WO2011132575A1 - Organic electroluminescent element, and charge transport material and compound having m-quinquephenyl structure - Google Patents

Organic electroluminescent element, and charge transport material and compound having m-quinquephenyl structure Download PDF

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WO2011132575A1
WO2011132575A1 PCT/JP2011/059119 JP2011059119W WO2011132575A1 WO 2011132575 A1 WO2011132575 A1 WO 2011132575A1 JP 2011059119 W JP2011059119 W JP 2011059119W WO 2011132575 A1 WO2011132575 A1 WO 2011132575A1
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group
general formula
substituted
represented
cyano
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哲 北村
徹 渡辺
誠之 林
郁雄 木下
俊大 伊勢
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富士フイルム株式会社
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    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium

Definitions

  • the present invention relates to an organic electroluminescence device, and a charge transport material and compound having an m-kinkphenyl structure.
  • Organic electroluminescent elements (hereinafter also referred to as “elements” and “organic EL elements”) are actively researched and developed because they can emit light with high luminance when driven at a low voltage.
  • An organic electroluminescent element has an organic layer between a pair of electrodes, and electrons injected from the cathode and holes injected from the anode recombine in the organic layer, and the generated exciton energy is used for light emission. To do.
  • Patent Document 1 discloses the use of a benzonitrile-based charge transport material having a substituent at the ortho position for further improving the light emission efficiency of the device and reducing the driving voltage.
  • Patent Documents 2 to 4 describe organic electroluminescent devices using an aromatic compound having a specific structure as a charge transport material.
  • Non-patent Document 1 describes a molecular model calculated as a nonlinear optical material, but there is no description of an actual compound synthesis example, and the molecule There is no description or suggestion of applying the model compounds to charge transport materials or organic electroluminescent devices.
  • Patent Documents 1 to 4 have problems that the luminous efficiency decreases when stored at high temperatures, the chromaticity changes greatly, and the durability deteriorates. This has been newly clarified by the study by the present inventors, and an improvement has been demanded. In particular, there is a demand for an element whose characteristics do not change even after high-temperature storage, such as in-vehicle use.
  • the present inventors use the charge transport material having the m-kinkphenyl structure of the present invention to suppress the decrease in luminous efficiency after storage of the device at a high temperature, and the chromaticity. It has been found that an organic electroluminescence device satisfying all of the suppression of change and the improvement of durability at a high level is provided.
  • an object of the present invention is to provide an organic electroluminescent device that satisfies all of the suppression of a decrease in luminous efficiency after storage of the device at a high temperature, the suppression of chromaticity change, and the improvement of durability at a high level. is there.
  • Another object of the present invention is to provide a compound and a charge transport material useful for the organic electroluminescence device described above.
  • another object of the present invention is to provide a light emitting device, a display device, and a lighting device including the organic electroluminescent element of the present invention.
  • An organic electroluminescent device having a pair of electrodes consisting of an anode and a cathode on a substrate, and at least one organic layer including a light emitting layer between the electrodes, Organic electroluminescence comprising at least one phosphorescent material in the light emitting layer, and at least one of the at least one organic layer comprising a compound having an m-kinkphenyl structure represented by the following general formula (1) element.
  • R 1 represents an alkyl group or an aryl group. However, the aryl group represented by R 1 does not have a condensed ring and may have an alkyl group or a cyano group. When R 1 there are a plurality, the plurality of R 1 may be the same or different.
  • m 1 is the number of cyano groups substituted in the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 10 or less.
  • n 1 is the number of R 1 substituted with the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 22 or less.
  • m 1 + n 1 is an integer of 1 or more and 22 or less.
  • the compound represented by the general formula (1) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 1 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  • R 2 represents an alkyl group or an aryl group. However, the aryl group represented by R 2 does not have a condensed ring and may have an alkyl group or a cyano group. When R 2 there are a plurality, the plurality of R 2 may be the same or different.
  • m 2 is the number of cyano groups substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 14 or less.
  • n 2 is the number of R 2 substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 30 or less.
  • m 2 + n 2 is 1 to 30 integer.
  • the compound represented by the general formula (2) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 2 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  • R 3 represents an alkyl group or an aryl group. However, the aryl group represented by R 3 does not have a condensed ring and may have an alkyl group or a cyano group. When R 3 there are a plurality, the plurality of R 3 may be the same or different.
  • m 3 is the number of cyano groups substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 14 or less.
  • n 3 is the number of R 3 substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 30 or less.
  • n 3 is an integer of 1 or more and 30 or less.
