Classifications

• • 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
• • 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
  • 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
  • H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
  • C09K2211/1048—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with oxygen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/18—Metal complexes
  • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
• • 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

Definitions

• the present invention relates to an organic electoluminescence element, a display device, and a lighting device.
• Organic-electric luminescence elements also referred to simply as organic EL elements
• organic EL elements are self-luminous, so they have excellent visibility and can be driven at low voltages from several volts to several tens of volts. ⁇ is possible. Therefore, organic EL devices are expected to be used as thin film displays, lighting, and knocklights.
• the organic EL element is also characterized by abundant color nomination. Another feature is that various colors can be emitted by combining colors.
• the need for white light emission is particularly high, and it can also be used as a backlight.
• Such an organic EL element that emits white light is formed by stacking two layers of a blue light-emitting layer that emits short wavelength light and a red light-emitting layer that emits long wavelength light. Proposals have been made to obtain color emission (for example, see Patent Document 1). O
• the two light emitting layers having different colors are laminated.
• the drive time of the element that is, the light emission time and the change in applied voltage
• the luminescent center moves due to changes in film quality in the two light-emitting layers or changes in the transportability of holes and electrons, and as a result, chromaticity changes are likely to occur.
• Non-Patent Document 1 As an example of achieving a white color by combining a plurality of light emitting layers, there is an example in which an intermediate layer is provided between two light emitting layers having different light emission colors (for example, Non-Patent Document 1). Reference.
• Patent Document 1 Japanese Patent Laid-Open No. 7-142169
• Patent Document 2 JP 2003-187977
• Patent Document 3 JP 2004-63349 A
• Non-Patent Document 1 APPLIED PHYSICS LETTERS Vol. 83, 2459 (2003) and A DVANCED MATERIALS, Vol. 14, No. 2, 147 (2002)
• An object of the present invention is to provide an organic-electric-mouth luminescence element, a display device, and a lighting device that have high external quantum efficiency, that is, high luminous efficiency and low chromaticity deviation! It is.
• One of the embodiments for achieving the above object of the present invention is to have at least two light emitting layers between the anode and the cathode, and between the two light emitting layers.
• the two light emitting layers each contain the same host compound A and different light emitting dopants A and B, respectively, and
• the organic electroluminescent mouth luminescence device is characterized in that the intermediate layer contains the host compound A.
• FIG. 1 is a schematic view showing an example of a display device configured with organic EL element power.
• FIG. 2 is a schematic diagram of display unit A.
• FIG. 3 is an equivalent circuit diagram of a drive circuit constituting a pixel.
• FIG. 4 is a schematic diagram of a passive matrix display device.
• FIG. 5 is a schematic diagram of a sealing structure of an organic EL element 11.
• FIG. 6 is a schematic diagram of a lighting device including an organic EL element.
• FIG. 7 is a schematic view showing an example of a vapor deposition apparatus used for forming a light emitting layer of an organic EL element.
• FIG. 8 is a schematic view showing an example of a vapor deposition apparatus used for forming a light emitting layer of an organic EL element.
• FIG. 9 An example of the layer structure of the organic EL element is shown.
• FIG. 10 is a view showing a layer structure of a light emitting layer of the organic EL device of the present invention.
• FIG. 11 is a view showing a layer structure of a light emitting layer of the organic EL device of the present invention.
• FIG. 12 is a view showing a layer structure of a light emitting layer of the organic EL device of the present invention.
• FIG. 13 is a view showing a layer structure of a light emitting layer of the organic EL device of the present invention.
• an organic electroluminescent device having at least two light emitting layers between an anode and a cathode, and having at least one intermediate layer between the two light emitting layers,
• the two layers of light-emitting layers each contain the same host ich compound A and different light-emitting dopants A and B, and the intermediate layer contains the host compound A. Nominescence element.
• the thickness of the intermediate layer is larger than the Forster distance between the light-emitting dopant A and the light-emitting dopant B, (1) to (3), Organic electroreductive element.
• At least one of the light-emitting layers has two or more light-emitting layers of the same type that exhibit the same light emission peak, and any one of the above (1) to (6) Organic eletroluminescence element.
• the light-emitting layer is composed of at least two types of light-emitting layers A and B, the light-emitting layer A or B is at least two layers, and the light-emitting layers A, B and intermediate layers are 2.
• the light emitting layer is composed of at least three types of light emitting layers A, B, and C, and at least one of the light emitting layers A, B, and C is two or more layers, and is periodically stacked. 2.
• the electron blocking layer is provided between the light emitting layer and the anode, and at least one layer of the electron blocking layer is provided as a layer adjacent to the light emitting layer. (1;) to (11) !, displacement force
• the light emitting layer contains a light emitting dopant having at least one of the partial structures represented by the following general formulas (A) to (C) The organic electoluminescence device according to any one of the above.
