WO2006041056A1 - Metal-containing coordination compound, coordination compound residue-containing polymer compound, organic electroluminescent material, white organic electroluminescent material, white light-emitting device, and light-emitting device - Google Patents
Metal-containing coordination compound, coordination compound residue-containing polymer compound, organic electroluminescent material, white organic electroluminescent material, white light-emitting device, and light-emitting device Download PDFInfo
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- WO2006041056A1 WO2006041056A1 PCT/JP2005/018696 JP2005018696W WO2006041056A1 WO 2006041056 A1 WO2006041056 A1 WO 2006041056A1 JP 2005018696 W JP2005018696 W JP 2005018696W WO 2006041056 A1 WO2006041056 A1 WO 2006041056A1
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- compound
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- light emitting
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- coordination compound
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000002524 organometallic group Chemical group 0.000 description 1
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- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
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- 239000012286 potassium permanganate Substances 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical group [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 150000003643 triphenylenes Chemical class 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/12—N-Vinylcarbazole
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- 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
- 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
- H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
-
- 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
- H10K85/151—Copolymers
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- 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
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
-
- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1475—Heterocyclic containing nitrogen and oxygen as heteroatoms
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- 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
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- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Definitions
- the present invention relates to a metal-containing coordination compound, a coordination compound residue-containing polymer compound, an organic electoluminescence material, a white organic electoluminescence material, a white light emitting device, and a light emitting device.
- Metal-containing coordination compounds that can be polymerized or dissolved in a solvent, for example, (8-hydroxyquinolate) -based metal coordination compounds, coordination compounds obtained by polymerizing the polymerizable metal-containing coordination compounds Residue-containing polymer compounds such as (8-hydroxyquinolate) polymer compounds, organic electroluminescent materials useful for the formation of light emitting devices, and white organic electoluminescent materials useful for the formation of white light emitting devices capable of emitting white light Materials, white light emitting elements capable of emitting white light, and layers such as an electron transport layer, a hole transport layer, and a light emitting layer formed by the organic electoluminescence material A light emitting element comprising a.
- An organic EL element has a light emitting layer, an electron transport layer, and a hole transport layer, and causes a light emitting substance to emit light by energy generated by recombination of electrons and holes injected from an electrode.
- Alq3 is still considered one of the most promising light emitting materials or electron injection materials.
- Various light-emitting materials other than Alq3 such as europium-based phosphorescent complexes, lithium-based blue light-emitting complexes, and phosphorescent phosphine metal complexes have been tried.
- gadolinium complex-doped metal complexes such as TPD have been tried as electron injection materials.
- Patent Document 1 http://www.chitose.ac.jp/ ⁇ kyoin/person/kawabe/LED/LEDindex.ht ml
- Non-Patent Document 2 Nihon Jitsugyo Publishing Co., Ltd., March 1st, 2004, 6th edition, “All about organic EL” (P47)
- Vapor deposition is usually performed by heating a metal complex to a vapor under high vacuum, and solidifying and fixing the vapor of the metal complex at a predetermined site. Therefore, the vapor deposition operation is extremely equipped with a vacuum evacuation device that realizes a high vacuum, a high-temperature heating device that heats the metal complex, and a device that solidifies the metal complex vapor on the electrode surface formed on the substrate. Large vapor deposition equipment is required.
- one object of research and development of organic EL devices is to provide an organic EL device that can emit white light and can be manufactured by a simple method.
- An object of the present invention is to provide a metal-containing coordination compound having characteristics equivalent to or higher than those of a metal complex and capable of being polymerized or dissolved in a solvent.
- An object of the present invention is to provide a coordination compound residue-containing polymer compound that is a polymer compound having properties equivalent to or higher than those of a metal complex.
- This invention can also be easily formed into a film by a processing method of an organic polymer compound, or can be easily formed into a film by a casting method in which a film is formed by dissolving in a solvent.
- Another object of the present invention is to provide a white organic-electric luminescence material that can emit white light using the organic-electric-luminescence material, and to provide a white light-emitting element that can emit white light.
- Claim 1 is a metal-containing coordination compound characterized by the following formula (1): [0011] [Chemical Formula 1]
- A represents a thiophene ring in a luminescent coordination complex containing a metal and a thiophene ring or an aromatic ring and having a ligand coordinated to the metal. Or, it is a residue obtained by extracting hydrogen from an aromatic ring, and B is any group represented by the following formulas (2) to (5). ]
- R 1 is a hydrogen atom or a methyl group.
- IT is a C1-C20 alkyl group.
- Claim 2 has a repeating unit represented by the following formula (6): A compound residue-containing polymer compound,
- A has the same meaning as in claim 1, Z is the following formula (7), (8) or a single bond, R 3 is When Z is a group represented by the formula (7), it is a hydrogen atom, and when Z is represented by the formula (8), it is a hydrogen atom or a methyl group. In the following formulas (7) and (8), the portion surrounded by the dotted line is not included in the group to be expressed by formulas (7) and (8). ]
- Claim 3 is an organic electorium luminescence characterized by containing the metal-containing coordination compound according to claim 1 and Z or the coordination compound residue-containing polymer compound according to claim 2.
- Claim 4 is the metal-containing coordination compound according to claim 1 and Z or the coordination compound residue-containing polymer compound according to claim 2 and the metal-containing coordination compound and Z or the coordination.
- a white organic electoluminescent material characterized by containing a light-emitting compound that emits light that is substantially complementary to the light-emitting color of the polymer residue-containing polymer compound,
- Claim 5 is a light emitting device comprising a layer containing the organic electoluminescence material according to claim 3,
- Claim 6 is a light emitting layer containing a light emitting color of the organic electroluminescent material according to claim 3 and a light emitting compound that emits light substantially in a complementary color relationship with the electroluminescent material. It is a white light emitting element characterized by having,
- Claim 7 is substantially complementary to the luminescent color of the first light-emitting layer containing the organic electoluminescence material of claim 3 and the organic electroluminescence material of claim 3.
- a white light-emitting element comprising: a second light-emitting layer containing a light-emitting compound that emits light having a relationship;
- Claim 8 is substantially equivalent to the light emitting layer containing the organic electoluminescent material according to claim 3 and the light emitting color of the organic electroluminescent material according to claim 3 in the light emitting layer.
- a white light source characterized by having a light emitting source that emits light in a complementary color relationship It is an optical element.
- the metal-containing coordination compound represented by the formula (1) contains a metal and a thiophene ring or an aromatic ring and has a ligand that coordinates to the metal.
- the thiophene ring or aromatic ring force has a residue A after abstracting hydrogen.
- Zinc-based yellow-green light emitting complex (“Thin Solid Films” Vol. 346 69-72 Publication year: 1999 El sevier Science ft Title: Yellow green electroluminescence generated from the thin films of ⁇ -diketone- zinc complex Author: Keizou Okada Yan- Feng Wang; Tian-Ming Chen; Tadao Nakaya) residue,
- Synthetic Metals Vol. I l l- 112 459-463 Publication year: 200 0 Elsevier Science t Title: Materials for organic electroluminescence: aluminum vs. born Author: Sally Anderson; Michael S. Weaver; Andrew J.
- a preferable residue A is a residue of an (8-hydroxyquinolate) -based metal coordination compound represented by the formula (9).
- M is a transition metal and a typical element in the periodic table of IUPAC of 1988.
- Z 1 is a hydrogen atom or a group represented by the formula (12).
- n is the valence of the metal indicated by M minus 1.
- R 5 is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 10 carbon atoms.
- the metal-containing coordination compound represented by the formula (1) contains the residue A, the oxadiazole ring, and the specific group B, so that the light emission characteristics in the residue A and the electron of the oxadiazole ring itself It is suitable for organic EL luminescence materials such as light-emitting materials, electron transport materials, and hole transport materials for organic EL devices, depending on the absorptivity and the characteristics of the group represented by B.
- the group B is an N-vinylcarbazole residue represented by the formula (2), a styrene residue represented by the formula (3), a formula
- the metal-containing coordination compound is polymerized to give a coordination compound residue-containing polymer compound represented by formula (6).
- the coordination compound residue-containing polymer represented by the formula (6) is a light-emitting material, an electron transport material, or a hole transport of an organic EL device depending on the characteristics of the residue A, the oxadiazole ring, and the group B. It is suitable for organic electoric luminescence materials such as materials. Since this high molecular weight compound containing coordination compound residues has a film-forming ability, the light emitting layer, the electron transport layer, and the hole transport layer in a light emitting device such as an organic EL device are not processed by a polymer processing technique without using a vapor deposition technology. Can be formed.
- the metal-containing group represented by the formula (1) has improved solubility in a solvent. Therefore, by selecting an appropriate polar solvent, dissolving the metal-containing coordination compound represented by the formula (1) in the solvent, preparing a solution, and applying the solution, the light emitting layer, the electron transport A layer or a hole transport layer can be easily formed.
- the metal-containing coordination compound represented by the formula (1) and the coordination compound residue-containing polymer compound having a repeating unit represented by the formula (6) are durable because the structure is robust.
- An organic electoluminescence material and a light emitting element are provided.
- the metal-containing coordination compound represented by the formula (1) is obtained by, for example, the Friedel-Crafts reaction or aldehyde synthesis using carbene and the acidity of the aldehyde as shown in the reaction formula (1).
- Lg—COOR 4 (where Lg [abbreviation of li gand] is a ligand in the metal-containing coordination compound represented by the formula (1)) synthesized by introduction reaction of carboxylic acid or ester and hydrazine To produce a hydrazide compound (a), and react this hydrazide compound (a) with a carboxylic acid chloride to synthesize a dicarbohydrazide compound (b).
- This dicarbohydrazide is synthesized by cyclization of the compound by heating, and the compound (c) is easily produced by reacting the ligand (c) with a metal that can be a central metal.
- R 4 is an alkyl group such as a methyl group or an ethyl group.
- reaction formula shows the principle in the synthesis of the compound represented by the formula (1), and various compounds included in the formula (1) are based on the following formula and refer to the knowledge of organic synthesis. Can be easily synthesized
- the metal-containing coordination compound represented by the formula (1) has a double bond when the group B has a structure containing a double bond represented by the formula (2), (3) or (4). Is polymerized as a polymerizable functional group to give a polymer compound containing a coordination compound residue having a repeating unit represented by the formula (6). Therefore, the above series of reactions is a basic reaction for polymerizing an organometallic complex (including a chelate compound) having luminescence properties.
- the coordination compound residue-containing polymer compound having a repeating unit represented by the formula (6) is a homopolymer having a repeating unit represented by the formula (6), and also represented by the formula (6). It can be a copolymer having repeating units. Examples of the copolymer include vinyl carbazole and a metatalylate monomer as comonomers.
- the coordination compound residue-containing polymer compound having a repeating unit represented by the formula (6) is prepared by using a technique for polymer processing, for example, a light-emitting layer, an electrode in a light-emitting device such as an organic EL device. It is suitable as an organic electoluminescence material capable of forming a load transport layer, a hole transport layer, and the like.
- the coordination compound residue-containing polymer compound having a repeating unit represented by the formula (6) is a suitable material that can form a light-emitting element without requiring an operation such as vapor deposition. .
- the white organic electoluminescence material according to the present invention includes a metal-containing coordination compound that forms a color from yellow to green according to a chemical structure, and a polymer compound containing Z or a coordination compound residue, and the yellow Since it contains a light emitting compound that emits light of a color substantially complementary to the color up to green, substantially white light emission is possible by applying energy.
- the reason that white light can be emitted substantially is that the observer's eyes recognize white that is bluish and warm white as white. This is because the color is white.
- the light-emitting compound that emits light having a substantially complementary color relationship may be appropriately determined according to the type of the metal-containing coordination compound and Z or coordination compound residue-containing polymer compound. Togashi.
- the white light emitting device has a light emitting layer.
- the light-emitting layer includes a metal-containing coordination compound that develops a color from yellow to green depending on the chemical structure, and a polymer compound containing Z or a coordination compound residue.
- the metal-containing coordination compound and the Z or coordination compound residue-containing polymer compound generate yellow or green light, and some of the light is generated from the light-emitting compound to the yellow to green color. Since light of a color that is substantially complementary to the color is generated, white light is emitted from the light emitting layer as a result of color mixing.
- the white light emitting element may contain a first light emitting layer and a second light emitting layer.
- the first light-emitting layer contains a metal-containing coordination compound that develops a color from yellow to green depending on the chemical structure and a polymer compound containing Z or a coordination compound residue
- the second light-emitting layer contains the above-described polymer.
- Yellow power Contains a light-emitting compound that emits light of a color substantially complementary to colors up to green.
- the first light emitting layer Yellow power up to green light is emitted, and the complementary light emission is generated from the second light emitting layer, so that the light emitting element as a whole emits white light.
- White light emission is obtained by mixing a color emitted from a metal-containing coordination compound and a polymer compound containing Z or a coordination compound residue with light that is substantially in a complementary color relationship. It is recognized as white for the eyes to observe. Therefore, as another example of the white light-emitting device according to the present invention, a light-emitting layer containing a metal-containing coordination compound and Z or a coordination compound residue-containing polymer compound, and the light-emitting layer and the complementary color of the light-emitting color And a white light emitting element having a light source that emits a color having the above relationship. Examples of the light source include a light emitting semiconductor such as a blue light emitting semiconductor.
- FIG. 1 is an explanatory view schematically showing an example of a light emitting device of the present invention.
- FIG. 2 is an NMR vector chart of the compound (15) in Example 1.
- FIG. 3 is an IR ⁇ vector chart of compound (16) in Example 1.
- FIG. 4 is an NMR vector chart of compound (16) in Example 1.
- FIG. 5 is an IR ⁇ vector chart of the compound (17) in Example 1.
- FIG. 6 is an NMR vector chart of the compound (17) in Example 1.
- FIG. 7 is an IR ⁇ vector chart of the compound (18) in Example 1.
- FIG. 8 is an NMR vector chart of the compound (18) in Example 1.
- FIG. 9 is an IR ⁇ vector chart of the compound (22) in Example 2.
- FIG. 10 is a NMR vector chart of the compound (22) in Example 2.
- FIG. 11 is an IR ⁇ vector chart of the compound (23) in Example 2.
- FIG. 12 is an NMR vector chart of compound (23) in Example 2.
- FIG. 13 is an IR ⁇ vector chart of compound (24) in Example 2.
- FIG. 14 is a NMR vector chart of the compound (24) in Example 2.
- FIG. 15 is a fluorescence spectrum chart of the compound (24) in Example 2.
- FIG. 16 is an IR ⁇ vector chart of the compound (19) in Example 2.
- FIG. 17 is a fluorescence spectrum chart of the compound (19) in Example 2.
- FIG. 18 is an IR spectrum chart of the homopolymer of compound (19) in Example 2. It is.
- FIG. 19 is a fluorescence spectrum chart of a homopolymer of compound (19) in Example 2.
- FIG. 20 is an IR ⁇ vector chart of a copolymer of compound (19) and MMA in Example 2.
- FIG. 21 is a fluorescence spectrum chart of the compound (25) in Example 3.
- FIG. 22 is a fluorescence spectrum chart of the compound (26) in Example 4.
- FIG. 23 is a fluorescence spectrum chart of the compound (27) in Example 5.
- FIG. 24 is a fluorescence spectrum chart of the compound (28) in Example 6.
- FIG. 25 is a fluorescence spectrum chart of the compound (29) in Example 7.
- FIG. 26 is a fluorescence spectrum chart of the compound (30) in Example 8.
- FIG. 27 is an IR ⁇ vector chart of a copolymer of compound (19) and N-bicarbcarbazole in Example 2.
- FIG. 28 is an IR ⁇ vector chart of compound (14) in Example 1.
- FIG. 29 is an NMR vector chart of compound (14) in Example 1.
- FIG. 30 is a fluorescence spectrum chart of the compound (14) in Example 1.
- FIG. 31 is a schematic view showing the structure of a light-emitting device employed in Example 9.
- FIG. 32 is an explanatory view schematically showing the structure of a white light emitting element as an example of the present invention.
- FIG. 33 is an explanatory view schematically showing the structure of a white light emitting device as another example of the present invention.
- FIG. 34 is an explanatory view schematically showing a structure of a white light emitting element as another example of the present invention.
- FIG. 35 is a fluorescence spectrum chart showing a spectrum of light emission generated by irradiating the light emitting layer obtained in Example 10 with excitation light having a wavelength of 340 nm.
- FIG. 36 is a fluorescence spectrum chart showing a spectrum of light emission generated by irradiating the light emitting layer obtained in Example 10 with excitation light having a wavelength of 365 nm.
- FIG. 37 shows the case where the light emitting layer obtained in Example 10 is irradiated with excitation light having a wavelength of 380 nm.
- 5 is a fluorescence spectrum chart showing a spectrum of light emission generated by the above.
- FIG. 38 is a fluorescence spectrum chart showing a spectrum of light emission generated by irradiating the light emitting layer obtained in Example 11 with excitation light having a wavelength of 340 nm.
- FIG. 39 is a fluorescence spectrum chart showing a spectrum of light emission generated by irradiating the light emitting layer obtained in Example 11 with excitation light having a wavelength of 365 nm.
- FIG. 40 is a fluorescence spectrum chart showing a spectrum of light emission generated by irradiating the light emitting layer obtained in Example 11 with excitation light having a wavelength of 380 nm.
- FIG. 41 is a fluorescence spectrum chart showing a spectrum of light emission generated by irradiating the light emitting layer obtained in Example 12 with excitation light having a wavelength of 340 nm.
- FIG. 42 is a fluorescence spectrum chart showing a spectrum of light emission generated by irradiating the light emitting layer obtained in Example 12 with excitation light having a wavelength of 365 nm.
- FIG. 43 is a fluorescence spectrum chart showing the spectrum of light emission generated by irradiating the light emitting layer obtained in Example 12 with excitation light having a wavelength of 380 nm.
- FIG. 44 is a fluorescence spectrum chart showing a spectrum of light emission generated by irradiating the light emitting layer obtained in Example 13 with excitation light having a wavelength of 365 nm.
- the (8-hydroxyquinolate) -based metal coordination compound can be represented by the formula (11).
- Y is any group represented by the following formulas (2) to (5), [0053] [Chemical 13]
- R 1 is a hydrogen atom or a methyl group.
- R 2 is an alkyl group having 1 to 20 carbon atoms.
- R 2 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n_pentyl group, sec- Pentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl , Nonadecyl group, and eicosyl group.
- an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is particularly preferable.
- M is a transition metal and a typical element in the 1988 IUPAC periodic table.
- Preferred M is a metal belonging to Group 2, Group 7, Group 12, and Group 13, and more preferred M is Mg, Zn, Al, Ga, In, Mn, and the like.
- n is a number obtained by subtracting 1 from the valence of the metal represented by M.
- n is 2 when the central metal is A1.
- Z 1 is a hydrogen atom or a group represented by the formula (12).
- R 5 is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms.
- the (8-hydroxyquinolate) -based metal coordination compound represented by the formula (11) emits fluorescence having a peak at a force of 500 to 550 nm depending on the type of ligand and metal. It is a fluorescent compound.
- This fluorescence property is based on the structure of the coordination compound consisting of a metal and its ligand, which is bonded to the oxaziazole ring, the electron withdrawing property derived from the oxaziazole ring, and the photoconductive property of the group Y, particularly the force rubazole group. It is thought that it is based on.
- the (8-hydroxyquinolate) -based metal coordination compound ( ⁇ ) which is a substituent represented by (2), (3) or (4) has a polymerizable double bond in the molecule, It can be a polymer.
- ⁇ ⁇ is a substituent represented by the formula (5)
- the (8-hydroxyquinolate) -based metal coordination compound ( ⁇ ) does not have polymerizability, but by adopting a casting method or the like that dissolves in a solvent to form a film, or By adopting polymer processing techniques by mixing with polymer compounds such as polybulcarbazole, the light emitting layer, charge transport layer, and hole in light emitting devices such as organic EL devices are used. It is an organic electoluminescence material that can suitably form a transport layer and the like.
- the (8-hydroxyquinolate) -based metal coordination compound represented by the formula (11) can be produced, for example, as follows.
- one COOR 4 is introduced into 8-hydroxyquinoline ((a) in the reaction formula (2)).
- R 4 has the same meaning as described above.
- Introduction of the group shown by COOR 4 is based on a method of introducing an acyl group on the benzene ring using the Friedel-Craft reaction and oxidizing it, and a carbene group on the benzene ring using carbene formation. This is possible by using a method of introducing and oxidizing this.
- the compound in which the carboxylic acid or carboxylic acid ester group is introduced ((b) in the reaction formula (2)) is reacted with hydrazine to derive a carbohydrazide derivative ((c) in the reaction formula (2)).
- the coordination compound residue-containing polymer compound according to the present invention will be described taking a (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound as an example of its preferred form.
- This (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound has a repeating unit represented by the formula (13).
- M, RZ, Z 1 and n have the same meaning as described above.
- the (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound may be a homopolymer having a repeating unit represented by formula (13) or may have another repeating unit. It may be a copolymer. Examples of the other monomer as the repeating unit include N-vinylcarbazole, methyl methacrylate, acrylate, and styrene.
- the number average molecular weight of the (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound is usually 500 to 500,000.
- (8-Hydroxyquinolate) -based metal coordination compound-containing polymer compound has a group Y represented by the formula (2),
- the polymerization may be homopolymerization or copolymerization.
- the polymerization reaction is any of radical polymerization, ion polymerization, and cationic polymerization. There may be.
- the polymerization method may be any of bulk polymerization method, suspension polymerization method, emulsion polymerization method and solution polymerization method, but the solution polymerization method is preferred.
- the polymerization reaction may be carried out under normal pressure, or under reduced pressure or under pressure, but is usually carried out under normal pressure.
- the polymerization process may be a batch process or a continuous process, but the power of manufacturing efficiency is preferred.
- the (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound is used by mixing with a coordination compound (X) represented by the following formula (X) Can be done.
- the coordination compound (X) can be used for a light emitting layer, an electron transport layer, or a hole transport layer by selecting a substituent in the molecule.
- R5 represents an alkyl group
- M and n have the same meaning as described above.
- organic electoluminescence materials are suitable as materials for forming a light emitting layer, an electron transport layer, a hole transport layer, and the like in a light emitting device.
- a low molecular (8 hydroxyquinolate) -based metal coordination compound represented by the formula (11) and Z or (8 hydroxyquinolate) -based metal coordination compound represented by the formula (12) A white organic electoluminescent material comprising a light emitting compound that emits a color that is substantially complementary to the color emitted by the containing polymer compound can be mentioned.
- the low molecular (8-hydroxyquinolate) -based metal coordination compound represented by the formula (11) and Z or the formula (12 ) Is appropriately selected according to the color emitted by the polymer compound containing a (8 hydroxyquinolate) -based metal coordination compound.
- Examples of the light emitting compound include a blue light emitting compound and a red light emitting compound.
- JP-A 2 As the light emitting compound that emits light having a substantially complementary color, for example, JP-A 2
- Nile red compound represented by the following formula (1),
- Nile red compounds represented by the following formula (1) described in JP-A-2003-277369
- Examples thereof include a coumarin red light emitting compound represented by the following formula (1) described in JP-A-2002-114773, and known Nile red.