  • the compound represented by the general formula (3) does not have a benzene ring substituted with 3 or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 3 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  • Z 1 and Z 2 each independently represent a carbon atom or a nitrogen atom.
  • a 1 represents an atomic group that forms a 5- or 6-membered heterocycle with Z 1 and a nitrogen atom.
  • B 1 represents an atomic group that forms a 5- or 6-membered ring with Z 2 and a carbon atom.
  • (XY) represents a monoanionic bidentate ligand.
  • n E1 represents an integer of 1 to 3.
  • a E1 to A E8 each independently represents a nitrogen atom or C—R E.
  • R E represents a hydrogen atom or a substituent.
  • (XY) represents a monoanionic bidentate ligand.
  • n E2 represents an integer of 1 to 3.
  • R 1a to R 1k each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, —CN, a perfluoroalkyl group, a trifluorovinyl group, —CO 2 R, —C (O) R, —NR 2 , —NO 2 , —OR, a halogen atom, an aryl group, or a heteroaryl group, which may further have a substituent Z.
  • Each R independently represents a hydrogen atom, an alkyl group, a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group. Any two of R 1a to R 1k may be bonded to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring may further have a substituent Z.
  • Z is each independently a halogen atom, —R ′′, —OR ′′, —N (R ′′) 2 , —SR ′′, —C (O) R ′′, —C (O) OR ′′, —C (O) N (R ") 2, -CN , -NO 2, -SO 2, -SOR", - SO 2 R “, or -SO 3 R” represents, R "are each independently a hydrogen atom, an alkyl group, A perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group is represented.
  • (XY) represents a monoanionic bidentate ligand.
  • n E6 represents an integer of 1 to 3.
  • An organic layer adjacent to the light emitting layer is provided between the light emitting layer and the cathode, and the organic layer contains a compound represented by any one of the general formulas (1) to (3).
  • the electron injection layer adjacent to the cathode between the pair of electrodes, the electron injection layer containing the compound represented by any one of the general formulas (1) to (3) [1]
  • the organic electroluminescence device as described in any one of [8].
  • a charge transport material represented by the following general formula (1) [15] A charge transport material represented by the following general formula (1).
  • R 1 represents an alkyl group or an aryl group. However, the aryl group represented by R 1 does not have a condensed ring and may have an alkyl group or a cyano group. When R 1 there are a plurality, the plurality of R 1 may be the same or different.
  • m 1 is the number of cyano groups substituted in the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 10 or less.
  • n 1 is the number of R 1 substituted with the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 22 or less.
  • m 1 + n 1 is an integer of 1 or more and 22 or less.
  • the compound represented by the general formula (1) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 1 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  • R 2 represents an alkyl group or an aryl group. However, the aryl group represented by R 2 does not have a condensed ring and may have an alkyl group or a cyano group. When R 2 there are a plurality, the plurality of R 2 may be the same or different.
  • m 2 is the number of cyano groups substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 14 or less.
  • n 2 is the number of R 2 substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 30 or less.
  • m 2 + n 2 is 1 to 30 integer.
  • the compound represented by the general formula (2) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 2 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  • R 3 represents an alkyl group or an aryl group. However, the aryl group represented by R 3 does not have a condensed ring and may have an alkyl group or a cyano group. When R 3 there are a plurality, the plurality of R 3 may be the same or different.
  • m 3 is the number of cyano groups substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 14 or less.
  • n 3 is the number of R 3 substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 30 or less.
  • n 3 is an integer of 1 or more and 30 or less.
  • the compound represented by the general formula (3) does not have a benzene ring substituted with 3 or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 3 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  • a composition comprising the charge transport material according to any one of [15] to [17].
  • a thin film comprising the charge transport material according to any one of [15] to [17].
  • R 1 represents an alkyl group or an aryl group. However, the aryl group represented by R 1 does not have a condensed ring and may have an alkyl group or a cyano group. When R 1 there are a plurality, the plurality of R 1 may be the same or different.
  • m 1 is the number of cyano groups substituted in the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 10 or less.
  • n 1 is the number of R 1 substituted with the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 22 or less.
  • m 1 + n 1 is an integer of 1 or more and 22 or less.
  • the compound represented by the general formula (1) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 1 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  • R 2 represents an alkyl group or an aryl group. However, the aryl group represented by R 2 does not have a condensed ring and may have an alkyl group or a cyano group. When R 2 there are a plurality, the plurality of R 2 may be the same or different.
  • m 2 is the number of cyano groups substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 14 or less.
  • n 2 is the number of R 2 substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 30 or less.
  • m 2 + n 2 is 1 to 30 integer.