• Ra represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group
• Rb or Rc represents a hydrogen atom or a substituent
• A1 forms an aromatic ring or an aromatic heterocyclic ring.
• M represents Ir, Pt.
• Ra represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group
• Ra represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group
• Rb or Rc represents a hydrogen atom or a substituent
• A1 forms an aromatic ring or an aromatic heterocyclic ring.
• M represents Ir or Pt.
• a display device comprising the organic electoluminescence device according to any one of (1) to (14).
• An illuminating device comprising the organic electoluminescence device according to any one of (1) to (14).
• the configuration defined in any one of the above (1) to (14) has high external quantum efficiency, that is, high luminous efficiency and high chromaticity. It was possible to provide an organic-elect mouth luminescence device with little deviation.
• a display device and a lighting device using the element can be provided together.
• the present inventors have determined There are two reasons for the deviation: one is that the exciton confinement is not enough, and the other is that the injection balance of holes and electrons through the intermediate layer is not constant. [0028] Therefore, in the organic EL device of the present invention, the drive voltage (current) is reduced by reducing the injection barrier between layers by using the same compound as the host material used for forming the intermediate layer and the light emitting layer. It was found that even when the slab was changed, the injection balance of holes and electrons became constant, and the color shift was remarkably reduced.
• the intermediate layer by using a material having higher triplet energy than the phosphorescent compound of the light emitting layer in the intermediate layer, it is possible to effectively confine triplet excitons in the light emitting layer. Successful . Furthermore, by making the film thickness of the intermediate layer more than the Förster distance, we succeeded in obtaining a highly efficient device by suppressing the energy shift of the exciton and suppressing the color shift.
• the permutation of the light emitting layers may be regular or random, and the intermediate layer may be provided only where it is necessary, instead of being provided at all.
• the light emitting layer according to the present invention will be described.
• the structure shown in element configuration 1 in FIG. 9 has a light emitting layer between a cathode and an anode, and the light emitting layer is sandwiched between an electron blocking layer and a hole blocking layer.
• these electron blocking layers or hole blocking layers are not necessarily required, the structure shown in FIG. It is preferable to provide these layers because the hole carriers can be confined in the light emitting layer, and also excitons generated by recombination of electrons and holes can be confined in the light emitting layer.
• the material forming the electron blocking layer is preferably smaller in electron affinity than the material forming the light emitting layer.
• the hole blocking layer is positive because it confines holes so that holes do not leak from the light emitting layer. It is preferable that the material forming the hole blocking layer has a larger ion potential than the material forming the light emitting layer.
• the material forming the hole blocking layer and the electron blocking layer is the excitation of the phosphorescent compound in the light emitting layer.
• Doublet energy is preferably greater than one
• a hole transport layer and an electron transport layer so as to sandwich them.
• Known materials can be used for the hole transport layer and the electron transport layer. It is preferable to use a material with high conductivity in terms of driving voltage reduction.
• the light emitting layer 11 to the light emitting layer 3-6 are obtained by extracting only the light emitting layer portion in the device configuration 1, respectively.
• the light-emitting layer is composed of at least two layers, and as shown in claim 7, at least one of the light-emitting layers exhibits the same emission peak, and two or more of the same type of light-emitting layers are present. As shown in claim 8, an embodiment in which at least two light emitting layers have two or more light emitting layers of the same type is preferably used.
• the two light emitting layers exhibiting the same light emission peak are the difference between the respective light emission maximum wavelengths when the two light emission peaks from the two light emitting layers are each subjected to PL measurement. Defined as less than 10 nm.
• a vapor deposition film is formed on a quartz substrate with a composition in which a light emitting dopant and a host compound are used in a light emitting layer, or a wet process such as a polymer is prepared by spin coating or A light emission maximum wavelength can be determined by preparing a thin film by dipping and measuring the light emission of the obtained deposited film or thin film with a fluorometer.
• the color when the organic EL device of the present invention is lit is not particularly limited, but white light emission is preferable.
• white when there are four light emitting layers having different emission peaks, white can be obtained by a combination of blue, blue green, yellow, and red.
• white it is possible to use another layer to correct the white color with three colors of blue, green and red.
• the emission color is not limited to white.
• the arrangement order of the plurality of light emitting layers may have a regular cycle or may be random.
• the light emitting layer has a regular period.
• the emission color can be changed even if the emission position is shifted in the thickness direction.
• the energy transfer of organic EL is mainly governed by the Forster type.
• the Forster type has a large energy transfer distance.
• Forster energy transfer is basically an important factor in that the overlap integral intensity of the emission spectrum of the donor molecule and the absorption spectrum of the acceptor molecule is large.