- JP-A-2004-3 As a light-emitting compound that emits light having a substantially complementary color, JP-A-2004-3
- Examples include a blue light-emitting compound represented by the following formula (1) described in JP-A-2004-18401.
- distyryl red light-emitting materials (Proceedings of the 60th Annual Conference of the Japan Society of Applied Physics" Sep. 3p— N— Page 18 Publication year: 1999 Applied physics Published by Title: Examination of distyryl derivative organic EL red light emitting material (2)), perylene red light emitting material ("Cho 11 Solid Films” Vol. 372 pages 163-168 Publication year: 2000 Issued by Elsevier Scien ce fitle: The influence Authors: P.Schouwink; AHSchafer; C.beidel; H.Fuchs) etc.
- aromatic light emission such as anthracene, methyl anthracene, naphthalene, phenanthrene, pyrene, taricene, perylene, butadiene derivatives, coumarin, atalidine, stilbene derivatives, etc. Compounds can be mentioned.
- This aromatic light-emitting compound is not only easily available, but also has a low molecular (8 hydroxyquinolate) -based metal coordination compound represented by the formula (11) and Z or the formula (12) (8)
- a polymer compound containing a (hydroxyquinolate) -based metal coordination compound By combining with a polymer compound containing a (hydroxyquinolate) -based metal coordination compound, an organic electoluminescence material capable of emitting white light with high luminance is formed.
- the low-molecular (8 hydroxyquinolate) -based metal coordination compound or the (8 hydroxyquinolate) -based metal coordination compound-containing polymer compound and the light-emitting compound are combined in a light-emitting layer.
- the formation will be described as an example.
- the low molecular (8-hydroxyquinolate) -based metal coordination compound or the (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound is used.
- a light emitting layer composed of two layers of a light emitting layer formed from the light emitting compound.
- the low molecular (8 hydroxyquinolate) -based metal coordination compound or the (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound Formed from a mixture of the blue light-emitting compound and the red light-emitting compound.
- An optical layer etc. can be mentioned.
- Mixing of the low molecular (8-hydroxyquinolate) metal coordination compound or the polymer compound containing the (8-hydroxyquinolate) metal coordination compound and the blue light emitting compound or the red light emitting compound in the mixture It is good to mix the two by mechanical and physical means so that the weight ratio is 1 (the former): 0.1 (the latter) to 1:10.
- a low molecular weight (8-hydroxyquinolate) -based metal coordination compound or a light-emitting layer formed from the (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound has a low molecular weight (8-Hydroxyquinolate) -based metal coordination compound or the above-mentioned (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound color which is substantially complementary to the color of light emitted It is possible to emit white light by irradiating light of substantially complementary color, for example, blue light from a light emitting light source that emits light.
- the best mode of the light emitting device according to the present invention is a device having a light emitting layer, an electron transport layer or a hole transport layer formed of the organic electoric luminescence material.
- the light-emitting layer, the electron transport layer, or the hole transport layer is formed of the organic electroluminescent material, and the organic electroluminescent material is soluble or soluble in the solvent.
- the organic electroluminescent material is soluble or soluble in the solvent.
- FIG. 1 is a cross-sectional view schematically showing an example of the light emitting device of the present invention.
- the light-emitting element 1 includes a transparent substrate 2, an anode 3, a hole injection layer 4, a hole transport layer 5, a light-emitting layer 6, an electron transport layer 7, an electron injection layer 8, and a cathode 9 stacked in that order. It is made up.
- Each layer constituting the light emitting element 1 is formed on the transparent substrate 2, and examples of the transparent substrate 2 include a glass substrate, a plastic substrate, and a silicon substrate.
- anode 3 various materials can be adopted as long as the work function is large and transparent.
- ITO indium tin oxide
- In O In O
- SnO Tin Oxide
- ZnO Zinc Oxide
- CdO CdO
- a conductive polymer material such as polyaline. This non-uniform thickness of anode 3 affects the film pressure of the light emitting layer, so smoothness is required.
- the anode 3 is formed on the transparent substrate 2 by chemical vapor deposition, spray pyrolysis, vacuum deposition, electron beam deposition, sputtering, ion beam sputtering, ion plating, ion assist. It can be formed by a method such as vapor deposition.
- the hole injection layer 4 includes a triphenylamine compound such as N, ⁇ '-diphenyl ⁇ , ⁇ '-di (m-tolyl) monobenzidine (TPD), ( ⁇ - Hydrazone compounds such as NPD), stilbene compounds such as stilbenbis [ ⁇ - (1 naphthyl)) phenol] benzidine compounds, heterocyclic compounds, ⁇ -electron starburst hole transport materials, etc.
- TPD triphenylamine compound
- NPD ⁇ - Hydrazone compounds
- stilbene compounds such as stilbenbis [ ⁇ - (1 naphthyl)) phenol] benzidine compounds
- heterocyclic compounds ⁇ -electron starburst hole transport materials, etc.
- the layer to be formed can be mentioned.
- the hole transport layer 5 includes the (8 hydroxyquinolate) -based metal coordination compound and the ⁇ or (8-hydroxyquinolate) -based metal coordination compound-containing high molecular compound. Is formed by.
- the hole transport layer 5 can be formed by, for example, a spin casting method, a coating method, a dip method, or the like, by an evaporation method.
- the light-emitting layer 6 is a layer containing a light-emitting compound, and examples of the light-emitting compound include red, blue, and white light-emitting compounds.
- This light emitting layer 6 is formed by vapor deposition or coating. It can be formed by a method such as spin casting, coating or dipping.
- the light-emitting layer 6 can contain a fluorescent light-emitting compound corresponding to the light-emitting characteristics, and the (8-hydroxyquinolate) -based metal coordination compound and Z or the (8-hydroxyquinoquinone) according to the present invention. (Rate) -based metal coordination compound-containing polymer compound can also be contained.
- the electron transport layer 7 is composed of the (8 hydroxyquinolate) -based metal coordination compound and Z or the (8-hydroxyquinolate) -based metal coordination compound-containing high molecular compound. Is formed.
- the electron transport layer 7 can be formed by, for example, a spin casting method, a coating method, a dip method, or the like, by an evaporation method.
- Examples of the electron injection layer 8 include 2,5 bis (1 naphthyl) -1,3,4 oxadiazole (BND), 2- (4-tert-butylphenol) -5- (4 biphenol- Ril) —oxadiazole derivatives such as 1,3,4-oxadiazole, 2,5 bis (5,1-tertbutyl-1,2-benzoxazolyl) thiophene, tris (8-quinolinolato) aluminum complex (A lq3), Mention may be made of layers in which forces are also formed, such as metal complex materials such as benzoquinolinol beryllium complex (Bebq2).
- the electron injection layer 8 can be formed by a vapor deposition method, a coating method, such as a spin casting method, a coating method, or a dipping method.
- the cathode 9 employs a substance having a small work function, and can be formed of, for example, a single metal such as Mg, Ag, an aluminum alloy, or calcium metal, or a metal alloy.
- a preferred cathode is an alloy electrode of aluminum and a small amount of lithium.
- the cathode 9 is formed on the surface of each layer formed on the transparent substrate 2 by chemical vapor deposition, spray pyrolysis, vacuum deposition, electron beam deposition, sputtering, ion beam sputtering, ion plating. It can form by methods, such as a method and an ion-assisted vapor deposition method.
- the light-emitting element 1 having such a layer configuration, holes are injected from the anode 3 into the hole injection layer 4 through the hole transport layer 5 by passing an electric current. In this case, electrons are injected toward the light emitting layer 6 containing the light emitting compound. In the light emitting layer 6, electrons and holes are combined to excite the phosphor (light emitting compound) of the light emitting layer 6, and when this excited state returns to its original state, light is emitted and energy is released.
- the thickness of the light-emitting element 1 is usually 0.1 to 0.
- the light-emitting device according to the present invention is not limited to the light-emitting device having the layer configuration shown in FIG. Including applied voltage polarity variable structure type EL element, temperature stable type multilayer EL element.
- the 8-hydroxyquinolate) metal coordination compound and Z or the (8-hydroxyquinolate) metal coordination compound-containing polymer compound are used as an electron injection / transport layer or a hole as an electron transport layer. It is also used as a hole injection transport layer as a transport layer.
- the white light emitting device comprises a light emitting layer 19 sandwiched between an anode 18 and a cathode 20, and the light emitting layer 19 is represented by the formula (11).
- Examples thereof include an element which is a layer containing a light emitting compound that emits light having a substantially complementary color.
- Low molecular (8-hydroxyquinolate) -based metal coordination compounds and polymer compounds containing Z or (8-hydroxyquinolate) -based metal coordination compounds are themselves charge transport materials or electron transport materials depending on their structures. Therefore, even if the charge transport layer and the electron transport layer are not provided, when a voltage is applied to the light emitting layer 19, a low molecular (8 hydroxyquinolate) -based metal arrangement is formed in the light emitting layer 19.
- White light is emitted by generating light from the compound and the Z or (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound and the light-emitting compound.
- a first light emitting layer 19a and a second light emitting layer 19b are sandwiched between an anode 18 and a cathode 20,
- the first light emitting layer 19a is a low molecular (8 hydroxyquinolate) -based metal coordination compound represented by the formula (11) and Z or the (8 hydroxyquinolate) system represented by the formula (12).
- the second light-emitting layer 19b is composed of a low molecular (8 hydroxyquinolate) -based metal coordination compound represented by the formula (11) and Z or the formula (12).
- the low molecular (8-hydroxyquinolate) -based metal coordination compound and the Z or (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound are themselves Depending on the structure, it has a function as a charge transport material or an electron transport material, and even if it has at least a charge transport layer and an electron transport layer, when a voltage is applied to the light emitting layer 19, a low molecular weight ( White light is emitted from the light-emitting compound and the polymer compound containing the 8-hydroxyquinolate) metal coordination compound and Z or (8-hydroxyquinolate) metal coordination compound and the light-emitting compound. .
- the light emitting layer 19, the first light emitting layer 19a, and the second light emitting layer 19b may be a white light emitting device in which a charge transport layer and an electron transport layer are further laminated.
- the other white light emitting device is a low molecular (8-hydroxyquinolate) -based metal coordination compound represented by the above formula (11) and Z or the above formula.
- An element having a light source 21 that develops a color complementary to the color emitted by the polymer compound containing a (hydroxyquinolate) -based metal coordination compound is included.
- the light source 21 can irradiate the light emitting layer 22 with a color having a complementary color relationship, the light emitting layer 22 and the light source 21 need to have a laminated structure as shown in FIG. Nah ... Since the light emitting layer 22 emits light by electric energy, an electrode composed of an anode and a cathode not shown in FIG. 34 is provided.
- the light-emitting layer can be a polymer film layer using polyvinyl carbazole, AS (acrylonitrile styrene) polymer, polystyrene, or burnaphthalene polymer as a matrix polymer.
- the thickness of this light emitting layer is usually Inn! ⁇ 5 cm, which is appropriately determined according to the use of the light emitting element.
- Example 1 the (8-hydroxyquinolate) -based metal coordination compound (14) represented by the formula (14) was synthesized as follows.
- Fig. 3 shows the infrared absorption (IR) spectrum of this solid
- Fig. 4 shows the NMR spectrum. From this IR ⁇ vector and NMR ⁇ vector, the solid was identified as a carbohydrazide compound (16) represented by formula (16).
- the solid is an (8-hydroxyquinolate) -based A1 coordination group represented by the formula (14). It was identified as Compound (14).
- This (8-hydroxyquinolate) A1 coordination compound (14) was dissolved in DMAC to prepare a sample solution. This sample solution was loaded into a Hitachi F-4500 spectrofluorometer and the fluorescence spectrum was measured under the following conditions. The obtained fluorescence spectrum is shown in FIG.
- Example 2 the (8 hydroxyquinolate) -based A1 coordination compound (19) represented by the formula (19) was synthesized as follows.
- the flask contained 4.02 g of the above compound (23), 5 g of KOHO., 50 ml of dimethinolehonolemamide, 30 ml of 1,4-dioxane and 20 ml of ethyl alcohol and stirred at 70 ° C. for 12 hours. . Subsequently, after neutralizing with acetic acid, the solvent was distilled off to obtain a solid. Fig. 13 shows the IR vector chart of this solid, and Fig. 14 shows the NMR ⁇ vector. From this IR ⁇ vector and N MR spectrum, the solid was identified as the compound (24) represented by the formula (24).
- This compound (24) was dissolved in DMAC to prepare a sample solution.
- This sample solution was loaded into a Shimadzu F-4500 spectrofluorometer and the fluorescence spectrum was measured under the same conditions as in Example 1. The obtained fluorescence spectrum is shown in FIG.
- This (8-hydroxyquinolate) A1 coordination compound (19) was dissolved in DMAC to prepare a sample solution.
- This sample solution was loaded into an F-4500 type spectrofluorometer manufactured by Shimadzu Corporation, and the fluorescence spectrum was measured under the above conditions. The obtained fluorescence spectrum is shown in FIG.
- A1 coordination compound (19) represented by the formula (19) 180 mg, AIB NO. 8 mg and DMF 30 cm 3 were sealed in a sealed tube and heated to 120 ° C. Time polymerization was carried out. [0153] After the polymerization was completed, the content of the sealed tube was concentrated, and then this concentrate was put into methanol to precipitate the produced polymer.
- FIG. 18 shows an IR spectrum chart of the obtained polymer
- FIG. 19 shows a fluorescence spectrum chart measured in the same manner as described above.
- FIG. 20 shows an IR ⁇ vector chart of the obtained copolymer.
- the polymerization was carried out for 48 hours while heating to ° C.
- Indium trichloride is used in place of magnesium nitrate in Example 3, 8 hydroxyquinoline is used in place of 1 equivalent, 8 hydroxyquinoline is used in 2 equivalents, and potassium t-butylalcoside is used in place of 2 equivalents of potassium.
- t (Butylquinolate) In coordination compound (28) represented by the formula (28) was produced in the same manner as in Example 3 except for using 3 equivalents of t-butylalcoside.
- the (8-hydroxyquinolate) -based Mn coordination compound (29) was prepared in the same manner as in Example 3 except that manganese sulfate was used instead of magnesium nitrate in Example 3. Manufactured.
- FIG. 31 A light emitting device having the structure shown in FIG. 31 was prepared.
- 10 is a light emitting element
- 12 is a glass substrate
- 13 is an ITO transparent electrode
- 14 is a hole injection layer
- 15 is a light emitting layer
- 16 is a Ca electrode layer
- 17 is an Ag electrode layer.
- the light emitting device shown in Fig. 31 was manufactured as follows.
- the glass substrate 12 was subjected to ultrasonic cleaning in an ion exchange aqueous solution containing an alkali cleaning agent, then ultrasonically cleaned with ion exchange water, then dried, and further subjected to ultraviolet cleaning.
- An ITO transparent electrode was formed by depositing ITO on the surface of the glass substrate 12.
- An Ag electrode layer 17 was formed.
- a fluorescence spectrum was measured using a spectrofluorometer (H-4500, manufactured by Hitachi, excitation wavelength: 34 Onm). This fluorescence spectrum chart is shown in FIG. From the fluorescence spectrum chart, white light emission of the light emitting layer was confirmed.
- Fig. 36 shows the fluorescence spectrum measured using an excitation wavelength of 365 nm
- Fig. 37 shows the fluorescence spectrum measured using an excitation wavelength of 380 nm.
- white light emission was observed from the light emitting layer even when the excitation wavelength ranged from 340 to 380 nm.
- White light emission could be observed from the light emitting layer even when irradiated with light from a mercury lamp having an excitation wavelength of about 250 nm.
- a fluorescence spectrum was measured using a spectrofluorometer (F-4500, manufactured by Hitachi, Ltd., excitation wavelength: 34 Onm). This fluorescence spectrum chart is shown in FIG. From the fluorescence spectrum chart, white light emission of the light emitting layer was confirmed. White light emission of the light emitting layer was confirmed.
- the fluorescence vector measured using an excitation wavelength of 365 nm is shown in FIG. 39, and the fluorescence spectrum measured using an excitation wavelength of 380 nm is shown in FIG.
- white light emission was observed from the light emitting layer even when the excitation wavelength ranged from 340 to 380 nm.
- White light emission could be observed from the light-emitting layer even when irradiated with light from a mercury lamp having an excitation wavelength of about 250 nm.
- a fluorescence spectrum was measured using a spectrofluorometer (H-4500, manufactured by Hitachi, Ltd., excitation wavelength: 34 Onm). This fluorescence spectrum chart is shown in FIG. From the fluorescence spectrum chart, white light emission of the light emitting layer was confirmed. White light emission of the light emitting layer was confirmed. Fig. 42 shows the fluorescence vector measured using the excitation wavelength of 365nm, and Fig. 43 shows the fluorescence spectrum measured using the excitation wavelength of 380nm. Thus, white light emission was observed from the light emitting layer even when the excitation wavelength ranged from 340 to 380 nm. White light emission could be observed from the light-emitting layer even when irradiated with light from a mercury lamp having an excitation wavelength of about 250 nm.
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Abstract
Disclosed is a metal-containing coordination compound represented by the formula (1) below and having characteristics equivalent to or better than those of metal complexes which can be polymerized or dissolved in a solvent. Also disclosed is a coordination compound residue-containing polymer compound which is a polymer compound having characteristics equivalent to or better than those of metal complexes. Further disclosed is an organic electroluminescent material having characteristics equivalent to or better than those of metal complexes such as Alq3 which can be easily formed into a film by a method for processing an organic polymer compound, or can be dissolved in a solvent and easily formed into a film by a casting method. Still further disclosed are a light-emitting device and a white light-emitting device which can be produced by using such an organic electroluminescent material without requiring a deposition process.
Description
明 細 書 Specification
金属含有配位化合物、配位化合物残基含有高分子化合物、有機エレク トロルミネッセンス材、白色有機エレクト口ルミネッセンス材、白色発光素子及び発 光素子 Metal-containing coordination compound, coordination compound residue-containing polymer compound, organic electroluminescence material, white organic electoluminescence material, white light emitting device and light emitting device
技術分野 Technical field
[0001] この発明は、金属含有配位化合物、配位化合物残基含有高分子化合物、有機ェ レクト口ルミネッセンス材、白色有機エレクト口ルミネッセンス材、白色発光素子及び発 光素子に関し、更に詳しくは、重合可能な、又は溶媒に溶解可能な金属含有配位ィ匕 合物例えば (8—ヒドロキシキノレート）系金属配位化合物、前記重合可能な金属含 有配位化合物を重合してなる配位化合物残基含有高分子化合物例えば (8—ヒドロ キシキノレート）系高分子化合物、発光素子の形成に有用な有機エレクト口ルミネッセ ンス材、白色発光可能な白色発光素子の形成に有用な白色有機エレクト口ルミネッ センス材、白色に発光可能な白色発光素子並びに前記有機エレクト口ルミネッセンス 材により形成された電子輸送層、正孔輸送層及び発光層等の層を有して成る発光素 子に関する。 [0001] The present invention relates to a metal-containing coordination compound, a coordination compound residue-containing polymer compound, an organic electoluminescence material, a white organic electoluminescence material, a white light emitting device, and a light emitting device. Metal-containing coordination compounds that can be polymerized or dissolved in a solvent, for example, (8-hydroxyquinolate) -based metal coordination compounds, coordination compounds obtained by polymerizing the polymerizable metal-containing coordination compounds Residue-containing polymer compounds such as (8-hydroxyquinolate) polymer compounds, organic electroluminescent materials useful for the formation of light emitting devices, and white organic electoluminescent materials useful for the formation of white light emitting devices capable of emitting white light Materials, white light emitting elements capable of emitting white light, and layers such as an electron transport layer, a hole transport layer, and a light emitting layer formed by the organic electoluminescence material A light emitting element comprising a.
背景技術 Background art
[0002] 有機 EL素子は、発光層、電子輸送層及びホール輸送層を有し、電極から注入され た電子とホールとが再結合することによって生じるエネルギーにより発光物質を発光 させる。 An organic EL element has a light emitting layer, an electron transport layer, and a hole transport layer, and causes a light emitting substance to emit light by energy generated by recombination of electrons and holes injected from an electrode.
[0003] 有機 EL素子に関する最初の著名な論文は、 Tang and VanSlyke (1987)により発表 された。その論文によると、 Tangらは、電子注入性発光層に Alq3 [トリス（8—ヒドロキ シキノレート）アルミニウム]を用いて 、た (非特許文献 1、 2)。 [0003] The first prominent paper on organic EL devices was published by Tang and VanSlyke (1987). According to the paper, Tang et al. Used Alq3 [tris (8-hydroxyquinolate) aluminum] for the electron-injecting light-emitting layer (Non-patent Documents 1 and 2).
[0004] その論文以後、発光層に Alq3に限らず様々の蛍光物質を用いることが試みられて きた力 Alq3は未だにもっとも有望な発光材料又は電子注入材料の一つと考えられ てきた。前記 Alq3以外の発光材料としてユーロピウム系燐光発光錯体、リチウム系 青色発光錯体、燐光発光性ホスフィン金属錯体等の様々の金属錯体が試みられて いる。電子注入材料として、例えばガドリニウム錯体ドープ TPD等の金属錯体が試み
られている (非特許文献 3)。 [0004] Since that paper, attempts have been made to use various fluorescent materials in addition to Alq3 in the light emitting layer. Alq3 is still considered one of the most promising light emitting materials or electron injection materials. Various light-emitting materials other than Alq3 such as europium-based phosphorescent complexes, lithium-based blue light-emitting complexes, and phosphorescent phosphine metal complexes have been tried. For example, gadolinium complex-doped metal complexes such as TPD have been tried as electron injection materials. (Non-Patent Document 3).
[0005] 特許文献 1： http://www.chitose.ac.jp/~kyoin/person/kawabe/LED/LEDindex.ht ml [0005] Patent Document 1: http://www.chitose.ac.jp/~kyoin/person/kawabe/LED/LEDindex.ht ml
非特許文献 2 :日本実業出版社、 2004年 3月 1日第 6刷発行、「有機 ELのすベて」 ( P47) Non-Patent Document 2: Nihon Jitsugyo Publishing Co., Ltd., March 1st, 2004, 6th edition, “All about organic EL” (P47)
特干文献 3： http://www.jpo.go.jp/ shiryou/ s— sonota/hyoujun— gijutsu/yuuKi— el/5— m okuji.html しかしながら、金属錯体である発光物質及び電子注入材料は、溶解可能 な適当な溶媒が存在しないので、発光層、電子注入層及びホール輸送層を形成す る場合には、前記金属錯体例えば Alq3を蒸着して 、た。 Special Reference 3: http://www.jpo.go.jp/ shiryou / s— sonota / hyoujun— gijutsu / yuuKi— el / 5— m okuji.html However, luminescent materials and electron injection materials that are metal complexes are Since there is no suitable solvent that can be dissolved, the metal complex such as Alq3 was vapor deposited when forming the light emitting layer, the electron injection layer, and the hole transport layer.