  • the compound represented by the general formula (2) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 2 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  • R 3 represents an alkyl group or an aryl group. However, the aryl group represented by R 3 does not have a condensed ring and may have an alkyl group or a cyano group. When R 3 there are a plurality, the plurality of R 3 may be the same or different.
  • m 3 is the number of cyano groups substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 14 or less.
  • n 3 is the number of R 3 substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 30 or less.
  • n 3 is an integer of 1 or more and 30 or less.
  • the compound represented by the general formula (3) does not have a benzene ring substituted with 3 or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 3 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  • an organic electroluminescent device that satisfies all of the suppression of a decrease in luminous efficiency after storage of the device at a high temperature, the suppression of chromaticity change, and the improvement of durability at a high level.
  • a hydrogen atom includes an isotope (deuterium atom and the like), and an atom constituting a substituent further includes the isotope.
  • the substituent when the term “substituent” is used, the substituent may be substituted.
  • the term “alkyl group” in the present invention includes an alkyl group substituted with a fluorine atom (for example, trifluoromethyl group) and an alkyl group substituted with an aryl group (for example, triphenylmethyl group).
  • alkyl group having 1 to 6 carbon atoms it means that all groups including substituted ones have 1 to 6 carbon atoms.
  • the substituent group A, the substituent group B, and the substituent Z ′ are defined as follows.
  • An alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as vinyl , Allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such
  • pyridyloxy pyrazyloxy, pyrimidyloxy, quinolyloxy and the like
  • an acyl group preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms.
  • alkoxycarbonyl group preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxy Carbonyl, etc.
  • aryloxycarbonyl group preferably carbon
  • the number of primes is 7 to 30, more preferably 7 to 20, and particularly preferably 7 to 12, and examples thereof include phenyloxycarbonyl.
  • An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy, benzoyloxy, etc.), an acylamino group (preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably 2-10 carbon atoms, and examples thereof include acetylamino, benzoylamino and the like, and alkoxycarbonylamino groups (preferably having 2-2 carbon atoms).
  • an aryloxycarbonylamino group preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl And sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino).
  • an aryloxycarbonylamino group preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl And sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino).
  • a sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenyl Sulfamoyl, etc.), carbamoyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, Phenylcarbamoyl etc.), alkylthio group ( Preferably, it has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio, ethylthio, etc.), an arylthio group (preferably 6 to 30 carbon atoms).
  • a sulfinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl.
  • a ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid
  • An amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenyl phosphoric acid amide), a hydroxy group , Mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group ( An aromatic heterocyclic group is also included, preferably having 1 to 30 carbon atoms, more preferably
  • Is for example, a nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom, selenium atom, tellurium atom, specifically pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, pyrrolyl, pyrazolyl, triazolyl, imidazolyl, oxazolyl, thiazolyl, And isoxazolyl, isothiazolyl, quinolyl, furyl, thienyl, selenophenyl, tellurophenyl, piperidyl, piperidino, morpholino, pyrrolidyl, pyrrolidino, benzoxazolyl, benzoimidazolyl, benzothiazolyl, carbazolyl group, azepinyl group, silolyl group and the like.
  • a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl).
  • a aryloxy group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyloxy, triphenylsilyloxy, etc.), phosphoryl group (for example, A diphenylphosphoryl group, a dimethylphosphoryl group, etc.).
  • These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group A described above.
  • alkyl group preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.
  • alkenyl groups preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as vinyl , Allyl, 2-butenyl, 3-pentenyl, etc.
  • alkynyl group preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as propargyl , 3-pentynyl, etc.
  • aryl groups preferably having 6 to 30 carbon
  • alkyl group preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, such as methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, n- Butyl, neopentyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl group (preferably having 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms, such as vinyl)
  • Aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, such as phenyl group, naphthyl group, anthracenyl group, tetracenyl group, pyrenyl group, perylenyl group, triphenylenyl group,
  • the organic electroluminescent device of the present invention is an organic electroluminescent device having a pair of electrodes comprising an anode and a cathode and at least one organic layer including a light emitting layer between the electrodes on the substrate, wherein the light emitting layer And at least one of the at least one organic layer contains a compound having an m-kinkphenyl structure represented by the following general formula (1).
  • this invention relates also to the compound represented by General formula (1).
  • the compound represented by the general formula (1) is preferably a compound represented by the following general formula (2) or (3).
  • R 1 represents an alkyl group or an aryl group. However, the aryl group represented by R 1 does not have a condensed ring and may have an alkyl group or a cyano group. When R 1 there are a plurality, the plurality of R 1 may be the same or different.