• the Förster distance refers to a 1: 1 distance between the probability of energy transfer and the probability of internal conversion. Energy transfer is dominant at shorter distances, and energy transfer occurs at longer distances. "Become. (For the Fenisterster type distance, see “Principles of Fluorescence Spectrocsopy JlJos eph R. Lakowicz Arrived Kluwer Academic Plenum Publishers p. D68) The results obtained are shown below. The structure of the phosphorescent compound is shown in the light emitting dopant described later.
• the Förster-type energy transfer distance was measured by the method described in “Principles of Fluoluminescence Spectrocsopy Jl Joseph” and akowicz arrival Kluwer Academic Plen urn Publishers.
• the Forster distance is 2.3 nm.
• V may be an undesirable problem.
• forster energy transfer is suppressed by providing an intermediate layer between two light emitting layers having different light emitting dopants (phosphorescent compounds).
• the film thickness of the intermediate layer (details of the intermediate layer will be described later) is 2.5 ⁇ ! Energy transfer can be effectively suppressed by setting the film thickness to -3nm or more.
• the film thickness of the intermediate layer can be reduced.
• the current-voltage characteristics can be changed by selecting a host material.
• the total thickness of the light emitting layer is not particularly limited, but is preferably 5 to lOOnm. More preferred is 7 to 50 nm, and most preferred is lOnm to 40 nm.
• each of the light emitting layers constituting the light emitting layer is preferably 1 to 20 nm, and more preferably 2 to 1 Onm.
• At least one layer of the structure of the light emitting layer contains a phosphorescent compound, and preferably, all the light emitting layers contain the phosphorescent compound. I prefer to do that.
• the mixing ratio of the light-emitting dopant to the light-emitting host that is the host compound that is the main component in the light-emitting layer is preferably adjusted to a range of 0.1% by mass to less than 30% by mass.
• the luminescent dopant may be a mixture of a plurality of types of compounds.
• the mixed partner may have a different structure, and other metal complexes or phosphorescent dopants or fluorescent dopants having other structures may be used.
• the dopants (phosphorescent dopant, fluorescent dopant, etc.) that may be used in combination with the metal complex used as the light emitting dopant will be described.
• the light-emitting dopant is roughly classified into two types: a fluorescent dopant that emits fluorescence and a phosphorescent dopant that emits phosphorescence.
• Representative examples of the former include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamines. And dyes such as a dye, a pyrylium dye, a perylene dye, a stilbene dye, a polythiophene dye, or a rare earth complex phosphor.
• a complex compound containing a metal of Group 8, Group 9, or Group 10 in the periodic table of elements is preferable, and an iridium compound, Sumium compounds, and most preferred are iridium compounds.
• JP 2002-100476 JP 2002-173674, JP 2002-359082, JP 2002-175884, JP 2002-363552, JP 2002-184582 Gazette, JP 2003-7469 gazette, special table 2002- 525 808, JP 2003-7471, JP 2002-525833, JP 2003-31366, JP 2002-226495, JP 2002-234894, JP 2002-235076 Publication, JP 2002-241751, JP 2001-319779, 2001-319780, 2002-62824, 2002-10 0474, 2002-203679 JP 2002-343572 A, JP 2 002-203678 A, and the like.
• a compound having a partial structure represented by general formulas (A) to (C) is preferable to use as a light-emitting dopant of at least one light-emitting layer of the light-emitting layer of the present invention.
• the light emitting dopa of the blue light emitting layer It is preferable to use it as a component.
• A1 is necessary to form an aromatic ring or an aromatic heterocyclic ring.
• the aromatic ring includes a benzene ring, biphenyl ring, naphthalene ring, azulene ring
• Phosphorus ring Phosphorus ring, quinazoline ring, phthalazine ring, force rubazole ring, carboline ring, diazacarbazole ring (One of the carbon atoms of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom.
• Ra represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group
• Rb, Rc, Rb, and Rc represent a hydrogen atom or a substituent.
• Ra is the same as Ra above.
• Rb, Rc, Rb, and Rc are the same as those represented by R to R, RA, and RB.
• the structures of the general formulas (A) to (C) are partial structures, and the light-emitting doppins themselves have a completed structure.
• a ligand corresponding to the valence of the central metal is necessary.
• halogen example For example, fluorine atom, chlorine atom, bromine atom or iodine atom
• aryl group eg
• -L group p chlorophenyl group, mesityl group, tolyl group, xylyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group, etc.), alkyl group (for example, methyl group, ethyl group, isopropyl group) Group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, tbutyl group, etc.), alkyloxy group, aryloxy group, alkylthio group, arylthio group, aromatic heterocyclic group (for example, furyl group, chael) Group, pyridyl group, pyridazil group
• M represents Ir or Pt, and Ir is particularly preferred! /.
• a tris body in which three partial structures of the general formulas (A) to (C) are completed is preferred.
• D-lacac, 4.0 g, phenol imidazole 2.6 g, and glycerin 300 ml are placed in a 500 ml three-necked flask, set on an oil bath stirrer with a thermometer and a cooling tube, and heated gradually. Adjust the bath temperature so that the temperature reaches 150 ° C and stir for 5 hours to complete the reaction.
• the light-emitting host (simply referred to as “host”! Means the compound with the highest mixing ratio (mass) in the light-emitting layer composed of two or more types of compounds.
• One pant compound also simply referred to as dopant) ".
• Compound C is a host compound.
• the light-emitting host used in the present invention is not particularly limited in terms of structure, but is typically a force rubazole derivative, triarylamine derivative, aromatic borane derivative, nitrogen-containing bicyclic compound, thiophene.
• carboline derivatives diaza force rubazole derivatives and the like are preferably used.