[0006] 蒸着は、通常高真空下に金属錯体を加熱して蒸気にし、金属錯体の蒸気を所定の 部位に固化定着させることにより行われる。したがって、蒸着操作には、高真空を実 現する真空排気装置、金属錯体を加熱させる高温加熱装置、基板上に形成した電 極表面に金属錯体蒸気を固化させるための装置等を備えた、極めて大型の蒸着装 置が必要である。 [0006] Vapor deposition is usually performed by heating a metal complex to a vapor under high vacuum, and solidifying and fixing the vapor of the metal complex at a predetermined site. Therefore, the vapor deposition operation is extremely equipped with a vacuum evacuation device that realizes a high vacuum, a high-temperature heating device that heats the metal complex, and a device that solidifies the metal complex vapor on the electrode surface formed on the substrate. Large vapor deposition equipment is required.
[0007] このような大型で、複雑な装置構成を有する蒸着装置の使用は、有機 EL素子製造 における一つのネックとなって!/、る。 [0007] The use of such a large-sized and complicated apparatus is a bottleneck in the production of organic EL elements!
[0008] 一方、有機 EL素子の開発研究の一つの目的は、白色発光が可能で、しかも簡便 な方法により製造することのできる有機 EL素子を提供することである。 [0008] On the other hand, one object of research and development of organic EL devices is to provide an organic EL device that can emit white light and can be manufactured by a simple method.
発明の開示 Disclosure of the invention
発明が解決しょうとする課題 Problems to be solved by the invention
[0009] この発明は、金属錯体と同等又はそれ以上の特性を有し、し力も高分子化可能な、 又は溶媒に溶解可能な金属含有配位化合物を提供することを目的とする。この発明 は、金属錯体と同等又はそれ以上の特性を有する高分子化合物である配位ィ匕合物 残基含有高分子化合物を提供することを目的とする。この発明は、また、有機高分子 化合物の加工法により容易にフィルム化することができ、又は溶媒に溶解してフィル ムを形成するキャスト法により容易にフィルム化することができ、し力も Alq3等の金属 錯体と同等又はそれ以上の特性を有する有機エレクト口ルミネッセンス材及びそれを 用いることにより蒸着操作によることなく製造されることのできる発光素子を提供する
ことを目的とする。また、この発明の他の目的は、前記有機エレクト口ルミネッセンス材 を用いて白色発光可能にする白色有機エレクト口ルミネッセンス材を提供すること、 白色発光可能な白色発光素子を提供することである。 [0009] An object of the present invention is to provide a metal-containing coordination compound having characteristics equivalent to or higher than those of a metal complex and capable of being polymerized or dissolved in a solvent. An object of the present invention is to provide a coordination compound residue-containing polymer compound that is a polymer compound having properties equivalent to or higher than those of a metal complex. This invention can also be easily formed into a film by a processing method of an organic polymer compound, or can be easily formed into a film by a casting method in which a film is formed by dissolving in a solvent. Provided are an organic electoluminescence material having characteristics equivalent to or better than those of the above metal complexes, and a light emitting device that can be produced without using a vapor deposition operation by using the same For the purpose. Another object of the present invention is to provide a white organic-electric luminescence material that can emit white light using the organic-electric-luminescence material, and to provide a white light-emitting element that can emit white light.
課題を解決するための手段 Means for solving the problem
[0010] この発明の前記課題を解決する手段として、 [0010] As means for solving the problems of the present invention,
(1)請求項 1は、下記式（1)で表されることを特徴とする金属含有配位ィ匕合物であり、 [0011] [化 1] (1) Claim 1 is a metal-containing coordination compound characterized by the following formula (1): [0011] [Chemical Formula 1]
B ノ C = N B no C = N
\C = N \ C = N
A … ) A…)
[0012] 〔前記式（1)において、 Aは、金属とチォフェン環又は芳香環を含有し、且つ前記 金属に配位する配位子とを有する発光性配位ィヒ合物における前記チォフェン環又 は芳香環から水素を引き抜いた残基であり、 Bは、下記式（2)〜（5)で表されるいず れかの基である。〕 [In the above formula (1), A represents a thiophene ring in a luminescent coordination complex containing a metal and a thiophene ring or an aromatic ring and having a ligand coordinated to the metal. Or, it is a residue obtained by extracting hydrogen from an aromatic ring, and B is any group represented by the following formulas (2) to (5). ]
[0013] [化 2] [0013] [Chemical 2]
— OH— H— OH— H
-■■ (3) -■■ (3)
[0015] [ィ匕 4] [0015] [4]
R1 R 1
…（4) …(Four)
[0016] 〔ただし、前記式 (4)にお 、て、 R1は、水素原子又はメチル基である。〕 [In the formula (4), R 1 is a hydrogen atom or a methyl group. ]
[0017] [化 5] [0017] [Chemical 5]
R 2-
R 2-
. ' . (5) . ' . (Five)
〔ただし、前記式（5)において、 ITは、炭素数 1〜20のアルキル基である。〕 [However, in said Formula (5), IT is a C1-C20 alkyl group. ]
(2)請求項 2は、下記式 (6)で表される繰り返し単位を有することを特徴とする配位ィ匕
合物残基含有高分子化合物であり、 (2) Claim 2 has a repeating unit represented by the following formula (6): A compound residue-containing polymer compound,
[化 6] [Chemical 6]
A A
(6) (6)
[0020] 〔ただし、前記式（6)において、 Aは請求項 1におけるのと同様の意味を有し、 Zは、 下記式（7)、（8)又は単結合であり、 R3は、 Zが式（7)で示される基であるときには水 素原子であり、 Zが式 (8)で示されるときには水素原子又はメチル基である。なお、下 記式（7)及び (8)において、点線により囲まれている部分は、式（7)及び (8)で示そう とする基に含まれない。〕 [In the above formula (6), A has the same meaning as in claim 1, Z is the following formula (7), (8) or a single bond, R 3 is When Z is a group represented by the formula (7), it is a hydrogen atom, and when Z is represented by the formula (8), it is a hydrogen atom or a methyl group. In the following formulas (7) and (8), the portion surrounded by the dotted line is not included in the group to be expressed by formulas (7) and (8). ]
[0021] [化 7] [0021] [Chemical 7]
[0022] [化 8]
[0022] [Chemical 8]
r r
…（8 ) ... (8)
(3)請求項 3は、請求項 1に記載の金属含有配位化合物及び Z又は請求項 2に記載 の配位化合物残基含有高分子化合物を含有することを特徴とする有機エレクト口ルミ ネッセンス材であり、 (3) Claim 3 is an organic electorium luminescence characterized by containing the metal-containing coordination compound according to claim 1 and Z or the coordination compound residue-containing polymer compound according to claim 2. Material,
(4)請求項 4は、請求項 1に記載の金属含有配位化合物及び Z又は請求項 2に記載 の配位化合物残基含有高分子化合物と前記金属含有配位化合物及び Z又は前記 配位化合物残基含有高分子化合物の発光色と実質的に補色の関係にある光を発 する発光化合物とを含有することを特徴とする白色有機エレクト口ルミネッセンス材で あり、 (4) Claim 4 is the metal-containing coordination compound according to claim 1 and Z or the coordination compound residue-containing polymer compound according to claim 2 and the metal-containing coordination compound and Z or the coordination. A white organic electoluminescent material characterized by containing a light-emitting compound that emits light that is substantially complementary to the light-emitting color of the polymer residue-containing polymer compound,
(5)請求項 5は、請求項 3に記載の有機エレクト口ルミネッセンス材を含有する層を有 して成ることを特徴とする発光素子であり、 (5) Claim 5 is a light emitting device comprising a layer containing the organic electoluminescence material according to claim 3,
(6)請求項 6は、前記請求項 3に記載の有機エレクト口ルミネッセンス材の発光色と、 前記エレクト口ルミネッセンス材と実質的に補色の関係にある光を発する発光化合物 とを含有する発光層を有することを特徴とする白色発光素子であり、 (6) Claim 6 is a light emitting layer containing a light emitting color of the organic electroluminescent material according to claim 3 and a light emitting compound that emits light substantially in a complementary color relationship with the electroluminescent material. It is a white light emitting element characterized by having,
(7)請求項 7は、請求項 3に記載の有機エレクト口ルミネッセンス材を含有する第 1発 光層と前記請求項 3に記載の有機エレクト口ルミネッセンス材の発光色と実質的に補 色の関係にある光を発する発光化合物を含有する第 2発光層とを備えてなることを特 徴とする白色発光素子であり、 (7) Claim 7 is substantially complementary to the luminescent color of the first light-emitting layer containing the organic electoluminescence material of claim 3 and the organic electroluminescence material of claim 3. A white light-emitting element comprising: a second light-emitting layer containing a light-emitting compound that emits light having a relationship;
(8)請求項 8は、請求項 3に記載の有機エレクト口ルミネッセンス材を含有する発光層 と、この発光層に前記請求項 3に記載の有機エレクト口ルミネッセンス材の発光色と実 質的に補色の関係にある光を発する発光源とを有して成ることを特徴とする白色発
光素子である。 (8) Claim 8 is substantially equivalent to the light emitting layer containing the organic electoluminescent material according to claim 3 and the light emitting color of the organic electroluminescent material according to claim 3 in the light emitting layer. A white light source characterized by having a light emitting source that emits light in a complementary color relationship It is an optical element.
発明の効果 The invention's effect
[0024] 前記式（1)で示される金属含有配位化合物は、金属とチオフ ン環又は芳香環を 含有し、且つ前記金属に配位する配位子とを有する発光性配位化合物における前 記チオフ ン環又は芳香環力 水素を引き抜 、た残基 Aを有する。 [0024] The metal-containing coordination compound represented by the formula (1) contains a metal and a thiophene ring or an aromatic ring and has a ligand that coordinates to the metal. The thiophene ring or aromatic ring force has a residue A after abstracting hydrogen.
[0025] この残基 Aとしては、例えば [0025] Examples of the residue A include
ォキサジァゾ一ルーベリリウム錯体（「Advanced Materials] Vol.11 No.17 1460p- 1463 p 発行年 1999 Title: A New Class of Blue-Emitting Materials Based on 1,3,5— Oxadi azole Mtal chelate Compounds for Electroluminescent Devices 著者： Nan-Xing Hu ； Mohammad Esteghamatian; Shuang Xie; Zoran Popovic; Ah— Me Hor; Beng Ong; S uning Wang)の残基、 Oxadiazole Mtal chelate Compounds for Electroluminescent Devices (Advanced Materials) Vol.11 No.17 1460p- 1463 p Publication year 1999 Title: A New Class of Blue-Emitting Materials Based on 1,3,5— : Nan-Xing Hu; Mohammad Esteghamatian; Shuang Xie; Zoran Popovic; Ah—Me Hor; Beng Ong;
而熱性リチウム系青色発光錯体（「Advanced Materials」 Vol. 11 No. 17 1463頁〜 1466頁 発行年： 1999 Advanced Materials発行 Title : Blue Light-Emitting Device Based on a Unidentate OrganoMtallic し omplex Containing Lithium as an Emission Layer 著者： Youngkyoo Kim; Lae- Gyoung Lee; Sunwook Kim)の残基、 Metathermal Lithium-based Blue Luminescent Complex (“Advanced Materials” Vol. 11 No. 17 pp. 1463–1466 Publication year: 1999 Published by Advanced Materials Title: Blue Light-Emitting Device Based on a Unidentate OrganoMtallic and omplex Containing Lithium as an Emission Layer Author: Youngkyoo Kim; Lae-Gyoung Lee; Sunwook Kim)
ユーロピウム系燐光発光錯体（「Advanced Materials」 Vol. 11 No. 7 533頁〜 536 M 発行年： 1999 Advanced Materials発行 ltle： Orange Electroluminescence from a Divalent Europium Complex 者： Cnristpner P.Shipley; Simone Capecchi; Oleg V.Salata; Mark Etchells; Peter J.Dobson; Victor Christou)の残基、 Europium-based phosphorescent light-emitting complex ("Advanced Materials" Vol. 11 No. 7 pp. 533 to 536 M Publication year: 1999 Advanced Materials published ltle: Orange Electroluminescence from a Divalent Europium Complex by Cnristpner P. Shipley; Simone Capecchi; Oleg V. Salata; Mark Etchells; Peter J. Dobson; Victor Christou),
燐光発光性ホスフィン 金錯体（「Applied Physics Letters」 Vol. 74 No. 10 1361 頁〜 1363頁 発行年： 1999 AMrican Institute of Physics発行 Title : Triplet lumine scent dinuclear— gold(l) complex-based light-emitting diodes with low turn-on voltag e 著者： Yuguang Ma; XueMi Zhou; Jiacong Shen; Hsiu- Yi Chao; Chi-Mingし he)の 残基、 Phosphorescent Phosphine Gold Complex (“Applied Physics Letters” Vol. 74 No. 10 1361-1363 Publication year: 1999 Published by AMrican Institute of Physics Title: Triplet lumine scent dinuclear— gold (l) complex-based light-emitting diodes with low turn-on voltag e Author: Yuguang Ma; XueMi Zhou; Jiacong Shen; Hsiu- Yi Chao;
テルビウム系発光錯体（Synthetic Metals」 Vol. 99 127頁〜 132頁 発行年： 1999 Elsevier Science発行 f itle： Photoluminescence and electroluminescence of a serie s of terbium complexes 著者： Xi- Cun Gao; Hong Cao; Chun- Hui Huang; Shigeo U mitani; Guang— Qiang Chen; Peng Jiang)の残基、
チォフヱンーァルミニゥム黄色発光錯体（「丁 3011(1
」 Vol. 342 8頁〜 10頁 発行年： 1999 Elsevier science発行 Title： Yellow organic electroluminescent device based on novel thiophene Al complex as an emitting layer 著者： Keizou Okada; Ya n-Feng Wang; Tadao Nakaya)の残基、 Synthetic Metals Vol. 99 127-132 Publication year: 1999 Published by Elsevier Science f itle: Photoluminescence and electroluminescence of a serie s of terbium complexes Author: Xi- Cun Gao; Hong Cao; Chun- Hui Huang ; Residue of Shigeo U mitani; Guang—Qiang Chen; Peng Jiang) Typhoon-Arminium Yellow Luminescent Complex (“Ding 3011 (1 Vol. 342 pp. 8-10 Publication year: 1999 Published by Elsevier science Title: Yellow organic electroluminescent device based on novel thiophene Al complex as an emitting layer Author: Keizou Okada; Yan-Feng Wang; Tadao Nakaya) residue,
亜鉛系黄緑発光錯体（「Thin Solid Films」 Vol. 346 69頁〜 72頁 発行年： 1999 El sevier Science発 ft Title： Yellow green electroluminescence generated from the thin films of β - diketone- zinc complex 著者： Keizou Okada; Yan- Feng Wang; Tian-Mi ng Chen; Tadao Nakaya)の残基、 Zinc-based yellow-green light emitting complex (“Thin Solid Films” Vol. 346 69-72 Publication year: 1999 El sevier Science ft Title: Yellow green electroluminescence generated from the thin films of β-diketone- zinc complex Author: Keizou Okada Yan- Feng Wang; Tian-Ming Chen; Tadao Nakaya) residue,
アモルファス性アルミニウム系緑色発光錯体（Synthetic Metals」 Vol. I l l- 112 10 9頁〜 112頁 発行年： 2000 Elsevier Science発行 Title： Improved efficiency of mole cular organic EL devices based on super molecular structure 著者： Shougen Yin; Y ulin Hua; Xiaohong Chen; Xiaohui Yang; Yanbing Hou; Xurong Xu)の残基、 ボロン系発光錯体（「Synthetic Metals」 Vol. I l l- 112 459頁〜 463頁 発行年： 200 0 Elsevier Science免 t Title： Materials for organic electroluminescence： aluminiu m vs. born 著者： Sally Anderson; Michael S.Weaver; Andrew J.Hudson)の残基、 テルビウム置換ユーロピウム系発光錯体（「Thin Solid Films」 Vol. 363 208頁〜 210 頁 発行年： 2000 Elsevier Science発ィ丁 Title： Enhanced electroluminescence of eur opium complex by terbium substitution in organic light emitting diodes 著者： Dongx u Zhao; Ziruo Hong;し hunjun Liang; Dan Zhao; Xingyuan Liu; Wenlian Li; C.S.Lee; S.T.Lee)の残基、 Synthetic Metals Vol. I l-112 10 9-112 Publication year: 2000 Published by Elsevier Science Title: Improved efficiency of mole cular organic EL devices based on super molecular structure Author: Shougen Yin Residues of Y ulin Hua; Xiaohong Chen; Xiaohui Yang; Yanbing Hou; Xurong Xu) Boron-based light-emitting complexes (“Synthetic Metals” Vol. I l l- 112 459-463 Publication year: 200 0 Elsevier Science t Title: Materials for organic electroluminescence: aluminum vs. born Author: Sally Anderson; Michael S. Weaver; Andrew J. Hudson), Terbium-substituted europium-based light-emitting complex ("Thin Solid Films" Vol. 363, p. 208- Page 210 Publication year: 2000 Elsevier Science title: Enhanced electroluminescence of europium complex by terbium substitution in organic light emitting diodes Author: Dongx u Zhao; Ziruo Hong; and hunjun Liang; Dan Zhao; Xingyuan Liu; Wenlian Li; CS Lee; STLee) Residue,
マグネシウム系発光錯体（Thin Solid Films) Vol. 363 134頁〜 137頁 発行年： 200 0 Elsevier Science免 t Title： Langmuir—Blodgett films and electroluminescent aevi ces of amphiphilic 8-hydroxyquinoline magnesium 著者： Jian- Ming Ouyang; Zhi-Mi ng Zhang)の残基、 Magnesium-based luminescent complexes (Thin Solid Films) Vol. 363 134-137 Publication year: 200 0 Elsevier Science immunity t Title: Langmuir—Blodgett films and electroluminescent aevices of amphiphilic 8-hydroxyquinoline magnesium -Mi ng Zhang) residue,
銅系燐光発光錯体（Synthetic Metals」 Vol. 121 1723頁〜 1724頁 発行年： 2001 ^lsevier science ィ丁 Title： Energy transfer from singlet to triplet excited states ι n organic light-emitting device 著者： Jingying Zhang; Shidong Kim; Yuguang Ma; Ji acong Shen; Winghan Chan; Chiming Che)の残基、及び
(8—ヒドロキシキノレート）系金属配位ィ匕合物の残基等を挙げることができる。 Synthetic Metals Vol. 121 pp. 1723-1724 Publication year: 2001 ^ lsevier science i-Title Title: Energy transfer from singlet to triplet excited states ι n organic light-emitting device Author: Jingying Zhang; Shidong Kim Residues of Yuguang Ma; Ji acong Shen; Winghan Chan; Chiming Che), and Examples include residues of (8-hydroxyquinolate) -based metal coordination compounds.
[0026] これらの残基 Aの中でも好ましい残基 Aは式（9)で示される（8—ヒドロキシキノレー ト）系金属配位ィ匕合物の残基である、 [0026] Among these residues A, a preferable residue A is a residue of an (8-hydroxyquinolate) -based metal coordination compound represented by the formula (9).
[0027] [化 9] [0027] [Chemical 9]
[0028] 〔但し、式（9)において、 Mは、 1988年の IUPACによる周期律表における遷移金 属及び典型元素である。 Z1は、水素原子又は式（12)で示される基である。 nは、 M で示される金属の価数から 1を引いた数である。〕 [In the formula (9), M is a transition metal and a typical element in the periodic table of IUPAC of 1988. Z 1 is a hydrogen atom or a group represented by the formula (12). n is the valence of the metal indicated by M minus 1. ]
[0029] [化 10]
[0029] [Chemical 10]
[0030] 但し、 R5はアルキル基であり、好ましくは炭素数 1〜20、特に好ましくは炭素数 1〜 10のアルキル基である。 [0030] However, R 5 is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 10 carbon atoms.
[0031] 前記式（1)で示される金属含有配位化合物は、前記の残基 Aとォキサジァゾール 環と特定の基 Bとを含有することにより、残基 Aにおける発光特性とォキサジァゾール 環自体の電子吸引性と Bで示される基の特性に応じて、有機 EL素子の発光材料、 電子輸送材料、ホール輸送材料等の有機エレクト口ルミネッセンス材に好適である。 [0031] The metal-containing coordination compound represented by the formula (1) contains the residue A, the oxadiazole ring, and the specific group B, so that the light emission characteristics in the residue A and the electron of the oxadiazole ring itself It is suitable for organic EL luminescence materials such as light-emitting materials, electron transport materials, and hole transport materials for organic EL devices, depending on the absorptivity and the characteristics of the group represented by B.
[0032] 前記式（1)で示される金属含有配位ィ匕合物において、基 Bが式（2)で示される N— ビニルカルバゾール残基、式（3)で示されるスチレン残基、式 (4)で示されるビニル 基であると、この金属含有配位化合物はこれを重合させることにより式 (6)で示される 配位化合物残基含有高分子化合物を与える。 [0032] In the metal-containing coordination compound represented by the formula (1), the group B is an N-vinylcarbazole residue represented by the formula (2), a styrene residue represented by the formula (3), a formula When the vinyl group is represented by (4), the metal-containing coordination compound is polymerized to give a coordination compound residue-containing polymer compound represented by formula (6).
[0033] 式 (6)で示される配位化合物残基含有高分子化合物は、残基 A、ォキサジァゾ一 ル環及び基 Bの特性に応じて有機 EL素子の発光材料、電子輸送材料、ホール輸送 材料等の有機エレクト口ルミネッセンス材に好適である。この配位化合物残基含有高 分子化合物はフィルム形成能を有するので、有機 EL素子等の発光素子における発 光層、電子輸送層及びホール輸送層を高分子加工技術により、蒸着技術を使用せ ずに、形成することができる。 [0033] The coordination compound residue-containing polymer represented by the formula (6) is a light-emitting material, an electron transport material, or a hole transport of an organic EL device depending on the characteristics of the residue A, the oxadiazole ring, and the group B. It is suitable for organic electoric luminescence materials such as materials. Since this high molecular weight compound containing coordination compound residues has a film-forming ability, the light emitting layer, the electron transport layer, and the hole transport layer in a light emitting device such as an organic EL device are not processed by a polymer processing technique without using a vapor deposition technology. Can be formed.
[0034] 基 Bが式（5)で示されるアルキルフエニル基であると、式（1)で示される金属含有配
位ィ匕合物は溶媒に対する溶解性が向上している。したがって、適宜の極性溶媒を選 択してその溶媒に前記式（1)で示される金属含有配位化合物を溶解して溶液を調 製し、その溶液を塗布することにより、発光層、電子輸送層又はホール輸送層を簡易 に形成することができる。 [0034] When the group B is an alkylphenyl group represented by the formula (5), the metal-containing group represented by the formula (1) The positional compound has improved solubility in a solvent. Therefore, by selecting an appropriate polar solvent, dissolving the metal-containing coordination compound represented by the formula (1) in the solvent, preparing a solution, and applying the solution, the light emitting layer, the electron transport A layer or a hole transport layer can be easily formed.