  • m 1 is the number of cyano groups substituted in the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 10 or less.
  • n 1 is the number of R 1 substituted with the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 22 or less.
  • m 1 + n 1 is an integer of 1 or more and 22 or less.
  • the compound represented by the general formula (1) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 1 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  • the alkyl group represented by R 1 is a linear, branched, or cyclic alkyl group and does not have a substituent such as a fluorine atom or a cyano group. That is, the alkyl group represented by R 1 is an unsubstituted alkyl group.
  • the alkyl group represented by R 1 is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and still more preferably an alkyl group having 1 to 6 carbon atoms. .
  • the alkyl group represented by R 1 is particularly preferably a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, i-butyl group, n-pentyl group, neopentyl group.
  • Group, t-amyl group, s-isoamyl group, cyclopentyl group, n-hexyl group and cyclohexyl group most preferably methyl group, i-propyl group, n-butyl group and t-butyl group One of them.
  • the aryl group represented by R 1 is an aryl group having no condensed ring such as a naphthalene ring or an anthracene ring.
  • the aryl group represented by R 1 does not include a heteroaryl group containing a hetero atom such as a nitrogen atom, a sulfur atom, or an oxygen atom. That is, the aryl group represented by R 1 does not have a heterocycle.
  • the aryl group represented by R 1 is typically an aromatic hydrocarbon ring carbon atom in which one monocyclic aromatic hydrocarbon or a plurality of monocyclic aromatic hydrocarbons are connected to each other by a single bond.
  • the aromatic ring contained in the aryl group represented by R 1 is preferably a benzene ring.
  • the aryl group represented by R 1 may be substituted with the aforementioned alkyl group or cyano group.
  • the aryl group represented by R 1 is preferably a phenyl group, a biphenyl group, a terphenyl group, a quarterphenyl group, or a kinkphenyl group, which may be substituted with an alkyl group or a cyano group, and more preferably an alkyl group.
  • the aryl group represented by R 1 includes a plurality of benzene rings, the plurality of benzene rings are preferably linked at the meta position (m-).
  • the preferred range of the alkyl group that may be substituted on the aryl group represented by R 1 is the same as the preferred range of the alkyl group represented by R 1 described above.
  • m 1 is the number of cyano groups substituted in the m-kinkphenyl structure in the general formula (1), that is, five benzene rings linked at the meta position shown as the structural formula in the general formula (1), Represents an integer of 0 to 10.
  • the substitution referred to here means a state in which any one hydrogen atom on the five benzene rings is replaced by a cyano group, and the cyano group optionally substituted by the aryl group represented by R 1 described above. Is not included in the number of m 1 . Further, as will be described later, three or more cyano groups are not substituted on any one of the five benzene rings.
  • At least one cyano group substituted on the m-kinkphenyl structure in the general formula (1) is present from the viewpoint of charge transportability and chemical stability (that is, m 1 is 1 or more and 10 or less. preferably of an integer that) is, more preferably m 1 is 1 to 5 integer, more preferably from 1 to 3 of an integer.
  • n 1 is the number of R 1 substituted in the m-kinkphenyl structure in the general formula (1), that is, five benzene rings linked at the meta position shown as the structural formula in the general formula (1), An integer from 0 to 22 is represented.
  • n 1 is preferably an integer of 1 to 5 and more preferably an integer of 1 to 3 from the viewpoint of charge transportability and chemical stability.
  • the compound represented by the general formula (1) has at least one cyano group substituted on the benzene ring.
  • the cyano group referred to here is not particularly limited as long as it is substituted on the benzene ring, and may be one of the cyano groups counted by m 1 or the benzene ring in the aryl group represented by R 1.
  • a cyano group substituted with may be used.
  • n 1 is an integer of 1 or more and 22 or less.
  • m 1 + n 1 is preferably an integer of 2 to 8, more preferably an integer of 3 to 6.
  • the compound represented by the general formula (1) does not have a benzene ring substituted with 3 or more cyano groups. This is because if three or more cyano groups are substituted on one benzene ring, the chemical stability of the compound is remarkably lowered, and this is one of the causes of deterioration in performance when the device is stored at high temperature. That is, in the compound represented by the general formula (1), the number of cyano groups substituted on one benzene ring is 2 or less, and 0 or 1 is preferable from the viewpoint of chemical stability.
  • the sum of the number of benzene rings in the compound represented by the general formula (1) and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  • the compound represented by the general formula (1) has a cyano group and R 1 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring falls within the above range.