• the light-emitting host used in the present invention may be a low-molecular compound or a high-molecular compound having a repeating unit, which may be a low-molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerization light-emitting (Host) But ...
• a compound having a hole transporting ability and an electron transporting ability and preventing a long wavelength of light emission and having a high Tg (glass transition temperature) is preferable.
• Each vapor deposition source is heated to adjust the vapor deposition rate of the light emitting dopant or the host material and the intermediate layer forming material to be appropriate. Therefore, the vapor deposition is appropriately blocked by the shutter 202. It is set to be possible!
• the shutter 202 for the vapor deposition source of the host material and intermediate layer material is open at any time, and does not stop.
• the co-deposition conditions can be adjusted by opening and closing the shutter 202 set in the light emitting dopant deposition crucible 203 as necessary.
• the case of opening is the time when the light emitting layer is formed by vapor deposition, and the intermediate layer can be formed by vapor deposition when all of the light emitting dopant shirter 202 is closed.
• the deposition conditions for layer formation can be switched by opening and closing a single shutter. Multi-layered light emitting layers can be easily formed.
• FIG. 8 shows an example in which a host material and intermediate layer forming materials 206a and 206b are loaded between vapor deposition crucibles 203 loaded with light-emitting dopants 205a, 205b and 205c.
• a method of evaporating a light emitting dopant and a host / intermediate layer material from an evaporation source arranged in parallel is also effective.
• a similar element configuration can be fabricated by moving the substrate at a predetermined speed (reciprocating left and right).
• the present invention is characterized in that a material common to the material constituting the intermediate layer and the host compound contained in the light emitting layer (the host compound will be described later) is used.
• a material common to the light emitting layer in this way, the injection barrier between the layers of the light emitting layer is reduced, and the injection balance of holes and electrons can be maintained even when the voltage (current) is changed. The effect was obtained. It was also found that the effect of improving the color shift when voltage (current) was applied was obtained. Furthermore, by using a common material, it was possible to eliminate the complexity of device fabrication, which is a major problem in device fabrication having a conventional intermediate layer.
• the triplet excitons of the light-emitting layer are effectively confined in the light-emitting layer by using a material having an excited triplet energy higher than that of the phosphorescent compound as the material for the intermediate layer and light-emitting host. An efficient element can be obtained.
• the film thickness of the intermediate layer more than the Förster distance, it is possible to suppress the Förster energy transfer between the layers of different light emitting layers, to suppress the color shift, and to further increase the efficiency of the element. I can.
• the material constituting the intermediate layer and the host material are known materials (about host compounds) Can be used later).
• interlayer materials and host materials having a larger excited triplet energy are preferred than phosphorescent compounds having the largest excited triplet energy.
• U the phosphorescent compounds contained in the light-emitting layer
• interlayer materials and host materials having a larger excited triplet energy are preferred than phosphorescent compounds having the largest excited triplet energy.
• the excited triplet energy of the blue phosphorescent compound is the largest. Larger than this blue phosphorescent compound! /, An intermediate layer material having excited triplet energy, and a host material are preferred.
• the intermediate layer and the host material are responsible for carrier transport, materials having carrier transport ability are preferable.
• Carrier mobility is used as a physical property that expresses carrier transport ability, but carrier mobility of organic materials generally depends on electric field strength. Materials with high field strength dependency tend to break the transport balance between hole and electron injection.
• As the intermediate layer material and the host material it is preferable to use a material whose mobility is less dependent on the electric field strength.
• the blocking layer for example, electron blocking layer, hole blocking layer
• the blocking layer for example, electron blocking layer, hole blocking layer
• the organic EL device material of the present invention is used for a hole blocking layer, an electron blocking layer, and the like. It is particularly preferable to use for the hole blocking layer.
• the metal complex according to the present invention described in any one of claims 1 to 17 is used.
• the hole blocking layer may be contained in a state of 100% by mass as a layer constituent component such as an electron blocking layer, or other organic compound (for example, a compound used in the constituent layer of the organic EL device of the present invention). Etc. may be mixed.
• the thickness of the blocking layer according to the present invention is preferably 3 ⁇ ! ⁇ lOOnm, more preferably ⁇ to 5 nm to 30 nm.
• the hole blocking layer has the function of an electron transport layer, which is a material force that has the function of transporting electrons while transporting holes and is extremely small, and blocks holes while transporting electrons. By doing so, the probability of recombination of electrons and holes can be improved.
• Examples of the hole blocking layer include those disclosed in JP-A-11-204258, JP-A-11204359, and “OLED device and its forefront of industrialization (November 30, 1998, NTT Corporation).
• the hole blocking (hole blocking) layer described in page 237 of “Issuance”) is applicable as the hole blocking layer according to the present invention.
• the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer based on this invention as needed.