[0035] 式（1)で示される金属含有配位化合物及び式 (6)で示される繰り返し単位を有する 配位化合物残基含有高分子化合物は、その構造が堅牢であるから、耐久性のある 有機エレクト口ルミネッセンス材及び発光素子を与える。 [0035] The metal-containing coordination compound represented by the formula (1) and the coordination compound residue-containing polymer compound having a repeating unit represented by the formula (6) are durable because the structure is robust. An organic electoluminescence material and a light emitting element are provided.
[0036] 式（1)で示される金属含有配位化合物は、例えば反応式（1)に示されるように、フリ 一デルクラフツ反応、又はカルベンを利用したアルデヒド合成とアルデヒドの酸ィ匕によ るカルボン酸又はエステルの導入反応等により合成された Lg— COOR4 (但し、 Lg [li gandの略〕は式（1)で示される金属含有配位化合物中の配位子である。 )とヒドラジン とを反応させてヒドラジドィ匕合物（a)を合成し、このヒドラジド化合物 (a)とカルボン酸塩 化物とを反応させてジカルボヒドラジドィ匕合物 (b)を合成し、このジカルボヒドラジドィ匕 合物を加熱により閉環することにより、化合物 (c)を合成し、この化合物 (c)と配位子 と中心金属となり得る金属とを反応させることにより、容易に製造される。なお、以下 の式において、 R4はアルキル基例えばメチル基又はェチル基である。また、以下の 反応式は式（1)で示される化合物の合成における原理を示し、式（1)に含まれる多 様な化合物は以下の式に基づ ヽて有機合成の知識を参酌して容易に合成され得る [0036] The metal-containing coordination compound represented by the formula (1) is obtained by, for example, the Friedel-Crafts reaction or aldehyde synthesis using carbene and the acidity of the aldehyde as shown in the reaction formula (1). Lg—COOR 4 (where Lg [abbreviation of li gand] is a ligand in the metal-containing coordination compound represented by the formula (1)) synthesized by introduction reaction of carboxylic acid or ester and hydrazine To produce a hydrazide compound (a), and react this hydrazide compound (a) with a carboxylic acid chloride to synthesize a dicarbohydrazide compound (b). This dicarbohydrazide The compound (c) is synthesized by cyclization of the compound by heating, and the compound (c) is easily produced by reacting the ligand (c) with a metal that can be a central metal. In the following formula, R 4 is an alkyl group such as a methyl group or an ethyl group. In addition, the following reaction formula shows the principle in the synthesis of the compound represented by the formula (1), and various compounds included in the formula (1) are based on the following formula and refer to the knowledge of organic synthesis. Can be easily synthesized
[0037] [化 11]
[0037] [Chemical 11]
反応式（1 ) Reaction formula (1)
.g -COOR4 + NH2NH2 Lg-CONHNH2 .g -COOR4 + NH2NH2 Lg-CONHNH2
(a) (a)
Lg-CONHNH2 + B-COCI Lg-CONHNHCO-BLg-CONHNH2 + B-COCI Lg-CONHNHCO-B
(a) (b) (a) (b)
0 0
g一し し _t g _t
Lg-CONHNHCO-B Lg-CONHNHCO-B
Cb) N— N Cb) N— N
(c) (c)
し g + M +
G + M +
Cc) 式（1〉 Cc) Equation (1)
[0038] 式（1)で示される金属含有配位化合物は、その基 Bが式 (2)、（3)又は (4)で示さ れる二重結合含有の構造を有するときには、その二重結合を重合性官能基として重 合させると、式 (6)で示される繰り返し単位を有する配位化合物残基含有高分子化 合物を与える。したがって、上記一連の反応は、発光特性を有する有機金属錯体 (キ レート化合物を含む。 )を高分子化するための基本的な反応である。 [0038] The metal-containing coordination compound represented by the formula (1) has a double bond when the group B has a structure containing a double bond represented by the formula (2), (3) or (4). Is polymerized as a polymerizable functional group to give a polymer compound containing a coordination compound residue having a repeating unit represented by the formula (6). Therefore, the above series of reactions is a basic reaction for polymerizing an organometallic complex (including a chelate compound) having luminescence properties.
[0039] 式 (6)で示される繰り返し単位を有する配位化合物残基含有高分子化合物は、式 ( 6)で示される繰り返し単位を有する単独重合体であり、また式 (6)で示される繰り返 し単位を有する共重合体であり得る。前記共重合体としては、そのコモノマーとしてビ 二ルカルバゾール、及びメタタリレート系モノマー等を挙げることができる。 [0039] The coordination compound residue-containing polymer compound having a repeating unit represented by the formula (6) is a homopolymer having a repeating unit represented by the formula (6), and also represented by the formula (6). It can be a copolymer having repeating units. Examples of the copolymer include vinyl carbazole and a metatalylate monomer as comonomers.
[0040] 式 (6)で示される繰り返し単位を有する配位化合物残基含有高分子化合物は、例 えば高分子加工技術の手法により、有機 EL素子等の発光素子における発光層、電
荷輸送層、ホール輸送層等を形成することのできる有機エレクト口ルミネッセンス材料 として好適である。 [0040] The coordination compound residue-containing polymer compound having a repeating unit represented by the formula (6) is prepared by using a technique for polymer processing, for example, a light-emitting layer, an electrode in a light-emitting device such as an organic EL device. It is suitable as an organic electoluminescence material capable of forming a load transport layer, a hole transport layer, and the like.
[0041] したがって、式 (6)で示される繰り返し単位を有する配位化合物残基含有高分子化 合物は、蒸着等の操作を要することなく発光素子を形成することのできる好適材であ る。 [0041] Therefore, the coordination compound residue-containing polymer compound having a repeating unit represented by the formula (6) is a suitable material that can form a light-emitting element without requiring an operation such as vapor deposition. .
[0042] この発明に係る白色有機エレクト口ルミネッセンス材は、化学構造に応じて黄色から 緑色までの発色をする金属含有配位化合物及び Z又は配位化合物残基含有高分 子化合物と、前記黄色力 緑色までの色と実質的補色関係にある色の発光をする発 光化合物とを含有するので、エネルギーの付与により実質的に白色発光が可能であ る。ここで実質的に白色発光が可能であるとしたのは、観察者の目においては青み のある白、暖色系の白等を白と認識することから、人間の目において白と感じる色は 全て白色であるとするためである。 [0042] The white organic electoluminescence material according to the present invention includes a metal-containing coordination compound that forms a color from yellow to green according to a chemical structure, and a polymer compound containing Z or a coordination compound residue, and the yellow Since it contains a light emitting compound that emits light of a color substantially complementary to the color up to green, substantially white light emission is possible by applying energy. The reason that white light can be emitted substantially is that the observer's eyes recognize white that is bluish and warm white as white. This is because the color is white.
[0043] 実質的補色関係にある色の発光をする発光化合物は、前記金属含有配位ィ匕合物 及び Z又は配位化合物残基含有高分子化合物の種類に応じて適宜に決定されるこ とがでさる。 [0043] The light-emitting compound that emits light having a substantially complementary color relationship may be appropriately determined according to the type of the metal-containing coordination compound and Z or coordination compound residue-containing polymer compound. Togashi.
[0044] この発明に係る白色発光素子は、発光層を有する。発光層が単層である場合には 、その発光層は、化学構造に応じて黄色から緑色までの発色をする金属含有配位化 合物及び Z又は配位化合物残基含有高分子化合物と、前記黄色から緑色までの色 と実質的補色関係にある色の発光をする発光化合物とを含有する。発光層内で、金 属含有配位化合物及び Z又は配位化合物残基含有高分子化合物により黄色から 緑までの!/、ずれかの光が発生し、前記発光化合物から前記黄色から緑色までの色と 実質的補色関係にある色の光が発生するので、この発光層からは混色された結果と しての白色が発光する。 The white light emitting device according to the present invention has a light emitting layer. When the light-emitting layer is a single layer, the light-emitting layer includes a metal-containing coordination compound that develops a color from yellow to green depending on the chemical structure, and a polymer compound containing Z or a coordination compound residue. A light emitting compound that emits light having a color substantially complementary to the color from yellow to green. Within the light-emitting layer, the metal-containing coordination compound and the Z or coordination compound residue-containing polymer compound generate yellow or green light, and some of the light is generated from the light-emitting compound to the yellow to green color. Since light of a color that is substantially complementary to the color is generated, white light is emitted from the light emitting layer as a result of color mixing.
[0045] 白色発光素子は、第 1発光層及び第 2発光層を含有することができる。例えば第 1 発光層には、化学構造に応じて黄色から緑色までの発色をする金属含有配位化合 物及び Z又は配位化合物残基含有高分子化合物が含有され、第 2発光層には前記 黄色力 緑色までの色と実質的補色関係にある色の発光をする発光化合物が含有 される。これら第 1発光層及び第 2発光層にエネルギーを付与すると、第 1発光層より
黄色力 緑色までの 、ずれかの発光が生じ、第 2発光層より前記補色の発光が生じ るから、発光素子全体として白色が発光する。 [0045] The white light emitting element may contain a first light emitting layer and a second light emitting layer. For example, the first light-emitting layer contains a metal-containing coordination compound that develops a color from yellow to green depending on the chemical structure and a polymer compound containing Z or a coordination compound residue, and the second light-emitting layer contains the above-described polymer. Yellow power Contains a light-emitting compound that emits light of a color substantially complementary to colors up to green. When energy is applied to the first light emitting layer and the second light emitting layer, the first light emitting layer Yellow power up to green light is emitted, and the complementary light emission is generated from the second light emitting layer, so that the light emitting element as a whole emits white light.
[0046] 白色の発光は、金属含有配位化合物及び Z又は配位化合物残基含有高分子化 合物から発する色と実質的に補色の関係にある光とを混色すると、混色された色を観 察する目には白色であると認識される。したがって、この発明に係る白色発光素子の 他の例として、金属含有配位化合物及び Z又は配位化合物残基含有高分子化合 物を含有する発光層と、この発光層に、前記発光色と補色の関係にある色を照射す る光源とを有する白色発光素子が挙げられる。この光源としては発光半導体例えば 青色発光半導体等が挙げられる。 [0046] White light emission is obtained by mixing a color emitted from a metal-containing coordination compound and a polymer compound containing Z or a coordination compound residue with light that is substantially in a complementary color relationship. It is recognized as white for the eyes to observe. Therefore, as another example of the white light-emitting device according to the present invention, a light-emitting layer containing a metal-containing coordination compound and Z or a coordination compound residue-containing polymer compound, and the light-emitting layer and the complementary color of the light-emitting color And a white light emitting element having a light source that emits a color having the above relationship. Examples of the light source include a light emitting semiconductor such as a blue light emitting semiconductor.
図面の簡単な説明 Brief Description of Drawings
[0047] [図 1]図 1は、この発明の発光素子の一例を模式的に示す説明図である。 FIG. 1 is an explanatory view schematically showing an example of a light emitting device of the present invention.
[図 2]図 2は、実施例 1における化合物（ 15)の NMR ^ベクトルチャートである。 FIG. 2 is an NMR vector chart of the compound (15) in Example 1.
[図 3]図 3は、実施例 1における化合物（16)の IR ^ベクトルチャートである。 FIG. 3 is an IR ^ vector chart of compound (16) in Example 1.
[図 4]図 4は、実施例 1における化合物（16)の NMR ^ベクトルチャートである。 FIG. 4 is an NMR vector chart of compound (16) in Example 1.
[図 5]図 5は、実施例 1における化合物（ 17)の IR ^ベクトルチャートである。 FIG. 5 is an IR ^ vector chart of the compound (17) in Example 1.
[図 6]図 6は、実施例 1における化合物（ 17)の NMR ^ベクトルチャートである。 FIG. 6 is an NMR vector chart of the compound (17) in Example 1.
[図 7]図 7は、実施例 1における化合物（18)の IR ^ベクトルチャートである。 FIG. 7 is an IR ^ vector chart of the compound (18) in Example 1.
[図 8]図 8は、実施例 1における化合物（18)の NMR ^ベクトルチャートである。 FIG. 8 is an NMR vector chart of the compound (18) in Example 1.
[図 9]図 9は、実施例 2における化合物（22)の IR ^ベクトルチャートである。 FIG. 9 is an IR ^ vector chart of the compound (22) in Example 2.
[図 10]図 10は、実施例 2における化合物（22)の NMR ^ベクトルチャートである。 FIG. 10 is a NMR vector chart of the compound (22) in Example 2.
[図 11]図 11は、実施例 2における化合物（23)の IR ^ベクトルチャートである。 FIG. 11 is an IR ^ vector chart of the compound (23) in Example 2.
[図 12]図 12は、実施例 2における化合物（23)の NMR ^ベクトルチャートである。 FIG. 12 is an NMR vector chart of compound (23) in Example 2.
[図 13]図 13は、実施例 2における化合物（24)の IR ^ベクトルチャートである。 FIG. 13 is an IR ^ vector chart of compound (24) in Example 2.
[図 14]図 14は、実施例 2における化合物（24)の NMR ^ベクトルチャートである。 FIG. 14 is a NMR vector chart of the compound (24) in Example 2.
[図 15]図 15は、実施例 2における化合物（24)の蛍光スペクトルチャートである。 FIG. 15 is a fluorescence spectrum chart of the compound (24) in Example 2.
[図 16]図 16は、実施例 2における化合物（19)の IR ^ベクトルチャートである。 FIG. 16 is an IR ^ vector chart of the compound (19) in Example 2.
[図 17]図 17は、実施例 2における化合物（ 19)の蛍光スペクトルチャートである。 FIG. 17 is a fluorescence spectrum chart of the compound (19) in Example 2.
[図 18]図 18は、実施例 2における化合物（19)の単独重合体の IRスペクトルチャート
である。 FIG. 18 is an IR spectrum chart of the homopolymer of compound (19) in Example 2. It is.
[図 19]図 19は、実施例 2における化合物（19)の単独重合体の蛍光スペクトルチヤ一 トである。 FIG. 19 is a fluorescence spectrum chart of a homopolymer of compound (19) in Example 2.
[図 20]図 20は、実施例 2における化合物（19)と MMAとの共重合体の IR ^ベクトル チャートである。 FIG. 20 is an IR ^ vector chart of a copolymer of compound (19) and MMA in Example 2.
[図 21]図 21は、実施例 3における化合物（25)の蛍光スペクトルチャートである。 FIG. 21 is a fluorescence spectrum chart of the compound (25) in Example 3.
[図 22]図 22は、実施例 4における化合物（26)の蛍光スペクトルチャートである。 FIG. 22 is a fluorescence spectrum chart of the compound (26) in Example 4.
[図 23]図 23は、実施例 5における化合物（27)の蛍光スペクトルチャートである。 FIG. 23 is a fluorescence spectrum chart of the compound (27) in Example 5.
[図 24]図 24は、実施例 6における化合物（28)の蛍光スペクトルチャートである。 FIG. 24 is a fluorescence spectrum chart of the compound (28) in Example 6.
[図 25]図 25は、実施例 7における化合物（29)の蛍光スペクトルチャートである。 FIG. 25 is a fluorescence spectrum chart of the compound (29) in Example 7.
[図 26]図 26は、実施例 8における化合物（30)の蛍光スペクトルチャートである。 FIG. 26 is a fluorescence spectrum chart of the compound (30) in Example 8.
[図 27]図 27は、実施例 2における化合物（19)と N—ビ-ルカルバゾールとの共重合 体の IR ^ベクトルチャートである。 FIG. 27 is an IR ^ vector chart of a copolymer of compound (19) and N-bicarbcarbazole in Example 2.
[図 28]図 28は、実施例 1における化合物（14)の IR ^ベクトルチャートである。 FIG. 28 is an IR ^ vector chart of compound (14) in Example 1.
[図 29]図 29は、実施例 1における化合物（14)の NMR ^ベクトルチャートである。 FIG. 29 is an NMR vector chart of compound (14) in Example 1.
[図 30]図 30は、実施例 1における化合物（14)の蛍光スペクトルチャートである。 FIG. 30 is a fluorescence spectrum chart of the compound (14) in Example 1.
[図 31]図 31は、実施例 9にて採用された発光素子の構造を示す模式図である。 FIG. 31 is a schematic view showing the structure of a light-emitting device employed in Example 9.
[図 32]図 32は、この発明の一例である白色発光素子の構造を模式的に示す説明図 である。 FIG. 32 is an explanatory view schematically showing the structure of a white light emitting element as an example of the present invention.
[図 33]図 33は、この発明の他の例である白色発光素子の構造を模式的に示す説明 図である。 FIG. 33 is an explanatory view schematically showing the structure of a white light emitting device as another example of the present invention.
[図 34]図 34は、この発明のその他の例である白色発光素子の構造を模式的に示す 説明図である。 FIG. 34 is an explanatory view schematically showing a structure of a white light emitting element as another example of the present invention.
[図 35]図 35は、実施例 10で得られた発光層に波長 340nmの励起光を照射すること により生じた発光のスペクトルを示す蛍光スペクトルチャートである。 FIG. 35 is a fluorescence spectrum chart showing a spectrum of light emission generated by irradiating the light emitting layer obtained in Example 10 with excitation light having a wavelength of 340 nm.
[図 36]図 36は、実施例 10で得られた発光層に波長 365nmの励起光を照射すること により生じた発光のスペクトルを示す蛍光スペクトルチャートである。 FIG. 36 is a fluorescence spectrum chart showing a spectrum of light emission generated by irradiating the light emitting layer obtained in Example 10 with excitation light having a wavelength of 365 nm.
[図 37]図 37は、実施例 10で得られた発光層に波長 380nmの励起光を照射すること
により生じた発光のスペクトルを示す蛍光スペクトルチャートである。 [FIG. 37] FIG. 37 shows the case where the light emitting layer obtained in Example 10 is irradiated with excitation light having a wavelength of 380 nm. 5 is a fluorescence spectrum chart showing a spectrum of light emission generated by the above.
[図 38]図 38は、実施例 11で得られた発光層に波長 340nmの励起光を照射すること により生じた発光のスペクトルを示す蛍光スペクトルチャートである。 FIG. 38 is a fluorescence spectrum chart showing a spectrum of light emission generated by irradiating the light emitting layer obtained in Example 11 with excitation light having a wavelength of 340 nm.
[図 39]図 39は、実施例 11で得られた発光層に波長 365nmの励起光を照射すること により生じた発光のスペクトルを示す蛍光スペクトルチャートである。 FIG. 39 is a fluorescence spectrum chart showing a spectrum of light emission generated by irradiating the light emitting layer obtained in Example 11 with excitation light having a wavelength of 365 nm.
[図 40]図 40は、実施例 11で得られた発光層に波長 380nmの励起光を照射すること により生じた発光のスペクトルを示す蛍光スペクトルチャートである。 FIG. 40 is a fluorescence spectrum chart showing a spectrum of light emission generated by irradiating the light emitting layer obtained in Example 11 with excitation light having a wavelength of 380 nm.
[図 41]図 41は、実施例 12で得られた発光層に波長 340nmの励起光を照射すること により生じた発光のスペクトルを示す蛍光スペクトルチャートである。 FIG. 41 is a fluorescence spectrum chart showing a spectrum of light emission generated by irradiating the light emitting layer obtained in Example 12 with excitation light having a wavelength of 340 nm.
[図 42]図 42は、実施例 12で得られた発光層に波長 365nmの励起光を照射すること により生じた発光のスペクトルを示す蛍光スペクトルチャートである。 FIG. 42 is a fluorescence spectrum chart showing a spectrum of light emission generated by irradiating the light emitting layer obtained in Example 12 with excitation light having a wavelength of 365 nm.
[図 43]図 43は、実施例 12で得られた発光層に波長 380nmの励起光を照射すること により生じた発光のスペクトルを示す蛍光スペクトルチャートである。 FIG. 43 is a fluorescence spectrum chart showing the spectrum of light emission generated by irradiating the light emitting layer obtained in Example 12 with excitation light having a wavelength of 380 nm.
[図 44]図 44は、実施例 13で得られた発光層に波長 365nmの励起光を照射すること により生じた発光のスペクトルを示す蛍光スペクトルチャートである。 FIG. 44 is a fluorescence spectrum chart showing a spectrum of light emission generated by irradiating the light emitting layer obtained in Example 13 with excitation light having a wavelength of 365 nm.
符号の説明 Explanation of symbols
1 発光素子 1 Light emitting element
2 透明基板 2 Transparent substrate
3 陽極 3 Anode
4 正孔注入層 4 Hole injection layer
5 正孔輸送層 5 Hole transport layer
6 発光層 6 Light emitting layer
7 電子輸送層 7 Electron transport layer
8 電子注入層 8 Electron injection layer
9 陰極 9 Cathode
10 発光素子 10 Light emitting element
12 基板 12 Board
13 ITO透明電極層
14 ホール輸送層 13 ITO transparent electrode layer 14 Hole transport layer
15 発光層 15 Light emitting layer
16 カルシウム電極層 16 Calcium electrode layer
17 銀電極層 17 Silver electrode layer
18 陽極 18 Anode
19 発光層 19 Light emitting layer
19a 第 1発光層 19a First light emitting layer
19b 第 2発光層 19b Second light emitting layer
20 陰極 20 cathode
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
[0049] 1. (8—ヒドロキシキノレート）系金属配位化合物 [0049] 1. (8-Hydroxyquinolate) metal coordination compounds
この発明の最良の形態につき、式（1)で示される金属含有配位ィ匕合物の一例とし て（8—ヒドロキシキノレート）系金属配位ィ匕合物を挙げて説明する。 The best mode of the present invention will be described by taking an (8-hydroxyquinolate) -based metal coordination compound as an example of the metal-containing coordination compound represented by the formula (1).
[0050] (8—ヒドロキシキノレート）系金属配位ィ匕合物は式（11)で示すことができる。 [0050] The (8-hydroxyquinolate) -based metal coordination compound can be represented by the formula (11).
[0051] [化 12] [0051] [Chemical 12]
[0052] ただし、前記式（11)において、 Yは、以下の式（2)〜（5)で表されるいずれかの基 である,
[0053] [化 13] [0052] However, in the formula (11), Y is any group represented by the following formulas (2) to (5), [0053] [Chemical 13]
[0054] [化 14] [0054] [Chemical 14]
(3) (3)
[0055] [化 15] [0055] [Chemical 15]
R
R
(4) (Four)
ただし、前記式 (4)において、 R1は、水素原子又はメチル基である。 However, in the formula (4), R 1 is a hydrogen atom or a methyl group.
[0057] [化 16]
[0057] [Chemical 16]
[0058] ただし、前記式（5)において、 R2は、炭素数 1〜20のアルキル基である。 [0058] However, in the above formula (5), R 2 is an alkyl group having 1 to 20 carbon atoms.
[0059] 前記 R2として、具体的には、メチル基、ェチル基、プロピル基、イソプロピル基、 n— ブチル基、イソブチル基、 sec—ブチル基、 tert—ブチル基、 n_ペンチル基、 sec-ペン チル基、 tert-ペンチル基、へキシル基、ヘプチル基、ォクチル基、ノニル基、デシル 基、ゥンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、へキ サデシル基、ヘプタデシル基、ォクタデシル基、ノナデシル基、及びエイコシル基等 を挙げることができる。これらアルキル基の中でも、炭素数 1〜10のアルキル基が好 ましぐ特に、炭素数 1〜5のアルキル基が好ましい。 R2における炭素数が多いほど 炭化水素系有機溶媒に溶解しやすくなるが逆に炭素数が多くなると立体障害を起こ す。 [0059] Specific examples of R 2 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n_pentyl group, sec- Pentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl , Nonadecyl group, and eicosyl group. Among these alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is particularly preferable. Becomes more soluble in a hydrocarbon-based organic solvents larger the number of carbon atoms in R 2 becomes more carbon atoms reversed to Oko steric hindrance.
