781B2 (ja) * 2004-04-14 2011-03-30 コニカミノルタホールディングス株式会社 有機エレクトロルミネッセンス素子、表示装置及び照明装置

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002038142A (ja) * 2000-05-19 2002-02-06 Sumitomo Chem Co Ltd 高分子蛍光体およびそれを用いた高分子発光素子
JP2002100476A (ja) * 2000-07-17 2002-04-05 Fuji Photo Film Co Ltd 発光素子及びアゾール化合物
JP2002117978A (ja) * 2000-07-17 2002-04-19 Fuji Photo Film Co Ltd 発光素子及びイリジウム錯体
JP2003109758A (ja) * 2001-09-27 2003-04-11 Konica Corp 有機エレクトロルミネッセンス素子
JP2004001429A (ja) * 2002-04-01 2004-01-08 Konica Minolta Holdings Inc 基板及びその基板を有する有機エレクトロルミネッセンス素子
JP2004103401A (ja) * 2002-09-10 2004-04-02 Konica Minolta Holdings Inc 素子および該素子の製造方法
JP2005203339A (ja) * 2003-12-16 2005-07-28 Matsushita Electric Ind Co Ltd 有機エレクトロルミネッセント素子およびその製造方法
JP2005263900A (ja) * 2004-03-17 2005-09-29 Dainippon Printing Co Ltd マレイミド系重合体

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009025286A1 (fr) * 2007-08-21 2009-02-26 Konica Minolta Holdings, Inc. Dispositif d'éclairage
JPWO2009025286A1 (ja) * 2007-08-21 2010-11-25 コニカミノルタホールディングス株式会社 照明装置
US8859110B2 (en) 2008-06-20 2014-10-14 Basf Se Cyclic phosphazene compounds and use thereof in organic light emitting diodes
JP2015214566A (ja) * 2011-12-23 2015-12-03 株式会社半導体エネルギー研究所 イリジウム錯体
JP2017103483A (ja) * 2011-12-23 2017-06-08 株式会社半導体エネルギー研究所 発光素子、発光装置、照明装置、電子機器
US9768396B2 (en) 2011-12-23 2017-09-19 Semiconductor Energy Laboratory Co., Ltd. Iridium complex, light-emitting element, light-emitting device, electronic device, and lighting device

Also Published As

Publication number Publication date
JP2013048253A (ja) 2013-03-07
JP5724979B2 (ja) 2015-05-27
JPWO2007060826A1 (ja) 2009-05-07

Similar Documents

Publication Publication Date Title
JP4893627B2 (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
EP1371709B1 (fr) Elément organique electroluminescent et leur méthode de fabrication
JP5424622B2 (ja) ペリレン化合物及びこれを用いた有機発光素子
CN101243561B (zh) 有机电致发光元件、显示装置、照明装置
JP2007208102A (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP2013093593A (ja) 有機エレクトロルミネッセンス素子、表示装置および照明装置
JP5724979B2 (ja) 有機エレクトロルミネッセンス素子
JP5192127B2 (ja) 有機エレクトロルミネッセンス素子の製造方法
JP2007059244A (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP2007042316A (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP5226187B2 (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP5546088B2 (ja) 有機エレクトロルミネッセンス素子
JP2007059687A (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP2007042728A (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP5286788B2 (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP2007234934A (ja) 有機エレクトロルミネッセンス素子、表示装置、照明装置及び有機エレクトロルミネッセンス素子の製造方法
JP2007059243A (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP2007012984A (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP5716759B2 (ja) 有機エレクトロルミネッセンス素子の製造方法
JP2007053044A (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP2007042726A (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP2007026978A (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP2007048732A (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP2007035678A (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置
JP2007049117A (ja) 有機エレクトロルミネッセンス素子、表示装置及び照明装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2007546392

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06823056

Country of ref document: EP

Kind code of ref document: A1