• the electron blocking layer has the function of a hole transport layer in a broad sense, and is a material force that has a function of transporting holes and an extremely small capacity of transporting electrons, and transports holes while transporting holes. The probability of recombination of electrons and holes can be improved by blocking the children.
• the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed.
• the organic EL element material of the present invention described above for the adjacent layer adjacent to the light emitting layer, that is, the hole blocking layer and the electron blocking layer. It is preferably used for the blocking layer.
• the hole transport layer includes a material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer.
• Hole transport layer is provided as a single layer or multiple layers be able to.
• a hole transport material there is no particular limitation. Conventionally, in a photoconductive material, it is commonly used as a hole charge injection / transport material and used for a hole injection layer or a hole transport layer of an EL element. Any one of known ones used can be selected and used.
• the hole transport material has either injection / transport of holes, electron barrier properties! /, Or a deviation, and may be either organic or inorganic.
• triazole derivatives oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives , Stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
• the hole transport material it is preferable to use a porphyrin compound, an aromatic tertiary amine compound, and a styrylamine compound, particularly an aromatic tertiary amine compound. ,.
• aromatic tertiary amine compounds and styrylamine compounds include N, N, N
• N 1 tetraphenyl 4, 4, 1, diaminophenol; N, N, 1 diphenyl N, N, 1 (3-methylphenol) — [1, 1, —biphenyl] — 4, 4, — Diamine (TPD); 2, 2 Bis (4 di-p-tri-laminophenol) propane; 1, 1 Bis (4-di-p-tri-amino-phenyl) cyclohexane; N, N, ⁇ ', ⁇ , monotetra ⁇ tril 1,4,4, 1 diaminobiphenyl; 1, 1 bis (4 di ⁇ triarylaminophenol) 4 phenol cyclohexane; bis (4 dimethylamino 2 methylphenol) phenylmethane; bis (4 di-rholylaminophenol) phenol; ⁇ ⁇ ⁇ , ⁇ , 1 diphenyl ⁇ , ⁇ , 1 di (4-methoxyphenyl) —4, 4'-diaminobiphenyl; ⁇ , ⁇ , ⁇
• inorganic compounds such as p-type Si and p-type SiC can also be used as the hole injection material and the hole transport material.
• the hole transport material preferably has a high Tg.
• the hole transport layer is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method. be able to.
• the thickness of the hole transport layer is not particularly limited, but is usually 5 ⁇ ! ⁇ 50 OOnm or so.
• the hole transport layer may have a single layer structure composed of one or more of the above materials.
• An impurity-doped hole transport layer with high p property can also be used. Examples thereof include those described in JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, R. Ap pi. Phys., 95, 5773 (2004), etc. It is done.
• the electron transport layer is a material force having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer.
• the electron transport layer can be a single layer or a plurality of layers.
• the electron transport layer is not particularly limited as long as it has a function of transmitting electrons injected from the cathode to the light emitting layer. It is possible to be.
• electron transport materials examples include: -to-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide oxide derivatives, Examples include heterocyclic tetracarboxylic anhydrides such as phthaleneperylene, carbodiimide, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, and oxadiazole derivatives.
• a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. I'll do it.
• a polymer material in which these materials are introduced into a polymer chain or these materials as a polymer main chain can also be used.
• metal complexes of 8 quinolinol derivatives such as tris (8 quinolinol) aluminum (Alq), tris (5,7-dichloro-1-8-quinolinol) aluminum, tris (5,7-dive mouth) 8 quinolinol) aluminum, tris (2methyl 8quinolinol) aluminum, tris (5-methyl 8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc.
• the central metals of these metal complexes are In, Mg, Metal complexes replacing Cu, Ca, Sn, Ga or Pb can also be used as electron transport materials.
• metal free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material.
• the distyrylvirazine derivative exemplified as the material for the light emitting layer can also be used as an electron transport material, and, like the hole injection layer and the hole transport layer, n-type-Si, n-type-SiC, etc. These inorganic semiconductors can also be used as electron transport materials.
• the electron transport layer may be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method. it can. Although there is no restriction
• This electron transport layer may have a single layer structure composed of one or more of the above materials.
• An impurity-doped electron transport layer with high n property can also be used. Examples thereof include those described in JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, R. Ap pi. Phys., 95, 5773 (2004), etc. It is done.
• the injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer. As described above, the injection layer exists between the anode and the light emitting layer or hole transport layer, and between the cathode and the light emitting layer or electron transport layer. May be present.
• the injection layer is a layer provided between the electrode and the organic layer in order to lower the driving voltage and improve the luminance of light emission.
• the organic EL element and its industrial front line June 30, 1998) Chapter 2 “Electrode materials” (pages 123-166) of “Part 2” of “Tees Co., Ltd.”) describes the details of the hole injection layer (anode buffer layer) and the electron injection layer (cathode buffer). One layer).
• anode buffer layer hole injection layer
• cathode buffer layer (electron injection layer) The details of the cathode buffer layer (electron injection layer) are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like.
• a metal buffer layer typified by aluminum or aluminum, an alkali metal compound buffer layer typified by lithium fluoride, an alkaline earth metal compound buffer layer typified by magnesium fluoride, or an aluminum oxide layer A single acid buffer.