[0060] 前記式（11)において、 Mは、 1988年の IUPACによる周期律表における遷移金 属及び典型元素である。好適な Mは、第 2族、第 7族、第 12族及び第 13族に属する 金属であり、更に好適な Mは、 Mg、 Zn、 Al、 Ga、 In、及び Mn等である。 [0060] In the above formula (11), M is a transition metal and a typical element in the 1988 IUPAC periodic table. Preferred M is a metal belonging to Group 2, Group 7, Group 12, and Group 13, and more preferred M is Mg, Zn, Al, Ga, In, Mn, and the like.
[0061] 前記式（11)において、 nは、 Mで示される金属の価数から 1を引いた数である。例 えば中心金属が A1であるときには、 nは 2である。 In the above formula (11), n is a number obtained by subtracting 1 from the valence of the metal represented by M. For example, n is 2 when the central metal is A1.
[0062] Z1は、水素原子又は式（12)で示される基である。 Z 1 is a hydrogen atom or a group represented by the formula (12).
[0063] [化 17]
[0063] [Chemical 17]
[0064] 但し、 R5はアルキル基であり、好ましくは炭素数 1〜20、特に好ましくは炭素数 1〜 10のアルキル基である。 [0064] However, R 5 is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms.
[0065] 前記式（11)で示される（8—ヒドロキシキノレート）系金属配位ィ匕合物は、配位子及 び金属の種類にもよる力 500〜550nmにピークを有する蛍光を発する蛍光性化合 物である。この蛍光特性は、ォキサジァゾール環に結合するところの、金属及びその 配位子からなる配位化合物の構造と、ォキサジァゾール環に由来する電子吸引性と 、基 Y、特に力ルバゾール基の光導電特性とに基づくものと、考えられる。 [0065] The (8-hydroxyquinolate) -based metal coordination compound represented by the formula (11) emits fluorescence having a peak at a force of 500 to 550 nm depending on the type of ligand and metal. It is a fluorescent compound. This fluorescence property is based on the structure of the coordination compound consisting of a metal and its ligand, which is bonded to the oxaziazole ring, the electron withdrawing property derived from the oxaziazole ring, and the photoconductive property of the group Y, particularly the force rubazole group. It is thought that it is based on.
[0066] 前記式（11)で示される（8—ヒドロキシキノレート）系金属配位ィ匕合物のうち、 Υが式 [0066] Among the (8-hydroxyquinolate) -based metal coordination compounds represented by the formula (11),
(2)、 (3)又は (4)で示される置換基である（8—ヒドロキシキノレート)系金属配位ィ匕 合物 (Α)は、分子内に重合性二重結合を有するので、重合体にすることができる。 Since the (8-hydroxyquinolate) -based metal coordination compound (Α) which is a substituent represented by (2), (3) or (4) has a polymerizable double bond in the molecule, It can be a polymer.
[0067] また前記式（11)で示される（8—ヒドロキシキノレート）系金属配位ィ匕合物のうち、 Υ が式（5)で示される置換基である（8—ヒドロキシキノレート）系金属配位ィ匕合物（Β)は 、 R2なるアルキル基を有するので溶媒に対する溶解性が良好である。したがって、（8 ーヒドロキシキノレート）系金属配位ィ匕合物（Β)は、重合性を有していないが、溶媒に 溶解してフィルムを形成するキャスト法等を採用することにより、またはポリビュルカル バゾール等の高分子化合物と混合することにより高分子加工技術の手法等を採用す ることにより、有機 EL素子等の発光素子における発光層、電荷輸送層、及びホール
輸送層等を好適に形成することのできる有機エレクト口ルミネッセンス材である。 [0067] Of the (8-hydroxyquinolate) -based metal coordination compounds represented by the above formula (11), あ る is a substituent represented by the formula (5) (8-hydroxyquinolate) Since the metal-based metal coordination compound (Β) has an alkyl group of R 2 , the solubility in a solvent is good. Therefore, the (8-hydroxyquinolate) -based metal coordination compound (Β) does not have polymerizability, but by adopting a casting method or the like that dissolves in a solvent to form a film, or By adopting polymer processing techniques by mixing with polymer compounds such as polybulcarbazole, the light emitting layer, charge transport layer, and hole in light emitting devices such as organic EL devices are used. It is an organic electoluminescence material that can suitably form a transport layer and the like.
[0068] 式（11)で示される（8—ヒドロキシキノレート）系金属配位ィ匕合物は、例えば以下の ようにして製造することができる。 [0068] The (8-hydroxyquinolate) -based metal coordination compound represented by the formula (11) can be produced, for example, as follows.
[0069] すなわち、 8—ヒドロキシキノリン (反応式（2)における（a) )に一 COOR4を導入する 。但し、 R4は前記と同様の意味を示す。— COOR4で示す基の導入は、フリーデルク ラフッ反応を利用してベンゼン環上にァシル基を導入してこれを酸化する方法、及 びカルベンの生成を利用してベンゼン環上にカルボ-ル基を導入してこれを酸化す る方法等を利用することにより可能である。カルボン酸又はカルボン酸エステル基が 導入された化合物 (反応式 (2)における (b) )とヒドラジンとを反応させてカルボヒドラ ジド誘導体 (反応式（2)における（c) )に誘導する。一方、式（11)における基 Yを与え るベンゼン環含有の Y前駆体 (反応式（2)における化合物（d) )におけるベンゼン環 上に酸クロライド基を導入して酸クロライド化合物 (反応式 (2)における化合物 (e) )を 得る。前記カルボヒドラジド誘導体と酸クロライドィ匕合物とを反応させてジカルボヒドラ ジド誘導体 (反応式（2)における（f) )を加熱することにより閉環してォキサジァゾール 環化合物 (反応式（2)における (g) )を得る。このォキサジァゾール環化合物と金属 M と 8—ヒドロキシキノリン誘導体とを反応させると、式（11)で示される目的化合物を得 ることがでさる。 That is, one COOR 4 is introduced into 8-hydroxyquinoline ((a) in the reaction formula (2)). R 4 has the same meaning as described above. — Introduction of the group shown by COOR 4 is based on a method of introducing an acyl group on the benzene ring using the Friedel-Craft reaction and oxidizing it, and a carbene group on the benzene ring using carbene formation. This is possible by using a method of introducing and oxidizing this. The compound in which the carboxylic acid or carboxylic acid ester group is introduced ((b) in the reaction formula (2)) is reacted with hydrazine to derive a carbohydrazide derivative ((c) in the reaction formula (2)). On the other hand, by introducing an acid chloride group onto the benzene ring in the benzene ring-containing Y precursor (compound (d) in the reaction formula (2)) that gives the group Y in the formula (11), an acid chloride compound (reaction formula ( Compound (e)) in 2) is obtained. The carbohydrazide derivative and the acid chloride compound are reacted to heat the dicarbohydrazide derivative ((f) in the reaction formula (2)) to form a oxaziazole ring compound ((g) in the reaction formula (2)). ) When this oxaziazole ring compound, metal M and an 8-hydroxyquinoline derivative are reacted, the target compound represented by the formula (11) can be obtained.
[0070] [化 18]
[0070] [Chemical 18]
反応式 (2) Reaction formula (2)
[0071] 2. (8—ヒドロキシキノレート)系金属配位ィ匕合物含有高分子化合物 [0071] 2. (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound
この発明に係る配位化合物残基含有高分子化合物にっき、その好適な形態として (8—ヒドロキシキノレート）系金属配位ィ匕合物含有高分子化合物を例に挙げて説明 する。 The coordination compound residue-containing polymer compound according to the present invention will be described taking a (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound as an example of its preferred form.
[0072] この（8—ヒドロキシキノレート）系金属配位ィ匕合物含有高分子化合物は、式（13)で 示す繰り返し単位を有する。 [0072] This (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound has a repeating unit represented by the formula (13).
[0073] [化 19]
[0073] [Chemical 19]
[0074] ただし、式（13)において、 M、 R Z、 Z1及び nは前記と同様の意味を示す。 [0074] However, in the formula (13), M, RZ, Z 1 and n have the same meaning as described above.
[0075] (8—ヒドロキシキノレート）系金属配位ィ匕合物含有高分子化合物は、式（13)で示 す繰り返し単位を有するホモポリマーであってもよぐまた他の繰り返し単位を有する コポリマーであっても良い。前記他の繰り返し単位と成るモノマーとしては、 N—ビ- ルカルバゾール、メチルメタタリレート、アタリレート、及びスチレン等を挙げることがで きる。 [0075] The (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound may be a homopolymer having a repeating unit represented by formula (13) or may have another repeating unit. It may be a copolymer. Examples of the other monomer as the repeating unit include N-vinylcarbazole, methyl methacrylate, acrylate, and styrene.
[0076] (8—ヒドロキシキノレート）系金属配位化合物含有高分子化合物の数平均分子量 は、通常 500〜500000である。 [0076] The number average molecular weight of the (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound is usually 500 to 500,000.
[0077] (8—ヒドロキシキノレート）系金属配位ィ匕合物含有高分子化合物は、基 Yが式 (2)、 [0077] (8-Hydroxyquinolate) -based metal coordination compound-containing polymer compound has a group Y represented by the formula (2),
(3)及び (4)の ヽずれかで示される基である場合に、その基 Y中に存在する二重結 合を重合させること〖こより得ることができる。重合は単独重合であっても共重合であつ ても良い。重合反応は、ラジカル重合、ァ-オン重合及びカチオン重合のいずれで
あっても良い。また、重合形式としては、塊状重合法、懸濁重合法、乳化重合法及び 溶液重合法の 、ずれであってもよ!ヽが、溶液重合法が好ま ヽ。 In the case of a group represented by any one of (3) and (4), it can be obtained by polymerizing a double bond present in the group Y. The polymerization may be homopolymerization or copolymerization. The polymerization reaction is any of radical polymerization, ion polymerization, and cationic polymerization. There may be. The polymerization method may be any of bulk polymerization method, suspension polymerization method, emulsion polymerization method and solution polymerization method, but the solution polymerization method is preferred.
[0078] 前記重合反応は、常圧下で実施しても、減圧下または圧力下で実施してもよいが、 通常は常圧下で実施される。重合プロセスは、回分式プロセスであっても、連続式プ ロセスであってもよ 、が、製造効率の観点力 連続式プロセスが好まし 、。 [0078] The polymerization reaction may be carried out under normal pressure, or under reduced pressure or under pressure, but is usually carried out under normal pressure. The polymerization process may be a batch process or a continuous process, but the power of manufacturing efficiency is preferred.
[0079] この発明における前記 (8—ヒドロキシキノレート）系金属配位ィ匕合物含有高分子化 合物は、以下の式 (X)で示される配位化合物 (X)と混合して使用されることができる 。また、前記配位化合物 (X)は、その分子内の置換基等を選択することによりそれ自 体で発光層、電子輸送層又はホール輸送層に用いることができる。なお、式 (X)中 の R5はアルキル基を示し、 M及び nは前記と同様の意味を示す。 [0079] In the present invention, the (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound is used by mixing with a coordination compound (X) represented by the following formula (X) Can be done. In addition, the coordination compound (X) can be used for a light emitting layer, an electron transport layer, or a hole transport layer by selecting a substituent in the molecule. In the formula (X), R5 represents an alkyl group, and M and n have the same meaning as described above.
[0080] [化 20]
[0080] [Chemical 20]
[0081] 3.有機エレクト口ルミネッセンス材 [0081] 3.Organic-elect luminescence material
この発明の有機エレクト口ルミネッセンス材の好適な形態として、前記式（11)で示さ れる低分子の（8—ヒドロキシキノレート）系金属配位化合物及び式（ 13)で示される ( 8—ヒドロキシキノレート）系金属配位ィ匕合物含有高分子化合物を挙げることができる As a preferred form of the organic electoluminescence material of the present invention, a low molecular (8-hydroxyquinolate) -based metal coordination compound represented by the above formula (11) and a compound represented by the following formula (13) (8-hydroxyquino) Rate) -based metal coordination compounds containing polymer compounds
[0082] これら有機エレクト口ルミネッセンス材は、発光素子における発光層、電子輸送層及 び正孔輸送層等を形成する材料として好適である。 [0082] These organic electoluminescence materials are suitable as materials for forming a light emitting layer, an electron transport layer, a hole transport layer, and the like in a light emitting device.
[0083] また、この発明の有機エレクト口ルミネッセンス材の好適な形態としては、前記式（1 1)で示される低分子の（8—ヒドロキシキノレート）系金属配位化合物及び Z又は前 記式（12)で示される（8—ヒドロキシキノレート）系金属配位ィ匕合物含有高分子化合
物と、前記式（11)で示される低分子の（8 ヒドロキシキノレート）系金属配位ィ匕合物 及び Z又は前記式（ 12)で示される (8 ヒドロキシキノレート）系金属配位化合物含 有高分子化合物により発せられる色と実質的に補色の関係にある色を発光させる発 光化合物とからなる白色有機エレクト口ルミネッセンス材を挙げることができる。 [0083] Further, as a preferable form of the organic electoluminescence material of the present invention, a low molecular (8-hydroxyquinolate) -based metal coordination compound represented by the formula (11) and Z or the above formula (8) (8-Hydroxyquinolate) -based metal coordination compounds containing polymer compounds And a low molecular (8 hydroxyquinolate) -based metal coordination compound represented by the formula (11) and Z or (8 hydroxyquinolate) -based metal coordination compound represented by the formula (12) A white organic electoluminescent material comprising a light emitting compound that emits a color that is substantially complementary to the color emitted by the containing polymer compound can be mentioned.
[0084] 前記実質的に補色の関係にある色を発光させる発光化合物として、前記式（11)で 示される低分子の（8—ヒドロキシキノレート）系金属配位化合物及び Z又は前記式（ 12)で示される（8 ヒドロキシキノレート）系金属配位化合物含有高分子化合物によ り発せられる色に応じて適宜に選択される。 [0084] As the light emitting compound that emits light having a substantially complementary color, the low molecular (8-hydroxyquinolate) -based metal coordination compound represented by the formula (11) and Z or the formula (12 ) Is appropriately selected according to the color emitted by the polymer compound containing a (8 hydroxyquinolate) -based metal coordination compound.
[0085] 前記発光化合物として、例えば青色発光化合物、赤色発光化合物等を挙げること ができる。 [0085] Examples of the light emitting compound include a blue light emitting compound and a red light emitting compound.
[0086] 前記実質的に補色の関係にある色を発光させる発光化合物として、例えば、特開 2 As the light emitting compound that emits light having a substantially complementary color, for example, JP-A 2
003— 277371の公報に記載の下記式（1)で示されるナイルレッド系化合物、 003-277371, Nile red compound represented by the following formula (1),
[0087] [化 21] [0087] [Chemical 21]
R R
[0088] 特開 2003— 277369の公報に記載の下記式（1)で示されるナイルレッド系化合物 [0088] Nile red compounds represented by the following formula (1) described in JP-A-2003-277369
[0089] [化 22]
[0089] [Chemical 22]
Ar Ar
[0090] 特開 2004— 18400の公報に記載の下記式（ 1 )で示されるナイルレッド系化合物、 [0091] [化 23] [0090] Nile red compounds represented by the following formula (1) described in JP-A-2004-18400, [0091]
[0092] 特開 2002— 114773の公報に記載の下記式（1)で示されるクマリン系赤色発光化 合物、並びに公知のナイルレッド等を挙げることができる。 [0092] Examples thereof include a coumarin red light emitting compound represented by the following formula (1) described in JP-A-2002-114773, and known Nile red.
[0093] [化 24] [0093] [Chemical 24]
5447の公報に記載の下記式（1)で示される青色発光化合物、及び A blue light-emitting compound represented by the following formula (1) described in publication 5447, and
[0095] [化 25] [0095] [Chemical 25]
[0096] 特開 2004— 18401の公報に記載の下記式（ 1 )で示される青色発光化合物等を 挙げることができる。 Examples include a blue light-emitting compound represented by the following formula (1) described in JP-A-2004-18401.
[0097] [化 26] [0097] [Chemical 26]
* — ( 1 ) c T ^ Ή ^ * — (1) c T ^ Ή ^
[0098] 前記青色発光化合物の外に、ジスチリルビフエニル系青色発光材、ジメシチルボリ ル基結合アモルファス発光材（「!¾¾^6 Preprints, Japan」 Vol. 48 No. 9 発行年： 1999)、ジピリリルジシァノベンゼン発光材（Synthetic Metals」 Vol. 102 発行年： 19 99)、ジビユルフェ-ル結合トリフエ-レン系発光材（ Synthetic MetalsJ Vol. 111-11 2 441頁〜 443頁 発行年： 2000 Elsevier Science発行 Title： Synthesis of 1,4- divin ylpnenyト bridged triphenylenes and application in OLEDs 著者： Roland Freudenma nn; Boris Behnisch; Frank Lange; Michael Hanack)、 (カノレノ ゾーノレ一シァノテレフタ リデン）系発光材（「Thin Solid FilmsJ Vol. 363 発行年： 2000)、ァリールェチュルべ ンゼン系青色蛍光発光材（「第 61回応用物理学会学術講演会講演予稿集」 9月号 発行年： 2000)、ォキサジァゾ一ルーベリリウム青色発光錯体（「Advanced Materials 」 Vol. 11 No. 17 1460頁〜 1463頁 発行年： 1999 Advanced Materials発行 Title ： A Newし lass of Blue-Emitting Materials Based on 1, «3, 5— Oxadiazole Metalし helate Compounds for Electroluminescent Devices 著者： Nan-Xing Hu; Mohammad Estegh
amatian; Shuang Xie; Zoran Popovic; Ah- Mee Hor; Beng Ong; Suning Wang)等を挙 げることができる。 [0098] In addition to the blue light-emitting compound, distyrylbiphenyl blue light-emitting material, dimesitylbolyl group-bonded amorphous light-emitting material ("! ¾¾ ^ 6 Preprints, Japan" Vol. 48 No. 9 Publication year: 1999), Pyrylyl dicyanbenzene luminescent material (Synthetic Metals) Vol. 102 Publication year: 19 99), di-biurel-bonded triphenylene-based luminescent material (Synthetic MetalsJ Vol. 111-11 2 pp. 441-443 publication year: 2000 Elsevier Science title: Synthesis of 1,4-divin ylpneny bridged triphenylenes and application in OLEDs Authors: Roland Freudenma nn; Boris Behnisch; Frank Lange; Michael Hanack) Vol. 363 Publication year: 2000), allylechurchbensen blue fluorescent material (September issue of the 61st Japan Society of Applied Physics, Proceedings) September issue year: 2000), Oxaziazo rubellium blue luminescent complex “Advanced Materials” Vol. 11 No. 17 1460-1463 Publication year: 1999 Advanced Materials Published Title: A New lass of Blue-Emitting Materials Based on 1, «3, 5— Oxadiazole Metal and helate Compounds for Electroluminescent Devices Author: Nan-Xing Hu; Mohammad Estegh amatian; Shuang Xie; Zoran Popovic; Ah-Mee Hor; Beng Ong; Suning Wang).
[0099] 前記赤色発光化合物のほかに、ジスチリル系赤色発光材（「第 60回応用物理学会 学術講演会講演予稿集」 9月号 3p— N— 18頁 発行年 : 1999 (社)応用物理学 会発行 Title：ジスチリル誘導体有機 EL赤色発光材料の検討 (2) )、ペリレン系赤色 発光材（「丁11 Solid Films」 Vol. 372 163頁〜 168頁 発行年： 2000 Elsevier Scien ce発行 fitle： The influence molecular aggregation on the device properties of organ ic light emitting diodes 著者： P.Schouwink; A.H.Schafer; C.beidel; H.Fuchs)等を举 げることができる。 [0099] In addition to the red light-emitting compounds, distyryl red light-emitting materials ("Proceedings of the 60th Annual Conference of the Japan Society of Applied Physics" Sep. 3p— N— Page 18 Publication year: 1999 Applied physics Published by Title: Examination of distyryl derivative organic EL red light emitting material (2)), perylene red light emitting material ("Cho 11 Solid Films" Vol. 372 pages 163-168 Publication year: 2000 Issued by Elsevier Scien ce fitle: The influence Authors: P.Schouwink; AHSchafer; C.beidel; H.Fuchs) etc.
[0100] また、前記式（11)で示される低分子の（8 ヒドロキシキノレート）系金属配位ィ匕合 物及び Z又は前記式（ 12)で示される (8 ヒドロキシキノレート）系金属配位ィ匕合物 含有高分子化合物と共に用いるのに好適な発光化合物として、アントラセン、メチル アントラセン、ナフタリン、フエナントレン、ピレン、タリセン、ペリレン、ブタジエン誘導 体、クマリン、アタリジン、スチルベン誘導体等の芳香族系発光化合物を挙げることが できる。この芳香族系発光化合物は入手が容易であるばかりか、前記式（11)で示さ れる低分子の（8 ヒドロキシキノレート）系金属配位化合物及び Z又は前記式（12) で示される（8—ヒドロキシキノレート)系金属配位化合物含有高分子化合物と組み合 わせることにより、輝度の大きな白色発光が可能な有機エレクト口ルミネッセンス材を 構成する。 [0100] Further, the low molecular (8 hydroxyquinolate) -based metal coordination compound represented by the above formula (11) and Z or the (8 hydroxyquinolate) based metal coordination represented by the above formula (12). As light emitting compounds suitable for use with polymer compounds containing coordinate compounds, aromatic light emission such as anthracene, methyl anthracene, naphthalene, phenanthrene, pyrene, taricene, perylene, butadiene derivatives, coumarin, atalidine, stilbene derivatives, etc. Compounds can be mentioned. This aromatic light-emitting compound is not only easily available, but also has a low molecular (8 hydroxyquinolate) -based metal coordination compound represented by the formula (11) and Z or the formula (12) (8) By combining with a polymer compound containing a (hydroxyquinolate) -based metal coordination compound, an organic electoluminescence material capable of emitting white light with high luminance is formed.
[0101] 前記低分子の（8 ヒドロキシキノレート）系金属配位ィ匕合物又は前記（8 ヒドロキ シキノレート）系金属配位化合物含有高分子化合物と前記発光化合物との組合せ態 様を発光層の形成を例として説明すると、前記低分子の（8—ヒドロキシキノレート)系 金属配位ィ匕合物又は前記 (8—ヒドロキシキノレート)系金属配位ィ匕合物含有高分子 化合物から形成された発光層と前記発光化合物から形成された発光層との二層から 成る発光層を挙げることがでさる。 [0101] The low-molecular (8 hydroxyquinolate) -based metal coordination compound or the (8 hydroxyquinolate) -based metal coordination compound-containing polymer compound and the light-emitting compound are combined in a light-emitting layer. The formation will be described as an example. The low molecular (8-hydroxyquinolate) -based metal coordination compound or the (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound is used. And a light emitting layer composed of two layers of a light emitting layer formed from the light emitting compound.
[0102] また、前記組合せ態様としては、前記低分子の（8 ヒドロキシキノレート）系金属配 位ィ匕合物又は前記 (8—ヒドロキシキノレート)系金属配位ィヒ合物含有高分子化合物 と前記青色発光化合物又は前記赤色発光化合物との混合物からから形成された発
光層などを挙げることができる。前記低分子の（8—ヒドロキシキノレート）系金属配位 化合物又は前記（8—ヒドロキシキノレート）系金属配位化合物含有高分子化合物と 前記青色発光化合物又は前記赤色発光化合物との前記混合物における混合重量 比が 1 (前者） : 0. 1 (後者)〜 1 : 10となるように、前記両者を機械的、物理的手段に よって混合するの力 良い。 [0102] In addition, as the combination mode, the low molecular (8 hydroxyquinolate) -based metal coordination compound or the (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound Formed from a mixture of the blue light-emitting compound and the red light-emitting compound. An optical layer etc. can be mentioned. Mixing of the low molecular (8-hydroxyquinolate) metal coordination compound or the polymer compound containing the (8-hydroxyquinolate) metal coordination compound and the blue light emitting compound or the red light emitting compound in the mixture It is good to mix the two by mechanical and physical means so that the weight ratio is 1 (the former): 0.1 (the latter) to 1:10.
[0103] さらに、前記低分子の（8—ヒドロキシキノレート）系金属配位化合物又は前記（8— ヒドロキシキノレート）系金属配位化合物含有高分子化合物から形成された発光層に 、低分子の（8—ヒドロキシキノレート）系金属配位ィ匕合物又は前記（8—ヒドロキシキノ レート)系金属配位ィ匕合物含有高分子化合物力 発せられる光の色と実質的に補色 となる色を発光する発光光源から実質的に補色となる光例えば青色を照射して、白 色を発光させることちできる。 [0103] Further, a low molecular weight (8-hydroxyquinolate) -based metal coordination compound or a light-emitting layer formed from the (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound has a low molecular weight (8-Hydroxyquinolate) -based metal coordination compound or the above-mentioned (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound color which is substantially complementary to the color of light emitted It is possible to emit white light by irradiating light of substantially complementary color, for example, blue light from a light emitting light source that emits light.
[0104] 前記低分子の（8—ヒドロキシキノレート）系金属配位ィ匕合物又は前記（8—ヒドロキ シキノレート）系金属配位化合物含有高分子化合物と前記青色発光化合物との組合 せにおいて、前記発光化合物に代えて、低分子の（8—ヒドロキシキノレート）系金属 配位ィ匕合物又は前記 (8—ヒドロキシキノレート)系金属配位ィ匕合物含有高分子化合 物から発せられる光の色と実質的に補色となる色を発光する無機発光化合物例えば 無機青色発光化合物を用いることができる。 [0104] In the combination of the low molecular (8-hydroxyquinolate) -based metal coordination compound or the (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound and the blue light-emitting compound, Instead of the light-emitting compound, it is emitted from a low molecular (8-hydroxyquinolate) -based metal coordination compound or a polymer compound containing the (8-hydroxyquinolate) -based metal coordination compound. An inorganic light emitting compound that emits a color that is substantially complementary to the color of light, such as an inorganic blue light emitting compound, can be used.
4.発光素子 4.Light emitting element
この発明に係る発光素子の最良の形態においては、前記有機エレクト口ルミネッセ ンス材により形成された発光層、電子輸送層又は正孔輸送層を有して成る素子であ る。 The best mode of the light emitting device according to the present invention is a device having a light emitting layer, an electron transport layer or a hole transport layer formed of the organic electoric luminescence material.
[0105] この発明の発光素子は、発光層、電子輸送層又は正孔輸送層が、前記有機エレク トロルミネッセンス材により形成されていて、この有機エレクト口ルミネッセンス材は、前 記溶媒に対する溶解性又は前記有機高分子物質との相溶性に優れた前記 (8—ヒド 口キシキノレート）系金属配位ィ匕合物及び Z又は前記（8—ヒドロキシキノレート）系金 属配位化合物含有高分子化合物から成って ヽることから、容易にフィルムに成形す ることができ、蒸着法を採用することなぐ簡便に発光層、電子輸送層又は正孔輸送 層を形成することができる。し力も、この発明の発光素子は、発光特性の良好な 8—ヒ
ドロキシキノレート）系金属配位化合物及び Z又は前記（8—ヒドロキシキノレート）系 金属配位化合物含有高分子化合物を含む発光層、電子輸送層又は正孔輸送層を 有しているため、発光輝度が高ぐ耐久性が良好すなわち堅牢である。 [0105] In the light-emitting device of the present invention, the light-emitting layer, the electron transport layer, or the hole transport layer is formed of the organic electroluminescent material, and the organic electroluminescent material is soluble or soluble in the solvent. From the above-mentioned (8-hydroxyquinolate) -based metal coordination compound and Z or (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound having excellent compatibility with the organic polymer substance Thus, the light emitting layer, the electron transport layer, or the hole transport layer can be easily formed without employing a vapor deposition method. However, the light emitting device of the present invention has an excellent light emission characteristic. Since it has a light emitting layer, an electron transport layer or a hole transport layer containing a droxyquinolate) -based metal coordination compound and Z or the above-mentioned (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound, Durability with high emission brightness is good, that is, it is robust.
[0106] この発明の発光素子を、図面に基づいて説明する。図 1は、この発明の発光素子の 一例を模式的に示す断面である。 The light emitting device of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing an example of the light emitting device of the present invention.
[0107] 発光素子 1は、透明基板 2、陽極 3、正孔注入層 4、正孔輸送層 5、発光層 6、電子 輸送層 7、電子注入層 8および陰極 9が、その順に積層されて成っている。 [0107] The light-emitting element 1 includes a transparent substrate 2, an anode 3, a hole injection layer 4, a hole transport layer 5, a light-emitting layer 6, an electron transport layer 7, an electron injection layer 8, and a cathode 9 stacked in that order. It is made up.
[0108] 発光素子 1を構成する各層は、透明基板 2上に形成され、この透明基板 2としては、 例えば、ガラス基板、プラスチック基板、シリコン基板等を挙げることができる。 [0108] Each layer constituting the light emitting element 1 is formed on the transparent substrate 2, and examples of the transparent substrate 2 include a glass substrate, a plastic substrate, and a silicon substrate.
[0109] 前記陽極 3としては、仕事関数が大きぐ透明である限り、種々の材料を採用するこ とができる。例えば、インジウムチンオキサイド (ITO)、 In O、 SnO、 ZnO、 CdOなど [0109] As the anode 3, various materials can be adopted as long as the work function is large and transparent. For example, indium tin oxide (ITO), In O, SnO, ZnO, CdO, etc.
2 3 2 2 3 2
、またはポリア-リンなどの導電性高分子材料などにより形成することができる。この 陽極 3の厚さの不均一は、発光層の膜圧に影響を与えるため、平滑性が要求される Or a conductive polymer material such as polyaline. This non-uniform thickness of anode 3 affects the film pressure of the light emitting layer, so smoothness is required.
[0110] この陽極 3は、前記透明基板 2上に、化学気相成長法、スプレーパイロリシス、真空 蒸着法、電子ビーム蒸着法、スパッタ法、イオンビームスパッタ法、イオンプレーティ ング法、イオンアシスト蒸着法等の方法により形成することができる。 [0110] The anode 3 is formed on the transparent substrate 2 by chemical vapor deposition, spray pyrolysis, vacuum deposition, electron beam deposition, sputtering, ion beam sputtering, ion plating, ion assist. It can be formed by a method such as vapor deposition.
[0111] 前記正孔注入層 4としては、トリフエニルァミン系化合物、例えば、 N, Ν'—ジフエ- ル一 Ν, Ν'—ジ（m—トリル）一ベンジジン（TPD)、 （α— NPD)など、ヒドラゾン系ィ匕 合物、スチルベンビス〔Ν—（1 ナフチル) Ν フエ-ル〕ベンジジンン系化合物等 のスチルベン系化合物、複素環系化合物、 π電子系スターバースト正孔輸送物質な ど力 形成される層を挙げることができる。 [0111] The hole injection layer 4 includes a triphenylamine compound such as N, Ν'-diphenyl Ν, Ν'-di (m-tolyl) monobenzidine (TPD), (α- Hydrazone compounds such as NPD), stilbene compounds such as stilbenbis [Ν- (1 naphthyl)) phenol] benzidine compounds, heterocyclic compounds, π-electron starburst hole transport materials, etc. The layer to be formed can be mentioned.
[0112] 発光素子 1においては、前記正孔輸送層 5が、前記（8 ヒドロキシキノレート）系金 属配位化合物及び Ζ又は前記（8—ヒドロキシキノレート）系金属配位化合物含有高 分子化合物によって形成されている。この正孔輸送層 5は、蒸着法によることなぐ例 えば、スピンキャスト法、コート法又はディップ法等により形成することができる。 [0112] In the light-emitting device 1, the hole transport layer 5 includes the (8 hydroxyquinolate) -based metal coordination compound and the Ζ or (8-hydroxyquinolate) -based metal coordination compound-containing high molecular compound. Is formed by. The hole transport layer 5 can be formed by, for example, a spin casting method, a coating method, a dip method, or the like, by an evaporation method.
[0113] 前記発光層 6は、発光化合物を含有する層であり、発光化合物としては、赤色、青 色または白色発光化合物などを挙げることができる。この発光層 6は、蒸着法、塗布
法、例えば、スピンキャスト法、コート法またはディップ法などにより形成することがで きる。この発光層 6は発光特性に応じた蛍光発光化合物を含有することができ、また 、この発明にける（8—ヒドロキシキノレート）系金属配位ィ匕合物及び Z又は前記（8— ヒドロキシキノレート）系金属配位ィ匕合物含有高分子化合物を含有することもできる。 [0113] The light-emitting layer 6 is a layer containing a light-emitting compound, and examples of the light-emitting compound include red, blue, and white light-emitting compounds. This light emitting layer 6 is formed by vapor deposition or coating. It can be formed by a method such as spin casting, coating or dipping. The light-emitting layer 6 can contain a fluorescent light-emitting compound corresponding to the light-emitting characteristics, and the (8-hydroxyquinolate) -based metal coordination compound and Z or the (8-hydroxyquinoquinone) according to the present invention. (Rate) -based metal coordination compound-containing polymer compound can also be contained.
[0114] 発光素子 1においては、前記電子輸送層 7が、前記（8 ヒドロキシキノレート）系金 属配位化合物及び Z又は前記（8—ヒドロキシキノレート）系金属配位化合物含有高 分子化合物によって形成されている。この電子輸送層 7は、蒸着法によることなぐ例 えば、スピンキャスト法、コート法又はディップ法等により形成することができる。 [0114] In the light-emitting element 1, the electron transport layer 7 is composed of the (8 hydroxyquinolate) -based metal coordination compound and Z or the (8-hydroxyquinolate) -based metal coordination compound-containing high molecular compound. Is formed. The electron transport layer 7 can be formed by, for example, a spin casting method, a coating method, a dip method, or the like, by an evaporation method.
[0115] 前記電子注入層 8としては、例えば、 2, 5 ビス（1 ナフチル）—1, 3, 4 ォキサ ジァゾール（BND)、 2- (4— tert ブチルフエ-ル）—5— (4 ビフエ-リル）— 1, 3, 4ーォキサジァゾール等のォキサジァゾール誘導体、 2, 5 ビス（5， 一 tert ブ チル一 2，一ベンゾキサゾリル）チォフェン、トリス（8 キノリノラト）アルミニウム錯体 (A lq3)、ベンゾキノリノールベリリウム錯体 (Bebq2)などの金属錯体系材料など力も形 成される層を挙げることができる。この電子注入層 8は、蒸着法、塗布法、例えば、ス ピンキャスト法、コート法又はディップ法などにより形成することができる。 [0115] Examples of the electron injection layer 8 include 2,5 bis (1 naphthyl) -1,3,4 oxadiazole (BND), 2- (4-tert-butylphenol) -5- (4 biphenol- Ril) —oxadiazole derivatives such as 1,3,4-oxadiazole, 2,5 bis (5,1-tertbutyl-1,2-benzoxazolyl) thiophene, tris (8-quinolinolato) aluminum complex (A lq3), Mention may be made of layers in which forces are also formed, such as metal complex materials such as benzoquinolinol beryllium complex (Bebq2). The electron injection layer 8 can be formed by a vapor deposition method, a coating method, such as a spin casting method, a coating method, or a dipping method.
[0116] また、前記陰極 9は、仕事関数の小さい物質が採用され、例えば、 Mg、 Ag、アルミ -ゥム合金、金属カルシウムなどの金属単体または金属の合金で形成することができ る。好適な陰極は、アルミニウムと少量のリチウムとの合金電極である。この陰極 9は、 例えば、透明基板 2の上に形成された各層の表面に、化学気相成長法、スプレーパ イロリシス、真空蒸着法、電子ビーム蒸着法、スパッタ法、イオンビームスパッタ法、ィ オンプレーティング法、イオンアシスト蒸着法等の方法により形成することができる。 [0116] Further, the cathode 9 employs a substance having a small work function, and can be formed of, for example, a single metal such as Mg, Ag, an aluminum alloy, or calcium metal, or a metal alloy. A preferred cathode is an alloy electrode of aluminum and a small amount of lithium. For example, the cathode 9 is formed on the surface of each layer formed on the transparent substrate 2 by chemical vapor deposition, spray pyrolysis, vacuum deposition, electron beam deposition, sputtering, ion beam sputtering, ion plating. It can form by methods, such as a method and an ion-assisted vapor deposition method.
[0117] このような層構成を有する発光素子 1は、電流を流すことによって、陽極 3から正孔 輸送層 5を介して正孔注入層 4に正孔 (ホール)が注入され、陰極 9からは、発光化合 物を含有する発光層 6に向けて電子が注入される。この発光層 6においては、電子と ホールとが結合して、エネルギーが発光層 6の蛍光体 (発光化合物)を励起し、この励 起状態が元に戻るときに発光してエネルギーを放出する。発光素子 1の厚さは、通常 、 0. 1〜0. である。 In the light-emitting element 1 having such a layer configuration, holes are injected from the anode 3 into the hole injection layer 4 through the hole transport layer 5 by passing an electric current. In this case, electrons are injected toward the light emitting layer 6 containing the light emitting compound. In the light emitting layer 6, electrons and holes are combined to excite the phosphor (light emitting compound) of the light emitting layer 6, and when this excited state returns to its original state, light is emitted and energy is released. The thickness of the light-emitting element 1 is usually 0.1 to 0.
[0118] この発明に係る発光素子は、図 1に示される層構成を有する発光素子に限られず、
印加電圧極性可変構造型 EL素子、温度安定型多層 EL素子等を含む。なお、 8—ヒ ドロキシキノレート）系金属配位化合物及び Z又は前記（8—ヒドロキシキノレート）系 金属配位化合物含有高分子化合物は、電子輸送層として電子注入輸送層、又はホ ール輸送層としてホール注入輸送層にも用いられる。 [0118] The light-emitting device according to the present invention is not limited to the light-emitting device having the layer configuration shown in FIG. Including applied voltage polarity variable structure type EL element, temperature stable type multilayer EL element. Note that the 8-hydroxyquinolate) metal coordination compound and Z or the (8-hydroxyquinolate) metal coordination compound-containing polymer compound are used as an electron injection / transport layer or a hole as an electron transport layer. It is also used as a hole injection transport layer as a transport layer.
[0119] この発明に係る白色発光素子としては、図 32に示されるように、陽極 18と陰極 20と の間に発光層 19を挟んでなり、前記発光層 19が、前記式（11)で示される低分子の (8 ヒドロキシキノレート）系金属配位化合物及び Z又は前記式（ 12)で示される (8 ーヒドロキシキノレート）系金属配位化合物含有高分子化合物と、前記式（11)で示さ れる低分子の（8 ヒドロキシキノレート）系金属配位化合物及び Z又は前記式（12) で示される（8—ヒドロキシキノレート)系金属配位化合物含有高分子化合物により発 せられる色と実質的に補色の関係にある色を発光させる発光化合物とを含有してな る層である素子を挙げることができる。低分子の（8—ヒドロキシキノレート）系金属配 位化合物及び Z又は（8—ヒドロキシキノレート)系金属配位化合物含有高分子化合 物は、それ自身がその構造により電荷輸送物質又は電子輸送物質としての機能を有 するから特に電荷輸送層及び電子輸送層を有していなくても発光層 19に電圧を印 加すると発光層 19にお 、て低分子の（8 ヒドロキシキノレート）系金属配位ィ匕合物 及び Z又は（8—ヒドロキシキノレート)系金属配位化合物含有高分子化合物と発光 化合物とから発光を生じて白色が発光される。 [0119] As shown in Fig. 32, the white light emitting device according to the present invention comprises a light emitting layer 19 sandwiched between an anode 18 and a cathode 20, and the light emitting layer 19 is represented by the formula (11). A low molecular (8-hydroxyquinolate) -based metal coordination compound represented by the formula (11) and Z or the (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound represented by the above formula (12); The color emitted by the low molecular (8-hydroxyquinolate) -based metal coordination compound represented by (1) and the polymer compound containing Z or (8-hydroxyquinolate) -based metal coordination compound represented by the formula (12) Examples thereof include an element which is a layer containing a light emitting compound that emits light having a substantially complementary color. Low molecular (8-hydroxyquinolate) -based metal coordination compounds and polymer compounds containing Z or (8-hydroxyquinolate) -based metal coordination compounds are themselves charge transport materials or electron transport materials depending on their structures. Therefore, even if the charge transport layer and the electron transport layer are not provided, when a voltage is applied to the light emitting layer 19, a low molecular (8 hydroxyquinolate) -based metal arrangement is formed in the light emitting layer 19. White light is emitted by generating light from the compound and the Z or (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound and the light-emitting compound.
[0120] この発明に係る他の白色発光素子としては、図 33に示されるように、陽極 18と陰極 20との間に第 1発光層 19aと第 2発光層 19bとを挟んでなり、前記第 1発光層 19aが 、前記式（11)で示される低分子の（8 ヒドロキシキノレート）系金属配位ィ匕合物及び Z又は前記式（ 12)で示される (8 ヒドロキシキノレート）系金属配位化合物含有高 分子化合物を含有してなり、第 2発光層 19bが、前記式（11)で示される低分子の（8 ヒドロキシキノレート）系金属配位化合物及び Z又は前記式（ 12)で示される（8 ヒ ドロキシキノレート）系金属配位化合物含有高分子化合物により発せられる色と実質 的に補色の関係にある色を発光させる発光化合物を含有してなる層である素子を挙 げることができる。低分子の（8—ヒドロキシキノレート）系金属配位化合物及び Z又は (8—ヒドロキシキノレート）系金属配位ィ匕合物含有高分子化合物は、それ自身がその
構造により電荷輸送物質又は電子輸送物質としての機能を有するから特に電荷輸 送層及び電子輸送層を有して ヽなくても発光層 19に電圧を印加すると発光層 19に おいて低分子の（8—ヒドロキシキノレート）系金属配位ィ匕合物及び Z又は（8—ヒドロ キシキノレート)系金属配位ィ匕合物含有高分子化合物と発光化合物とから発光を生 じて白色が発光される。 [0120] As another white light emitting device according to the present invention, as shown in Fig. 33, a first light emitting layer 19a and a second light emitting layer 19b are sandwiched between an anode 18 and a cathode 20, The first light emitting layer 19a is a low molecular (8 hydroxyquinolate) -based metal coordination compound represented by the formula (11) and Z or the (8 hydroxyquinolate) system represented by the formula (12). The second light-emitting layer 19b is composed of a low molecular (8 hydroxyquinolate) -based metal coordination compound represented by the formula (11) and Z or the formula (12). (8) hydroxyquinolate-based metal coordination compound-containing polymer compound, and a device comprising a light-emitting compound that emits a color that is substantially complementary to the color emitted by the polymer compound. I can list them. The low molecular (8-hydroxyquinolate) -based metal coordination compound and the Z or (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound are themselves Depending on the structure, it has a function as a charge transport material or an electron transport material, and even if it has at least a charge transport layer and an electron transport layer, when a voltage is applied to the light emitting layer 19, a low molecular weight ( White light is emitted from the light-emitting compound and the polymer compound containing the 8-hydroxyquinolate) metal coordination compound and Z or (8-hydroxyquinolate) metal coordination compound and the light-emitting compound. .
[0121] また、前記発光層 19、第 1発光層 19a及び第 2発光層 19bには電荷輸送層及び電 子輸送層が更に積層されてなる白色発光素子であっても良 ヽ。 [0121] The light emitting layer 19, the first light emitting layer 19a, and the second light emitting layer 19b may be a white light emitting device in which a charge transport layer and an electron transport layer are further laminated.
[0122] この発明に係るその他の白色発光素子は、図 34に示されるように、前記式（11)で 示される低分子の（8—ヒドロキシキノレート）系金属配位化合物及び Z又は前記式（ 12)で示される（8—ヒドロキシキノレート）系金属配位化合物含有高分子化合物を含 有する発光層 22と、前記（8—ヒドロキシキノレート）系金属配位化合物及び Z又は前 記 (8—ヒドロキシキノレート）系金属配位ィヒ合物含有高分子化合物が発する色と補 色の関係にある色を発色する光源 21とを有する素子を挙げることができる。前記光 源 21は前記発光層 22に補色の関係にある色を照射することができるのであれば、 図 34に示されるように発光層 22と光源 21とが積層構造と成って 、る必要はな 、。発 光層 22は電気的エネルギーにより発光するのであるから、図 34には示されていない 陽極及び陰極から成る電極が設置される。 As shown in FIG. 34, the other white light emitting device according to the present invention is a low molecular (8-hydroxyquinolate) -based metal coordination compound represented by the above formula (11) and Z or the above formula. A light emitting layer 22 containing the (8-hydroxyquinolate) -based metal coordination compound-containing polymer compound represented by (12), the (8-hydroxyquinolate) -based metal coordination compound and Z or the above (8) An element having a light source 21 that develops a color complementary to the color emitted by the polymer compound containing a (hydroxyquinolate) -based metal coordination compound is included. If the light source 21 can irradiate the light emitting layer 22 with a color having a complementary color relationship, the light emitting layer 22 and the light source 21 need to have a laminated structure as shown in FIG. Nah ... Since the light emitting layer 22 emits light by electric energy, an electrode composed of an anode and a cathode not shown in FIG. 34 is provided.
[0123] いずれの発光素子及び白色発光素子においても発光層は、ポリビニルカルバゾー ル、 AS (アクリロニトリル 'スチレン）ポリマー、ポリスチレン、ビュルナフタレンポリマー をマトリックスポリマーとするポリマーフィルム層とすることができる。この発光層の厚み は通常 Inn！〜 5cm程度であり、発光素子の用途に応じて適宜に決定される。 [0123] In any of the light-emitting elements and the white light-emitting element, the light-emitting layer can be a polymer film layer using polyvinyl carbazole, AS (acrylonitrile styrene) polymer, polystyrene, or burnaphthalene polymer as a matrix polymer. The thickness of this light emitting layer is usually Inn! ˜5 cm, which is appropriately determined according to the use of the light emitting element.