• the buffer layer (injection layer) preferably has a very thin film thickness, but the film thickness is preferably in the range of 0.1 nm to 100 nm.
• This injection layer can be formed by thin-filming the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method.
• the thickness of the injection layer is not particularly limited, but is usually about 5 to 5000 nm.
• the injection layer may have a single layer structure that can be one or more of the above materials.
• an electrode material made of a metal, an alloy, an electrically conductive compound or a mixture thereof having a high work function (4 eV or more) is preferably used.
• electrode materials include metals such as Au, and conductive transparent materials such as Cul, indium tin oxide (ITO), SnO, and ZnO.
• ITO indium tin oxide
• SnO indium tin oxide
• ZnO ZnO.
• An amorphous material such as ZnO) that can produce a transparent conductive film may be used.
• these electrode materials can be formed into a thin film by vapor deposition or sputtering, and a pattern with a desired shape can be formed by a single photolithography method. m or more), a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered.
• the film thickness depends on the material. Usually ⁇ ! ⁇ 1000 nm, preferably 10 nm to 200 nm.
• the cathode according to the present invention a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof is used.
• an electron injecting metal a material having a low work function (4 eV or less) metal
• an alloy a material having a low work function (4 eV or less) metal
• an alloy a material having a low work function (4 eV or less) metal
• an alloy referred to as an electron injecting metal
• an alloy referred to as an electron injecting metal
• an alloy an electrically conductive compound
• a mixture thereof a mixture thereof.
• electrode materials include sodium, sodium-powered rhodium alloy, magnesium, lithium, magnesium Z copper mixture, magnesium Z silver mixture, magnesium / aluminum mixture, magnesium Z indium mixture, aluminum Z acid aluminum (Al 2 O 3) mixture, indium, lithium
• Lithium Z aluminum mixture, aluminum and the like are preferred.
• the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
• the sheet resistance as the cathode is preferably several hundred ⁇ or less.
• the film thickness is usually selected in the range of 10 nm to 1000 nm, preferably 50 nm to 200 nm.
• either the anode or the cathode of the organic EL element is transparent or A translucent structure is advantageous because it improves light emission luminance.
• the substrate of the organic EL device of the present invention is not particularly limited in the type of glass, plastic, etc., and is not particularly limited as long as it is transparent, but preferably used substrates include, for example, glass, quartz And a light-transmitting resin film. Particularly preferred V, the substrate is a resin film that can give flexibility to the organic EL element.
• Examples of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylenesulfide, polyarylate, polyimide, polycarbonate (PC). , Cellulose triacetate (TAC), cellulose acetate propionate (CAP) and the like.
• PET polyethylene terephthalate
• PEN polyethylene naphthalate
• PES polyethersulfone
• PES polyetherimide
• polyetheretherketone polyphenylenesulfide
• PC polycarbonate
• TAC Cellulose triacetate
• CAP cellulose acetate propionate
• an inorganic film or an organic film, or a hybrid film of both of them may be formed, and a water vapor permeability of 0.01 gZm 2 'dayatm or less is used. I prefer to be there.
• the external extraction efficiency at room temperature of light emission of the organic electoluminescence device of the present invention is preferably 1% or more, more preferably 2% or more.
• external extraction quantum efficiency (%) number of photons emitted outside the organic EL element Z number of electrons flowing through the organic EL element X 100.
• a hue improving filter such as a color filter may be used in combination.
• a roughened film (such as an antiglare film) can be used in combination in order to reduce unevenness in light emission.
• the organic EL element When used as a multicolor display device, the organic EL element having at least two different emission maximum wavelengths will be described. A preferred example of producing an organic EL element will be described.
• an anode / hole injection layer / hole transport layer As an example of a method for producing the organic EL device of the present invention, an anode / hole injection layer / hole transport layer
• a desired electrode material for example, a thin film having a material force for an anode
• a desired electrode material for example, a thin film having a material force for an anode
• An anode is formed by a method such as vapor deposition or sputtering so as to have a film thickness of ⁇ 200 nm.
• a thin film containing an organic compound such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer, which is an element material, is formed thereon.
• the deposition conditions may vary due to kinds of materials used, generally baud preparative heating temperature 50 ° C ⁇ 450 ° C, vacuum degree of 10- 6 Pa to: LO- It is desirable to select appropriately within the range of 2 Pa, deposition rate of 0.01 nm to 50 nm / second, substrate temperature—50 ° C to 300 ° C, and film thickness of 0.1 nm to 5 ⁇ m.
• a thin film having a cathode material force is formed thereon by a method such as vapor deposition or sputtering so that the film thickness is 1 ⁇ m or less, preferably in the range of 50 nm to 200 nm.
• a desired organic EL device can be obtained. It is preferable that the organic EL device is manufactured from the hole injection layer to the cathode consistently by a single evacuation, but it does not matter if it is taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.
• the display device of the present invention will be described.
• the display device of the present invention may be monochromatic or multicolor, but here, the multicolor display device will be described.
• a shadow mask is provided only when forming a light emitting layer, and a film can be formed on one side by vapor deposition, casting, spin coating, ink jet, printing, etc.