実施例 1 Example 1
[0124] 以下、実施例を挙げて、この発明をさらに具体的に説明する力 この実施例によつ て、この発明はなんら限定されることはない。 [0124] Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the examples.
[0125] (実施例 1) [0125] (Example 1)
この実施例 1にお ヽては、式（14)で示される（8—ヒドロキシキノレート）系金属配位 化合物（14)を以下のようにして合成した。 In Example 1, the (8-hydroxyquinolate) -based metal coordination compound (14) represented by the formula (14) was synthesized as follows.
[0126] [化 27]
CH [0126] [Chemical 27] CH
(14) (14)
[0127] 三口フラスコに、 8—ヒドロキシキノリン 25g(172mmol)、 CC1110g [0127] In a three-necked flask, 8-hydroxyquinoline 25 g (172 mmol), CC1110 g
4 、 C H OH13 4, C H OH13
2 5 twenty five
Og及び KOHllOgを収容し、 12時間の間、還流した。次いで、 CH COOHで中和 Og and KOHllOg were housed and refluxed for 12 hours. Then neutralize with CH COOH
3 Three
した後、 CC1とじ H OHを留去し、 C H OHによって再結晶した。得られた結晶は、 After that, CC 1 and H 2 OH were distilled off and recrystallized with C 2 H 4 OH. The resulting crystals are
4 2 5 2 5 4 2 5 2 5
図 2に示される核磁気共鳴 (NMR)スペクトルから、式（ 15)で示される化合物（ 15)と 同定した。 From the nuclear magnetic resonance (NMR) spectrum shown in FIG. 2, the compound (15) represented by the formula (15) was identified.
[0128] [化 28] [0128] [Chemical 28]
COOCH.つ CH3 COOCH. One CH 3
fX '丫つ 、 fX '
OH (15)
[0129] フラスコに、前記化合物（15) 6. lg (28mmol)及び NH NH ·Η 012gを収容し、 OH (15) [0129] The flask was charged with 6. lg (28 mmol) of the compound (15) and 012 g NH NH · Η,
2 2 2 2 2 2
100°Cに加熱しながら 12時間、撹拌した。次いで、ろ過し、ろ過物を CH OHで洗浄 The mixture was stirred for 12 hours while being heated to 100 ° C. Then filter and wash the filtrate with CH OH
3 して、固形物を得た。この固形物の赤外線吸収（IR)スペクトルを図 3に、 NMR^ぺク トルを図 4に示す。この IR ^ベクトル及び NMR ^ベクトルによって、前記固开物は、 式（ 16)で示されるカルボヒドラジドィ匕合物（ 16)と同定された。 3 to obtain a solid. Fig. 3 shows the infrared absorption (IR) spectrum of this solid, and Fig. 4 shows the NMR spectrum. From this IR ^ vector and NMR ^ vector, the solid was identified as a carbohydrazide compound (16) represented by formula (16).
[0130] [化 29] [0130] [Chemical 29]
CO NH H 2 CO NH H 2
-丫- 、 ノ -丫-
OH 'l i ) OH 'l i)
[0131] フラスコに、前記カルボヒドラジド化合物（16) 2. 0g、及び 1—メチルピロリドン 100g を収容し、 0°Cに冷却しつつ 4 t ブチル安息香酸クロリド 2. Ogの 1 メチルピロリ ドン溶液を滴下した。次いで 100°Cに昇温し、 2時間、撹拌した。次いで、 1—メチル ピロリドンを留去し、水 50gを添カ卩した後、メチルアルコール次いでアセトンで洗浄し て、固形物を得た。この固形物の IR ^ベクトルを図 5に、 NMR ^ベクトルを図 6に示 す。この IR ^ベクトル及び NMR ^ベクトルによって、前記固开物は、ジカルボヒドラジ ド化合物（17)と同定された。 [0131] 2.0 g of the carbohydrazide compound (16) and 100 g of 1-methylpyrrolidone were placed in a flask, and 4 t-butylbenzoic acid chloride 2. Og in 1 methylpyrrolidone was added dropwise while cooling to 0 ° C. did. Next, the temperature was raised to 100 ° C., and the mixture was stirred for 2 hours. Next, 1-methylpyrrolidone was distilled off, 50 g of water was added, and the solid was washed with methyl alcohol and then with acetone. The IR ^ vector of this solid is shown in Fig. 5, and the NMR ^ vector is shown in Fig. 6. From this IR ^ vector and NMR ^ vector, the solid was identified as a dicarbohydrazide compound (17).
[0132] [化 30]
[0132] [Chemical 30]
CO MHNH CO MHNH
、、 :、 ,, : ,
OH .. . (1 7) OH ... (1 7)
フラスコに、前記化合物（17) 3. lg、ポリリン酸 20g及び 1， 4一ジォキサン 10gを収 容し、 100°Cで 12時間、撹拌した。次いで、氷を投入し、温アセトンにより洗浄し、さら に、アセトンとジォキサンとの混合液により洗浄して、固形物を得た。この固形物の IR スペクトルを図 7に、 NMR ^ベクトルを図 8に示す。この IRスペクトル及び NMRスぺ タトルによって、前記固形物は、以下の式（18)で示される化合物（18)と同定された [化 31]
In a flask, 3. lg of the compound (17), 20 g of polyphosphoric acid and 10 g of 1,4-dioxane were placed and stirred at 100 ° C. for 12 hours. Next, ice was added, washed with warm acetone, and further washed with a mixture of acetone and dioxane to obtain a solid. The IR spectrum of this solid is shown in FIG. 7, and the NMR vector is shown in FIG. From this IR spectrum and NMR spectrum, the solid was identified as the compound (18) represented by the following formula (18).
[0135] フラスコに、前記化合物（18) 345mg、 8—ヒドロキシキノリン 290mg、トリイソプロボ キシアルミニウム 204mg及びジメチルホルムアミド 200mlを収容し、 70°Cで 4時間、 撹拌した。次いで、ジメチルホルムアミドを留去した後、水を加えてろ過し、固形物を 得た。この固形物を乾燥し、クロ口ホルムに溶解した後、ろ過して得られたろ液に、さ らにジェチルエーテルをカ卩え、ろ過、乾燥して、固形物を得た。 [0135] The flask was charged with 345 mg of the compound (18), 290 mg of 8-hydroxyquinoline, 204 mg of triisopropoxyaluminum and 200 ml of dimethylformamide, and stirred at 70 ° C for 4 hours. Subsequently, after distilling off dimethylformamide, water was added and filtered to obtain a solid. This solid was dried, dissolved in black mouth form, and then filtered to obtain a solid.
[0136] 前記固形物の IR ^ベクトル（図 28)及び NMR ^ベクトル（図 29)から、前記固形物 は、前記式（14)で示される（8—ヒドロキシキノレート）系 A1配位ィ匕合物（14)と同定さ れた。この（8—ヒドロキシキノレート）系 A1配位化合物（14)を DMACに溶解して試 料液を調製した。この試料液を、 日立製作所製の F— 4500型分光蛍光光度計に装 填して、以下の条件にて蛍光スペクトルを測定した。得られた蛍光スペクトルを図 30 に示した。 [0136] From the IR ^ vector (Fig. 28) and the NMR ^ vector (Fig. 29) of the solid, the solid is an (8-hydroxyquinolate) -based A1 coordination group represented by the formula (14). It was identified as Compound (14). This (8-hydroxyquinolate) A1 coordination compound (14) was dissolved in DMAC to prepare a sample solution. This sample solution was loaded into a Hitachi F-4500 spectrofluorometer and the fluorescence spectrum was measured under the following conditions. The obtained fluorescence spectrum is shown in FIG.
[0137] 測定条件 [0137] Measurement conditions
測定モード 波長スキャン Measurement mode Wavelength scan
励起波長 365nm Excitation wavelength 365nm
蛍光開始波長 380nm Fluorescence start wavelength 380nm
蛍光終了波長 700nm
スキャンスピード 1200nm/分 Fluorescence end wavelength 700nm Scan speed 1200nm / min
励起側スリット 2. 5nm Excitation side slit 2.5 nm
蛍光側スリット 2. 5nm Fluorescent side slit 2.5 nm
実施例 2 Example 2
[0138] この実施例 2においては、式（19)で示される（8 ヒドロキシキノレート）系 A1配位化 合物（19)を以下のようにして合成した。 [0138] In Example 2, the (8 hydroxyquinolate) -based A1 coordination compound (19) represented by the formula (19) was synthesized as follows.
[0139] [化 32] [0139] [Chemical 32]
• . , (1 9) •, (1 9)
[0140] 2Lの三口フラスコ内に、 N— (2 クロロェチル）力ルバゾール 50gとトリクロ口ォキシ 燐 334. 3gと DMF157. Ogと 1, 2 ジク口口エタン 240mLとを挿人し、 85°Cで 2時 間反応を行った。反応生成液を氷中に投入し、クロ口ホルムで抽出し、再結晶操作を することにより N— (2 クロロェチル） 3 ホルミルカルバゾールを得た。この N— (
2—クロ口ェチル）—3—ホルミルカルバゾール 20gと、 1, 4—塩キサン 270mLと、過 マンガン酸カリ 0. 155モルと、水 630mLとを 2Lの二つ口フラスコに収容し、 80°Cに 加熱しながら 2時間反応させた。反応終了後に、反応生成液を氷冷し、 pHを 2にする ことにより沈殿を析出させた。この析出物を濾別し、メタノールで洗浄することにより式 (20)で示される化合物（20)を得た。フラスコに、化合物（20) 3g及び SOC1 10gを [0140] In a 2 L three-necked flask, insert 50 g of N- (2 chloroethyl) force rubazole, 334. 3 g of triclo-mouth oxyphosphorus, DMF157. Og, 240 mL of 1,2 dic-mouthed ethane at 85 ° C. The reaction was performed for 2 hours. The reaction product solution was put into ice, extracted with black mouth form, and recrystallized to obtain N- (2 chloroethyl) 3 formylcarbazole. This N— ( 2) 2-formylcarbazole) 20g, 1,4-formylcarbazole 270mL, potassium permanganate 0.155mol and water 630mL were placed in a 2L two-necked flask at 80 ° C The mixture was reacted for 2 hours with heating. After completion of the reaction, the reaction product solution was ice-cooled and the pH was adjusted to 2 to precipitate a precipitate. The precipitate was filtered off and washed with methanol to obtain the compound (20) represented by the formula (20). In a flask, add 3 g of compound (20) and 10 g of SOC1.
2 採取し、 70°Cで 2時間、撹拌して、式（21)で示される酸クロライドィ匕合物（21)を得た 2 was collected and stirred at 70 ° C for 2 hours to obtain an acid chloride compound (21) represented by the formula (21)
[0141] [化 33] [0141] [Chemical 33]
OH OH
(20) (20)
[0142] [化 34] [0142] [Chemical 34]
し h 9 H 2し I
H 9 H 2 I
C C
■' (21 )
[0143] フラスコに、前記化合物（16) 2. Og、及び 1—メチルピロリドン lOOgを収容し、 0°C に冷却しつつ前記化合物（21) 2. 9gの 1—メチルピロリドン溶液を滴下した。次いで 100°Cに昇温し、 2時間、撹拌した。次いで、 1—メチルピロリドンを留去し、水 50gを 添カ卩した後、メチルアルコール次いでアセトンで洗浄して、固形物を得た。この固形 物の IR ^ベクトルを図 9に、 NMRスペクトルを図 10に示す。この IR ^ベクトル及び N MRスペクトルによって、前記固形物は、以下の式（22)で示されるジカルボヒドラジド 化合物（22)と同定された。 ■ '(21) [0143] The compound (16) 2. Og and 1-methylpyrrolidone lOOg were accommodated in a flask, and the compound (21) 2.9 g of 1-methylpyrrolidone solution was added dropwise while cooling to 0 ° C. Next, the temperature was raised to 100 ° C., and the mixture was stirred for 2 hours. Next, 1-methylpyrrolidone was distilled off, 50 g of water was added, and the solid was washed with methyl alcohol and then with acetone. The IR ^ vector of this solid is shown in Fig. 9, and the NMR spectrum is shown in Fig. 10. From this IR ^ vector and NMR spectrum, the solid was identified as a dicarbohydrazide compound (22) represented by the following formula (22).
[0144] [化 35] [0144] [Chemical 35]
CO NHNH
CO NHNH
[0145] フラスコに、前記化合物（22) 4. 51g及びポリリン酸 50gを収容し、 100°Cで 12時 間、撹拌した。次いで、氷を投入して遠心分離、水を加えて遠心分離、さらにアセトン を加えて遠心分離した後、ろ過した。得られたろ過物を真空乾燥し、 3回のアセトン洗 浄、 2回のジェチルエーテル洗浄を行って、以下の式（23)で示される化合物（23)を 得た。以下の化合物（23)の IR ^ベクトルチャートを図 11に、 NMR ^ベクトルチヤ一 トを図 12に示した。 [0145] The flask was charged with 4.51 g of the compound (22) and 50 g of polyphosphoric acid, and the mixture was stirred at 100 ° C for 12 hours. Next, ice was added for centrifugation, water was added for centrifugation, and acetone was further added for centrifugation, followed by filtration. The obtained filtrate was vacuum-dried, washed with acetone three times and washed with jetyl ether twice to obtain a compound (23) represented by the following formula (23). The IR ^ vector chart of the following compound (23) is shown in Fig. 11, and the NMR ^ vector chart is shown in Fig. 12.
[0146] [化 36]
[0146] [Chemical 36]
OH (23) OH (23)
フラスコに、前記ィ匕合物（23) 4. 02g、 KOHO. 5g、ジメチノレホノレムアミド 50ml、 1, 4—ジォキサン 30ml及びエチルアルコール 20mlを収容し、 70°Cで 12時間、撹拌し た。次いで、酢酸で中和した後、溶媒を留去して、固形物を得た。この固形物の IRス ベクトルチャートを図 13に、 NMR ^ベクトルを図 14に示す。この IR ^ベクトル及び N MRスペクトルによって、前記固形物は、式（24)で示される化合物（24)と同定された [化 37]
The flask contained 4.02 g of the above compound (23), 5 g of KOHO., 50 ml of dimethinolehonolemamide, 30 ml of 1,4-dioxane and 20 ml of ethyl alcohol and stirred at 70 ° C. for 12 hours. . Subsequently, after neutralizing with acetic acid, the solvent was distilled off to obtain a solid. Fig. 13 shows the IR vector chart of this solid, and Fig. 14 shows the NMR ^ vector. From this IR ^ vector and N MR spectrum, the solid was identified as the compound (24) represented by the formula (24).
OH - (24) OH-(24)
[0149] この化合物（24)を DMACに溶解して試料液を調製した。この試料液を、島津製作 所製の F— 4500型分光蛍光光度計に装填して、前記実施例 1におけるのと同様の 条件にて蛍光スペクトルを測定した。得られた蛍光スペクトルを図 15に示した。 [0149] This compound (24) was dissolved in DMAC to prepare a sample solution. This sample solution was loaded into a Shimadzu F-4500 spectrofluorometer and the fluorescence spectrum was measured under the same conditions as in Example 1. The obtained fluorescence spectrum is shown in FIG.
[0150] フラスコに、前記化合物（24) 300mg、 8—ヒドロキシキノリン 215mg、トリイソプロボ キシアルミニウム 150mg及びジメチ口ホルムアミド 100mlを収容し、 70°Cに加熱しな 力 3時間、撹拌した。次いで、ジメチ口ホルムアミドを留去した後、水を加えてろ過し 、得られた固形物をメチルアルコールによる洗浄、ジェチルエーテルによる洗浄を行 い、乾燥することにより、図 16の IRスペクトルチャートを与える前記式（19)で示される (8—ヒドロキシキノレート）系 A1配位ィ匕合物（19)を得た。 [0150] 300 mg of the compound (24), 215 mg of 8-hydroxyquinoline, 150 mg of triisopropoxyaluminum and 100 ml of dimethylformamide were placed in a flask, and the mixture was stirred for 3 hours without heating to 70 ° C. Next, after dimethiformformamide was distilled off, water was added and the mixture was filtered. The obtained solid was washed with methyl alcohol, washed with jetyl ether, and dried to obtain the IR spectrum chart of FIG. The (8-hydroxyquinolate) -based A1 coordination compound (19) represented by the above formula (19) was obtained.
[0151] この（8—ヒドロキシキノレート）系 A1配位化合物（19)を DMACに溶解して試料液 を調製した。この試料液を、島津製作所製の F— 4500型分光蛍光光度計に装填し て、前記条件にて蛍光スペクトルを測定した。得られた蛍光スペクトルを図 17に示し た。 [0151] This (8-hydroxyquinolate) A1 coordination compound (19) was dissolved in DMAC to prepare a sample solution. This sample solution was loaded into an F-4500 type spectrofluorometer manufactured by Shimadzu Corporation, and the fluorescence spectrum was measured under the above conditions. The obtained fluorescence spectrum is shown in FIG.
[0152] 式（19)で示される（8—ヒドロキシキノレート）系 A1配位化合物（19) 180mgと AIB NO. 8mgと DMF30cm3とを封管に封入し、 120°Cに加熱しながら 48時間の重合を 行った。
[0153] 重合の終了後に封管の内容物を濃縮した後にこの濃縮物をメタノール中に投入し て、生成したポリマーを沈殿させた。得られたポリマーの IRスペクトルチャートを図 18 に、前記と同様にして測定された蛍光スペクトルチャートを図 19に示す。 [0152] (8-Hydroxyquinolate) A1 coordination compound (19) represented by the formula (19) 180 mg, AIB NO. 8 mg and DMF 30 cm 3 were sealed in a sealed tube and heated to 120 ° C. Time polymerization was carried out. [0153] After the polymerization was completed, the content of the sealed tube was concentrated, and then this concentrate was put into methanol to precipitate the produced polymer. FIG. 18 shows an IR spectrum chart of the obtained polymer, and FIG. 19 shows a fluorescence spectrum chart measured in the same manner as described above.
[0154] 式（19)で示される（8—ヒドロキシキノレート）系 A1配位化合物（19) 180mgとメチル メタタリレート（MMA) 50mgと AIBN1. 8mgと DMF30cm3とを封管に封入し、 100 °Cに加熱しながら 36時間の重合を行った。 [0154] (8-hydroxyquinolate) -based A1 coordination compound (19) represented by the formula (19) 180 mg, methyl metatalylate (MMA) 50 mg, AIBN 1.8 mg, and DMF 30 cm 3 are sealed in a sealed tube at 100 ° C. Polymerization was carried out for 36 hours while heating to C.
[0155] 重合の終了後に封管の内容物を濃縮した後にこの濃縮物をメタノール中に投入し て、生成したコポリマーを沈殿させた。得られたコポリマーの IR ^ベクトルチャートを図 20に示す。 [0155] After the polymerization was completed, the content of the sealed tube was concentrated, and then this concentrate was put into methanol to precipitate the produced copolymer. FIG. 20 shows an IR ^ vector chart of the obtained copolymer.
[0156] 式（19)で示される（8—ヒドロキシキノレート）系 A1配位化合物（19) 180mgと N— ビ-ルカルバゾール 242mgと AIBN5. Omgと DMF50cm3とを封管に封入し、 140[0156] formula represented by (19) (8-hydroxy quinolate) system A1 coordination compound (19) 180 mg and N- bi -. Carbazole 242mg and AIBN5 the Omg and DMF50cm 3 was sealed in a sealed tube, 140
°Cに加熱しながら 48時間の重合を行った。 The polymerization was carried out for 48 hours while heating to ° C.
[0157] 重合の終了後に封管の内容物を濃縮した後にこの濃縮物をメタノール中に投入し て、生成したコポリマーを沈殿させた。得られたコポリマーの IR ^ベクトルチャートを図[0157] After the polymerization was completed, the content of the sealed tube was concentrated, and then this concentrate was put into methanol to precipitate the produced copolymer. The IR ^ vector chart of the copolymer obtained is shown.
27に示す。 Shown in 27.
実施例 3 Example 3
[0158] 化合物（24) 1当量及び 8—ヒドロキシキノリン 1当量を DMFに懸濁した。この懸濁 液にカリウム t—ブチルアルコキシド 2当量を添カ卩し、硝酸マグネシウム 1当量を添カロ し、 30分還流した。反応生成液をろ過し、濃縮し、得られた濃縮物に水を加えて生成 する沈殿物をろ過し、濾過物を水、メタノール及びエーテルで洗浄することにより式（ 25)で示される（8—ヒドロキシキノレート）系 Mg配位ィ匕合物（25)を製造した。 [0158] 1 equivalent of compound (24) and 1 equivalent of 8-hydroxyquinoline were suspended in DMF. To this suspension, 2 equivalents of potassium t-butyl alkoxide was added, and 1 equivalent of magnesium nitrate was added and refluxed for 30 minutes. The reaction product solution is filtered and concentrated, water is added to the resulting concentrate, and the resulting precipitate is filtered. The filtrate is washed with water, methanol and ether, and expressed by the formula (25) (8 —Hydroxyquinolate) -based Mg coordination compound (25) was produced.
[0159] [化 38]
[0159] [Chemical 38]
[0160] この式（25)で示される（8—ヒドロキシキノレート）系 Mg配位化合物（25)にっき前 記と同様にして蛍光スペクトルを測定した。その蛍光スペクトルチャートを図 21に示し た。 [0160] The fluorescence spectrum of the (8-hydroxyquinolate) -based Mg coordination compound (25) represented by the formula (25) was measured in the same manner as described above. The fluorescence spectrum chart is shown in FIG.
実施例 4 Example 4
[0161] 前記実施例 3にお 、て硝酸マグネシウムの代わりに硫酸亜鉛を用いた外は前記実 施例 3と同様にして式（26)で示される（8—ヒドロキシキノレート）系 Zn配位ィ匕合物（2 6)を製造した。 [0161] The (8-hydroxyquinolate) -based Zn coordination represented by the formula (26) in the same manner as in Example 3 except that zinc sulfate was used instead of magnesium nitrate. A composite (2 6) was produced.
[0162] [化 39]
[0162] [Chemical 39]
(28) (28)
[0163] この式（26)で示される（8 ヒドロキシキノレート）系 Zn配位化合物（26)にっき前記 と同様にして蛍光スペクトルを測定した。その蛍光スペクトルチャートを図 22に示した 実施例 5 [0163] The fluorescence spectrum of the (8 hydroxyquinolate) -based Zn coordination compound (26) represented by the formula (26) was measured in the same manner as described above. The fluorescence spectrum chart is shown in FIG.