• the method is not limited, but a vapor deposition method, an inkjet method, and a printing method are preferable.
• a vapor deposition method patterning using a shadow mask is preferred.
• the multicolor display device can be used as a display device, a display, and various light sources. Display devices and displays can be displayed in full color by using three types of organic EL elements that emit blue, red, and green light.
• Display devices and displays include televisions, personal computers, mono equipment, AV equipment, text broadcast displays, information displays in automobiles, and the like.
• the driving method when used as a display device for reproducing moving images which may be used as a display device for reproducing still images or moving images, may be either a simple matrix (passive matrix) method or an active matrix method.
• Light emitting sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sensors Although a light source etc. are mentioned, it is not limited to this.
• the lighting device of the present invention will be described.
• the organic EL device having a resonator structure may be used as an organic EL device having a resonator structure in the organic EL device of the present invention.
• Examples include, but are not limited to, photocopier light sources, optical communication processor light sources, and optical sensor light sources. Further, it may be used for the above-mentioned applications by causing laser oscillation.
• the organic EL device of the present invention may be used as a kind of lamp such as an illumination or exposure light source, a projection device of a type for projecting an image, a still image or a moving image. It may be used as a display device (display) of the type that is directly visually recognized.
• the drive system when used as a display device for video playback is a simple matrix (passive matrix) Either the method or the active matrix method may be used.
• a full color display device can be produced by using two or more organic EL elements of the present invention having different emission colors.
• FIG. 1 is a schematic diagram showing an example of a display device configured with organic EL element power.
• FIG. 2 is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.
• the display 1 also has a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.
• the control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of the plurality of pixels based on image information from the outside. Sequentially emit light according to the image data signal, scan the image, and display the image information on the display unit A.
• FIG. 2 is a schematic diagram of the display unit A.
• the display unit A has a wiring unit including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3 and the like on a substrate.
• the main members of the display unit A will be described below.
• the light power emitted from the pixel 3 is extracted in the direction of the white arrow (downward).
• the scanning lines 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at orthogonal positions ( Details are not shown).
• the pixel 3 When a scanning signal is applied from the scanning line 5, the pixel 3 receives an image data signal from the data line 6, and emits light in accordance with the received image data.
• Full color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.
• FIG. 3 is a schematic diagram of a pixel.
• the pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like.
• a full-color display can be performed by using an organic EL element that emits white light as the organic EL element 10 divided into multiple pixels and combining it with a BGR color filter.
• an image data signal is also applied to the drain of the switching transistor 11 via the data line 6 in the control unit B force.
• a scanning signal is applied to the gate of the switching transistor 11 via the control unit B force scanning line 5
• the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is transferred to the capacitor 13 and the driving transistor. It is transmitted to the gate of the star 12.
• the capacitor 13 is charged according to the potential of the image data signal, and the drive of the drive transistor 12 is turned on.
• the drive transistor 12 has a drain connected to the power supply line 7 and a source connected to the electrode of the organic EL element 10, and the organic EL element is connected from the power supply line 7 according to the potential of the image data signal applied to the gate. Current is supplied to element 10.
• the driving of the switching transistor 11 is turned off. However, even if the driving of the switching transistor 11 is turned off, the capacitor 13 holds the potential of the charged image data signal, so that the driving of the driving transistor 12 is kept on and the next scanning signal is applied.
• the organic EL device 10 continues to emit light until it is seen.
• the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.
• the organic EL element 10 emits light by providing a switching transistor 11 and a driving transistor 12 as active elements for each of the organic EL elements 10 of the plurality of pixels.
• Element 10 is emitting light.
• Such a light emitting method is called an active matrix method.
• the light emission of the organic EL element 10 is a multi-value image data signal having a plurality of gradation potentials. You can use multiple levels of light emission, or you can use a binary image data signal to turn on or turn on a predetermined amount of light! /.
• the potential of the capacitor 13 may be maintained until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.
• FIG. 4 is a schematic diagram of a display device based on a noisy matrix method.
• a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.
• the pixel 3 connected to the applied scanning line 5 emits light in accordance with the image data signal.
• the noisy matrix method pixel 3 has no active elements, and manufacturing costs can be reduced.
• the organic EL material according to the present invention can also be applied to an organic EL element that emits substantially white light as a lighting device.
• a plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by mixing colors.