[0164] 前記実施例 3における硝酸マグネシウムの代わりに三塩ィ匕ガリウムを用い、 8 ヒド 口キシキノリン 1当量の代わりに 8 ヒドロキシキノリン 2当量を使用し、かつカリウム t— ブチルアルコシド 2当量の代わりにカリウム t ブチルアルコシド 3当量を用 、た外は 前記実施例 3と同様に実施して式（27)で示される（8 ヒドロキシキノレート）系 Ga配 位化合物（27)を製造した。 [0164] Instead of magnesium nitrate in Example 3, trisalt gallium is used, 8 hydroxyquinoline is used in place of 1 equivalent, 8 hydroxyquinoline is used in 2 equivalents, and potassium t-butylalcoside is used in place of 2 equivalents The same procedure as in Example 3 was used except that 3 equivalents of potassium t-butylalcoside was used to prepare an (8 hydroxyquinolate) -based Ga coordination compound (27) represented by the formula (27).
[0165] [化 40]
[0165] [Chemical 40]
(27) (27)
[0166] この式（27)で示される（8 ヒドロキシキノレート）系 Ga配位ィ匕合物（27)にっき前記 と同様にして蛍光スペクトルを測定した。その蛍光スペクトルチャートを図 23に示した 実施例 6 [0166] The fluorescence spectrum was measured in the same manner as described above for the (8 hydroxyquinolate) -based Ga coordination complex (27) represented by the formula (27). The fluorescence spectrum chart is shown in FIG. 23. Example 6
[0167] 前記実施例 3における硝酸マグネシウムの代わりに三塩化インジウムを用い、 8 ヒ ドロキシキノリン 1当量の代わりに 8 ヒドロキシキノリン 2当量を使用し、かつカリウム t ブチルアルコシド 2当量の代わりにカリウム t ブチルアルコシド 3当量を用 、た外 は前記実施例 3と同様に実施して式（28)で示される（8 ヒドロキシキノレート）系 In 配位化合物（28)を製造した。 [0167] Indium trichloride is used in place of magnesium nitrate in Example 3, 8 hydroxyquinoline is used in place of 1 equivalent, 8 hydroxyquinoline is used in 2 equivalents, and potassium t-butylalcoside is used in place of 2 equivalents of potassium. t (Butylquinolate) In coordination compound (28) represented by the formula (28) was produced in the same manner as in Example 3 except for using 3 equivalents of t-butylalcoside.
[0168] [化 41]
[0168] [Chemical 41]
« - (28) «-(28)
[0169] この式（28)で示される（8—ヒドロキシキノレート）系 In配位化合物（28)にっき前記 と同様にして蛍光スペクトルを測定した。その蛍光スペクトルチャートを図 24に示した 実施例 7 [0169] The fluorescence spectrum was measured in the same manner as described above for the (8-hydroxyquinolate) -based In coordination compound (28) represented by the formula (28). The fluorescence spectrum chart is shown in FIG. 24. Example 7
[0170] 前記実施例 3における硝酸マグネシウムの代わりに硫酸マンガンを使用した外は前 記実施例 3におけるのと同様にして（8—ヒドロキシキノレート）系 Mn配位ィ匕合物（29 )を製造した。 [0170] The (8-hydroxyquinolate) -based Mn coordination compound (29) was prepared in the same manner as in Example 3 except that manganese sulfate was used instead of magnesium nitrate in Example 3. Manufactured.
[0171] [化 42]
[0171] [Chemical 42]
(29) (29)
[0172] この式（29)で示される（8—ヒドロキシキノレート）系 Mn配位化合物（29)にっき前 記と同様にして蛍光スペクトルを測定した。その蛍光スペクトルチャートを図 25に示し た。 [0172] The fluorescence spectrum was measured in the same manner as described above for the (8-hydroxyquinolate) -based Mn coordination compound (29) represented by the formula (29). The fluorescence spectrum chart is shown in FIG.
実施例 8 Example 8
[0173] 前記実施例 2における化合物（24) 300mg、 8—ヒドロキシキノリン 215mg及びトリ イソプロポキシアルミニウム 150mgの代わりに、化合物（24) 1当量、化合物（18) 2当 量及びトリイソプロポキシアルミニウム 1当量を用いた外は前記実施例 2と同様に実施 して式（30)で示される（8—ヒドロキシキノレート）系 A1配位ィ匕合物（30)を製造した。 [0173] Instead of 300 mg of compound (24) in Example 2 above, 215 mg of 8-hydroxyquinoline and 150 mg of triisopropoxyaluminum, 1 equivalent of compound (24), 2 equivalents of compound (18) and 1 equivalent of triisopropoxyaluminum The (8-hydroxyquinolate) -based A1-coordinated compound (30) represented by the formula (30) was produced in the same manner as in Example 2 except that was used.
[0174] [化 43]
[0174] [Chemical 43]
[0175] この式（30)で示される（8—ヒドロキシキノレート）系 Al配位ィ匕合物（30)にっき前記 と同様にして蛍光スペクトルを測定した。その蛍光スペクトルチャートを図 26に示した 実施例 9 A fluorescence spectrum was measured in the same manner as described above for the (8-hydroxyquinolate) -based Al coordination compound (30) represented by the formula (30). The fluorescence spectrum chart is shown in FIG. 26. Example 9
[0176] この実施例は発光素子に関する,
[0177] 図 31に示される構造を有する発光素子を用意した。図 31において、 10は発光素 子を、 12はガラス基板を、 13は ITO透明電極を、 14はホール注入層を、 15は発光 層を、 16は Ca電極層を、及び 17は Ag電極層を夫々示す。図 31に示される発光素 子は次のようにして製造された。 [0176] This example relates to a light emitting device, A light emitting device having the structure shown in FIG. 31 was prepared. In FIG. 31, 10 is a light emitting element, 12 is a glass substrate, 13 is an ITO transparent electrode, 14 is a hole injection layer, 15 is a light emitting layer, 16 is a Ca electrode layer, and 17 is an Ag electrode layer. Respectively. The light emitting device shown in Fig. 31 was manufactured as follows.
[0178] すなわち、ガラス基板 12を、アルカリ洗浄剤を含有するイオン交換水溶液中で超音 波洗浄し、後、イオン交換水で超音波洗浄し、その後に乾燥し、更に紫外線洗浄を 行った。 That is, the glass substrate 12 was subjected to ultrasonic cleaning in an ion exchange aqueous solution containing an alkali cleaning agent, then ultrasonically cleaned with ion exchange water, then dried, and further subjected to ultraviolet cleaning.
[0179] このガラス基板 12の表面に ITOを蒸着することにより ITO透明電極を形成した。 [0179] An ITO transparent electrode was formed by depositing ITO on the surface of the glass substrate 12.
[0180] 上記のようにして清浄にしたガラス基板 12における ITO透明電極層の表面に、スピ ンコータの表面に市販の PEDOT (バイエル社製)含有の水性溶液 lmLを滴下し、 3 500rpmにて 30秒間回転させることにより、基板表面に膜厚 ΙΟθΑのホール注入層 を形成した。 [0180] On the surface of the ITO transparent electrode layer on the glass substrate 12 cleaned as described above, 1 mL of an aqueous solution containing a commercially available PEDOT (manufactured by Bayer) was dropped on the surface of the spin coater, and the solution was added at 3 500 rpm. By rotating for 2 seconds, a hole injection layer having a thickness of ΙΟθΑ was formed on the substrate surface.
[0181] ポリビニルカルバゾール 90mgと、式（31)で示される化合物（31) 10mgと以下の式 [0181] Polyvinylcarbazole 90 mg, compound (31) 10 mg represented by formula (31) and the following formula
(31)で示される黄色発光化合物（31) 0. 5mgとを 5mLの 1, 2—ジクロロェタンに溶 解した。得られた 1, 2—ジクロロェタン溶液 lmLを前記ホール注入層の表面に滴下 し、次いで 1500rpmで 5秒間スピンコータを回転させ、次いで 120°Cに加熱された 炉内に 10分間収容することにより乾燥を行い、これによつて厚み 100Aの発光層 15 を形成した。 0.5 mg of the yellow light-emitting compound (31) represented by (31) was dissolved in 5 mL of 1,2-dichloroethane. The obtained 1,2-dichloroethane solution (1 mL) was dropped on the surface of the hole injection layer, and then the spin coater was rotated at 1500 rpm for 5 seconds, and then dried in a furnace heated to 120 ° C. for 10 minutes. As a result, a light emitting layer 15 having a thickness of 100 A was formed.
[0182] 前記発光層 15の表面に蒸着により厚み 300 Aの Ca電極層 16及び厚み 1000 Aの [0182] 300 A thick Ca electrode layer 16 and 1000 A thick
Ag電極層 17を形成した。 An Ag electrode layer 17 was formed.
[0183] [化 44]
[0183] [Chemical 44]
CH3 (31 ) CH 3 (31)
[0184] 前記発光素子 1における電極層 13と電極層 16, 17との間に 50V及び 14. 1mAの 電圧及び電流を印加すると、この発光素子 1から 107cdZm2の輝度、色度座標の X 値 0. 39及び Y値 0. 61の発光が観察された。 [0184] When a voltage and current of 50 V and 14.1 mA are applied between the electrode layer 13 and the electrode layers 16 and 17 in the light-emitting element 1, X values of luminance and chromaticity coordinates of the light-emitting elements 1 to 107 cdZm 2 are applied. Luminescence of 0.39 and Y value 0.61 was observed.
実施例 10 Example 10
[0185] 前記式（25)で示される（8—ヒドロキシキノレート）系 Mg配位化合物 0. 8mg、ポリビ 二ルカルバゾール 50. Omg及びアントラセン 1. Omgを採取し、これらをクロ口ホルム ( 溶媒） 2mlに溶解した。得られた溶液をガラスプレートにスピンコート法（回転数 1000 rpm)で塗布し、大気中で自然乾燥して、発光層を形成した。 [0185] (8-Hydroxyquinolate) -based Mg coordination compound represented by the above formula (25) 0.8 mg, polyvinylcarbazole 50. Omg and anthracene 1. Collect Omg, ) Dissolved in 2 ml. The obtained solution was applied to a glass plate by a spin coating method (rotation speed: 1000 rpm) and naturally dried in the air to form a light emitting layer.
[0186] 前記発光層について、分光蛍光光度計（日立製作所製 F— 4500型、励起波長 34 Onm)を用いて蛍光スペクトルを測定した。この蛍光スペクトルチャートを図 35に示し た。この蛍光スペクトルチャートによって、前記発光層の白色発光が確認された。又、 励起波長 365nmを用いて測定した蛍光スペクトルを図 36に、励起波長 380nmを用 いて測定した蛍光スペクトルを図 37に示した。このように、励起波長が 340〜380nm の範囲にわたっていても、前記発光層から白色発光が観察された。励起波長が 250 nm程度の水銀ランプの光を照射することによつても前記発光層からは白色発光が観 察できた。 [0186] With respect to the light emitting layer, a fluorescence spectrum was measured using a spectrofluorometer (H-4500, manufactured by Hitachi, excitation wavelength: 34 Onm). This fluorescence spectrum chart is shown in FIG. From the fluorescence spectrum chart, white light emission of the light emitting layer was confirmed. Fig. 36 shows the fluorescence spectrum measured using an excitation wavelength of 365 nm, and Fig. 37 shows the fluorescence spectrum measured using an excitation wavelength of 380 nm. Thus, white light emission was observed from the light emitting layer even when the excitation wavelength ranged from 340 to 380 nm. White light emission could be observed from the light emitting layer even when irradiated with light from a mercury lamp having an excitation wavelength of about 250 nm.
実施例 11 Example 11
[0187] 前記式（19)で示される（8—ヒドロキシキノレート）系 A1系配位ィ匕合物（19)とビュル 力ルバゾールとの共重合体（ィヒ合物（19)：ビュル力ルバゾール = 1 : 10 (重量比） ) 0
. 8mg、ポリビ-ルカルバゾール 50. Omg及びアントラセン 1. Omgを採取し、以下、 実施例 10と同様にして、発光層を形成した。 [0187] Copolymer of (8-hydroxyquinolate) -based A1-coordinated compound (19) represented by the above formula (19) and bull force rubazole (Ich compound (19): Bull force) Luvazole = 1:10 (weight ratio)) 0 8 mg, polycarbcarbazole 50. Omg and anthracene 1. Omg was collected, and a light emitting layer was formed in the same manner as in Example 10 below.
[0188] 前記発光層について、分光蛍光光度計（日立製作所製 F— 4500型、励起波長 34 Onm)を用いて蛍光スペクトルを測定した。この蛍光スペクトルチャートを図 38に示し た。この蛍光スペクトルチャートによって、前記発光層の白色発光が確認された。前 記発光層の白色発光が確認された。又、励起波長 365nmを用いて測定した蛍光ス ベクトルを図 39に、励起波長 380nmを用いて測定した蛍光スペクトルを図 40に示し た。このように、励起波長が 340〜380nmの範囲にわたっていても、前記発光層から 白色発光が観察された。励起波長が 250nm程度の水銀ランプの光を照射すること によっても前記発光層からは白色発光が観察できた。 [0188] With respect to the light emitting layer, a fluorescence spectrum was measured using a spectrofluorometer (F-4500, manufactured by Hitachi, Ltd., excitation wavelength: 34 Onm). This fluorescence spectrum chart is shown in FIG. From the fluorescence spectrum chart, white light emission of the light emitting layer was confirmed. White light emission of the light emitting layer was confirmed. In addition, the fluorescence vector measured using an excitation wavelength of 365 nm is shown in FIG. 39, and the fluorescence spectrum measured using an excitation wavelength of 380 nm is shown in FIG. Thus, white light emission was observed from the light emitting layer even when the excitation wavelength ranged from 340 to 380 nm. White light emission could be observed from the light-emitting layer even when irradiated with light from a mercury lamp having an excitation wavelength of about 250 nm.
実施例 12 Example 12
[0189] 前記式（25)で示される（8—ヒドロキシキノレート）系 Mg配位ィ匕合物 0. 2mg、前記 式（26)で示される（8—ヒドロキシキノレート）系 Zn配位化合物 0. 2mg、ポリビ-ルカ ルバゾール 50. Omg及びアントラセン 1. Omgを採取し、以下、実施例 10と同様にし て、発光層を形成した。 [0189] 0.2 mg of (8-hydroxyquinolate) -based Mg coordination compound represented by the formula (25), and (8-hydroxyquinolate) -based Zn coordination compound represented by the formula (26) 0.2 mg, polyvinylcarbazole 50. Omg and anthracene 1. Omg was collected, and a light emitting layer was formed in the same manner as in Example 10 below.
[0190] 前記発光層について、分光蛍光光度計（日立製作所製 F— 4500型、励起波長 34 Onm)を用いて蛍光スペクトルを測定した。この蛍光スペクトルチャートを図 41に示し た。この蛍光スペクトルチャートによって、前記発光層の白色発光が確認された。前 記発光層の白色発光が確認された。又、励起波長 365nmを用いて測定した蛍光ス ベクトルを図 42に、励起波長 380nmを用いて測定した蛍光スペクトルを図 43に示し た。このように、励起波長が 340〜380nmの範囲にわたっていても、前記発光層から 白色発光が観察された。励起波長が 250nm程度の水銀ランプの光を照射すること によっても前記発光層からは白色発光が観察できた。 [0190] With respect to the light emitting layer, a fluorescence spectrum was measured using a spectrofluorometer (H-4500, manufactured by Hitachi, Ltd., excitation wavelength: 34 Onm). This fluorescence spectrum chart is shown in FIG. From the fluorescence spectrum chart, white light emission of the light emitting layer was confirmed. White light emission of the light emitting layer was confirmed. Fig. 42 shows the fluorescence vector measured using the excitation wavelength of 365nm, and Fig. 43 shows the fluorescence spectrum measured using the excitation wavelength of 380nm. Thus, white light emission was observed from the light emitting layer even when the excitation wavelength ranged from 340 to 380 nm. White light emission could be observed from the light-emitting layer even when irradiated with light from a mercury lamp having an excitation wavelength of about 250 nm.
実施例 13 Example 13
[0191] 前記式（25)で示される（8—ヒドロキシキノレート）系 Mg配位化合物 3. Omg、ポリビ 二ルカルバゾール 50. Omg及びナイルレッド 0. 2mgを採取し、以下、実施例 10と同 様にして、発光層を形成した。前記実施例 10と同様にして発光層の蛍光スペクトル を測定した。蛍光スペクトルを図 44に示した。
[0191] (8-Hydroxyquinolate) -based Mg coordination compound represented by the above formula (25) 3. Omg, polyvinylcarbazole 50. Omg and Nile red 0.2mg were collected. Similarly, a light emitting layer was formed. In the same manner as in Example 10, the fluorescence spectrum of the light emitting layer was measured. The fluorescence spectrum is shown in FIG.
Claims
請求の範囲 The scope of the claims
下記式（1)で表されることを特徴とする金属含有配位化合物。 A metal-containing coordination compound represented by the following formula (1):
前記式（1)において、 Aは、金属とチォフェン環又は芳香環を含有し、且つ前記金 属に配位する配位子とを有する発光性配位ィ匕合物における前記チォフェン環又は 芳香環力も水素を引き抜いた残基であり、 Bは、下記式（2)〜（5)で表されるいずれ かの基である。〕 In the formula (1), A represents a thiophene ring or an aromatic ring in a luminescent coordination complex comprising a metal and a thiophene ring or an aromatic ring and having a ligand coordinated to the metal. The force is also a residue from which hydrogen is extracted, and B is any group represented by the following formulas (2) to (5). ]
[化 2] [Chemical 2]
CH=CH2
[化 3] CH = CH 2 [Chemical 3]
[化 4] [Chemical 4]
R1 R1
C =CH2 C = CH 2
- - - (4) - - - (Four)
〔ただし、前記式 (4)において、 R1は、水素原子又はメチル基である。〕 [化 5][In the formula (4), R 1 is a hydrogen atom or a methyl group. ] [Chemical 5]
(5) (Five)
〔ただし、前記式（5)において、 R2は、炭素数 1〜20のアルキル基である。〕 [However, in the formula (5), R 2 is an alkyl group having 1 to 20 carbon atoms. ]
[2] 下記式 (6)で表される繰り返し単位を有することを特徴とする配位化合物残基含有 高分子化合物。
化 6][2] A coordination compound residue-containing high molecular compound having a repeating unit represented by the following formula (6): [6]
〔ただし、前記式（6)において、 Αは請求項 1におけるのと同様の意味を有し、 Zは、 下記式（7)、（8)又は単結合であり、 R3は、 Zが式（7)で示される基であるときには水 素原子であり、 Zが式 (8)で示されるときには水素原子又はメチル基である。なお、下 記式（7)及び (8)において、点線により囲まれている部分は、式（7)及び (8)で示そう とする基に含まれない。〕 [In the above formula (6), Α has the same meaning as in claim 1, Z is the following formula (7), (8) or a single bond, R 3 is When it is a group represented by (7), it is a hydrogen atom, and when Z is represented by formula (8), it is a hydrogen atom or a methyl group. In the following formulas (7) and (8), the portion surrounded by the dotted line is not included in the group to be expressed by formulas (7) and (8). ]
[化 7]
[Chemical 7]
[化 8] [Chemical 8]
( 8 ) (8)
[3] 請求項 1に記載の金属含有配位化合物及び Ζ又は請求項 2に記載の配位化合物 残基含有高分子化合物を含有することを特徴とする有機エレクト口ルミネッセンス材。 [3] An organic electoluminescence material comprising the metal-containing coordination compound according to claim 1 and the coordination compound according to claim 2 or a residue-containing polymer compound.
[4] 請求項 1に記載の金属含有配位化合物及び Ζ又は請求項 2に記載の配位化合物
残基含有高分子化合物と前記金属含有配位化合物及び z又は前記配位化合物残 基含高分子化合物の発光色と実質的に補色の関係にある光を発する発光化合物と を含有することを特徴とする白色有機エレクト口ルミネッセンス材。 [4] The metal-containing coordination compound according to claim 1 and the coordination compound according to claim 2 or claim 2. A residue-containing polymer compound, the metal-containing coordination compound, and z or a light-emitting compound that emits light substantially in a complementary color relationship with the emission color of the coordination compound residue-containing polymer compound. A white organic-elect luminescence material.
[5] 請求項 3に記載の有機エレクト口ルミネッセンス材を含有する層を有して成ることを 特徴とする発光素子。 [5] A light-emitting element comprising a layer containing the organic electoluminescence material according to claim 3.
[6] 前記請求項 3に記載の有機エレクト口ルミネッセンス材の発光色と、前記エレクト口 ルミネッセンス材と実質的に補色の関係にある光を発する発光化合物とを含有する 発光層を有することを特徴とする白色発光素子。 [6] It has a light emitting layer containing a light emitting color of the organic electoluminescent material according to claim 3 and a light emitting compound that emits light substantially in a complementary color relationship with the electroluminescent material. A white light emitting element.
[7] 請求項 3に記載の有機エレクト口ルミネッセンス材を含有する第 1発光層と前記請求 項 3に記載の有機エレクト口ルミネッセンス材の発光色と実質的に補色の関係にある 光を発する発光化合物を含有する第 2発光層とを備えてなることを特徴とする白色発 光素子。 [7] Light emission that emits light that is substantially complementary to the light emission color of the first light emitting layer containing the organic electroluminescent material according to claim 3 and the organic electroluminescent material according to claim 3. A white light emitting device comprising a second light emitting layer containing a compound.
[8] 請求項 3に記載の有機エレクト口ルミネッセンス材を含有する発光層と、この発光層 に前記請求項 3に記載の有機エレクト口ルミネッセンス材の発光色と実質的に補色の 関係にある光を発する発光源とを有して成ることを特徴とする白色発光素子。
[8] A light emitting layer containing the organic electoluminescent material according to claim 3, and light having a substantially complementary color relationship with the light emitting color of the organic electroluminescent material according to claim 3. And a light emitting source that emits light.
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Cited By (2)
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|---|---|---|---|---|
| WO2010089393A3 (en) * | 2009-02-06 | 2010-10-21 | Solvay Sa | Complex salts for light emitting devices |
| WO2018021406A1 (en) * | 2016-07-29 | 2018-02-01 | 大電株式会社 | Metal complex and electron-transporting material using same |
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| CN112961275B (en) * | 2021-02-09 | 2022-04-26 | 福建师范大学 | Method for synthesizing metal-free heavy atom-free long-life room temperature phosphorescent polymer by microwave radiation |
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| JPH05331460A (en) * | 1992-03-31 | 1993-12-14 | Sanyo Electric Co Ltd | Electroluminescent element |
| JPH10259372A (en) * | 1997-03-19 | 1998-09-29 | Toyota Central Res & Dev Lab Inc | Electroluminescent element |
| JP2005120071A (en) * | 2003-09-22 | 2005-05-12 | Hirose Engineering Co Ltd | Light emitting compound and light emitting element |
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| JPH05331460A (en) * | 1992-03-31 | 1993-12-14 | Sanyo Electric Co Ltd | Electroluminescent element |
| JPH10259372A (en) * | 1997-03-19 | 1998-09-29 | Toyota Central Res & Dev Lab Inc | Electroluminescent element |
| JP2005120071A (en) * | 2003-09-22 | 2005-05-12 | Hirose Engineering Co Ltd | Light emitting compound and light emitting element |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010089393A3 (en) * | 2009-02-06 | 2010-10-21 | Solvay Sa | Complex salts for light emitting devices |
| WO2018021406A1 (en) * | 2016-07-29 | 2018-02-01 | 大電株式会社 | Metal complex and electron-transporting material using same |
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