• the combination of multiple emission colors may include the three maximum emission wavelengths of the three primary colors of blue, green, and blue, or the complementary colors such as blue and yellow, blue green and orange are used 2 It may be one containing two emission maximum wavelengths.
• a combination of light emitting materials for obtaining a plurality of emission colors includes a combination of a plurality of phosphorescent or fluorescent materials (light emitting dopants), a light emitting material that emits fluorescent or phosphorescent light, and Any combination of a dye material that emits light from the light emitting material as excitation light may be used, but in the white organic electoluminescence device according to the present invention, a method of combining a plurality of light emitting dopants is preferred.
• the layer structure of the organic electoluminescence device for obtaining a plurality of emission colors includes a method in which a plurality of emission dopants exist in one emission layer, a plurality of emission layers, and each emission Examples thereof include a method in which dopants having different emission wavelengths are present in the layer, and a method in which minute pixels emitting light of different wavelengths are formed in a matrix.
• the Patterning may be performed by a metal mask or an inkjet printing method at the time of film formation.
• the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire device layer may be patterned.
• the light emitting material used for the light emitting layer is not particularly limited.
• the platinum complex according to the present invention is adapted so as to conform to the wavelength range corresponding to the CF (color filter) characteristics. It is also possible to select any of the known luminescent materials and combine them to whiten.
• the white light-emitting organic EL device of the present invention is not limited to the display device or the display, but as a variety of light-emitting light sources and lighting devices, such as home lighting, interior lighting, and exposure light source.
• a lamp it is also useful for a display device such as a backlight of a liquid crystal display device.
• the emission crucible 204a is irradiated with the light emitting donor Mr-12 and the vapor deposition crucible 204b is irradiated with Ir-9.
• CDBP which is a host material and an intermediate layer forming material, was loaded in each of the crucibles 204d for vapor deposition in the optimum amounts for device fabrication.
• the crucible for vapor deposition used what was produced with the resistance heating material made from molybdenum.
• the evaporation crucible containing HTM1 was energized and heated to deposit 15 nm of HTM1 at a deposition rate of 0. InmZ seconds.
• a light emitting layer A, an intermediate layer, and a light emitting layer B were formed using the materials shown in Table 1 and Table 2, and then Compound H-13 as a hole blocking layer on the light emitting layer B was formed. LOnm evaporated.
• the evaporation crucible containing Alq was energized and heated, and the deposition rate was 0. InmZ seconds.
• An electron transport layer having a thickness of 30 nm was provided by vapor deposition on the hole blocking layer.
• the substrate temperature during vapor deposition was adjusted to room temperature.
• the organic EL device 1-1 In the production of the organic EL device 1-1, except that the configuration of the light emitting layer (configuration of the light emitting layer and the intermediate layer) was changed as shown in Table 1 and Table 2, the organic EL devices 1 2 to 1 12 were Each was produced.
• H-13 lr-13 3% by mass 4nm
• H-13 Ir 1 16% by mass 1.5nm
• the external extraction quantum efficiency (%) when a constant current of Zcm 2 was applied was measured.
• a spectral radiance meter CS-1000 manufactured by Minolta was used.
• Chromaticity deviation is Te you!, The CIE chromaticity diagram, which represents the deviation of the chromaticity coordinates at the time of chromaticity coordinates and 5000cdZ m 2 brightness in LOOcdZm 2 brightness. Specifically, measurement was performed using CS-1000 (manufactured by Minolta) at 23 ° C in a dry nitrogen gas atmosphere.
• the device of the present invention exhibits a high external extraction quantum efficiency, that is, the luminous efficiency is high and the chromaticity shift is small compared to the comparative device.
• organic EL devices 2-1 to 2-12 were produced. It was confirmed that the driving voltage of the organic EL elements 2-1 to 2-12 was 3-6V lower than that of the organic EL elements 1 1 to 112.
• FIG. 6 is a schematic view of the lighting device, (a) is a schematic plan view, and (b) is a schematic cross-sectional view of the lighting device.
• An organic EL layer 102 provided on a glass substrate 101 with a transparent electrode was covered with a glass sealing can 104, and an ultraviolet curable adhesive 107 was used to attach the glass sealing can.
• 103 is a cathode.
• the glass sealing can 104 is filled with nitrogen gas, and a water catching agent 105 is provided.
• an organic electoluminescence element a display device, and an illumination device that have high external quantum efficiency, that is, high light emission efficiency and little shift in chromaticity.

Priority Applications (4)

Applications Claiming Priority (2)

Related Child Applications (2)

Publications (1)

Family

ID=35785139

Family Applications (1)

Country Status (4)

Cited By (529)

Families Citing this family (18)

Citations (6)

Family Cites Families (44)

• 2005
  • 2005-07-13 EP EP05765803A patent/EP1784056B1/en not_active Expired - Fee Related
  • 2005-07-13 WO PCT/JP2005/012889 patent/WO2006009024A1/ja active Application Filing
  • 2005-07-13 JP JP2006529076A patent/JP4858169B2/ja not_active Expired - Fee Related
  • 2005-07-13 EP EP10152814A patent/EP2178348B1/en not_active Expired - Fee Related
  • 2005-07-13 EP EP10188489.8A patent/EP2271183B1/en not_active Expired - Fee Related
  • 2005-07-13 US US11/632,758 patent/US7504657B2/en active Active
• 2008
  • 2008-12-15 US US12/335,321 patent/US7897421B2/en not_active Expired - Fee Related
• 2011
  • 2011-09-05 JP JP2011192229A patent/JP2012028792A/ja active Pending