  • the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is preferably 9 or more and 17 or less, and more preferably 9 or more and 14 or less.
  • the benzene ring is connected at the meta position (m-) from the viewpoint of the lowest excited triplet (T 1 ) energy and chemical stability. It is particularly preferable that all benzene rings are linked at the meta position (m-).
  • the number of benzene rings in the compound represented by the general formula (1) is preferably 5 or more and 19 or less, more preferably 6 or more and 13 or less, and still more preferably 6 or more and 10 or less.
  • the number of cyano groups substituted on the benzene ring in the compound represented by the general formula (1) is 1 or more and 12 or less. Preferably, it is 1 or more and 7 or less, more preferably 1 or more and 5 or less.
  • the compound represented by the general formula (1) is preferably a compound represented by the following general formula (2) from the viewpoint of charge transportability and chemical stability.
  • R 2 represents an alkyl group or an aryl group. However, the aryl group represented by R 2 does not have a condensed ring and may have an alkyl group or a cyano group. When R 2 there are a plurality, the plurality of R 2 may be the same or different.
  • m 2 is the number of cyano groups substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 14 or less.
  • n 2 is the number of R 2 substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 30 or less.
  • m 2 + n 2 is 1 to 30 integer.
  • the compound represented by the general formula (2) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 2 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  • the alkyl group and aryl group represented by R 2 have the same meanings as the alkyl group and aryl group represented by R 1 described above, and their preferred ranges are also the same.
  • m 2 is the number of cyano groups substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), that is, the seven benzene rings linked at the meta position shown as the structural formula in the general formula (2). Yes, and represents an integer from 0 to 14.
  • the substitution mentioned here refers to a state in which any one hydrogen atom on the seven benzene rings is replaced with a cyano group, and the benzene ring in the aryl group represented by R 2 described above is substituted.
  • the good cyano group is not included in the number of m 2 . Further, for the same reason as described above, any one of the seven benzene rings is not substituted with three or more cyano groups.
  • At least one cyano group substituted on the biphenyl-m-kinkphenyl structure in the general formula (2) is present (that is, m 2 is 1). It is preferably an integer of 14 or less, and more preferably m 2 is an integer of 1 to 7, more preferably an integer of 1 to 5.
  • n 2 is the number of R 2 substituted in the biphenyl-m-kinkphenyl structure in the general formula (2), that is, seven benzene rings linked at the meta position shown as the structural formula in the general formula (2). Yes, and represents an integer of 0 to 30.
  • n 2 is preferably an integer of 0 to 7, more preferably an integer of 0 to 4, from the viewpoint of charge transportability and chemical stability.
  • the compound represented by the general formula (2) has at least one cyano group substituted on the benzene ring for the same reason as described above.
  • the cyano group referred to here is not particularly limited as long as it is substituted on the benzene ring, and may be one of the cyano groups counted by m 2 or the benzene ring in the aryl group represented by R 2.
  • a cyano group substituted with may be used.
  • m 2 is 0, a cyano group substituted on the benzene ring is included in R 2
  • m 2 + n 2 is an integer of 1 or more and 30 or less.
  • m 2 + n 2 is preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and even more preferably an integer of 1 to 3.
  • the compound represented by the general formula (2) does not have a benzene ring substituted with 3 or more cyano groups for the same reason as described above. That is, in the compound represented by the general formula (2), the number of cyano groups substituted on one benzene ring is 2 or less, and 0 or 1 is preferable from the viewpoint of chemical stability.
  • the sum of the number of benzene rings in the compound represented by the general formula (2) and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less for the same reason as described above.
  • the compound represented by the general formula (2) has a cyano group and R 2 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring falls within the above-mentioned range.
  • a preferable range of the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is the same as the range in the general formula (1).
  • the benzene ring should be linked at the meta position (m-) from the viewpoint of the lowest excited triplet (T 1 ) energy and chemical stability. It is particularly preferred that all benzene rings are linked at the meta position (m-).
  • the number of benzene rings in the compound represented by the general formula (2) is preferably 7 or more and 19 or less, more preferably 7 or more and 13 or less, and still more preferably 7 or more and 10 or less.
  • the number of cyano groups substituted on the benzene ring in the compound represented by the general formula (2) (that is, the sum of m 2 and the number of cyano groups contained in R 2 ) is 1 or more and 12 or less. Preferably, it is 1 or more and 7 or less, more preferably 1 or more and 5 or less.
  • the compound represented by the general formula (1) is preferably a compound represented by the following general formula (3) from the viewpoint of charge transportability and chemical stability.
  • R 3 represents an alkyl group or an aryl group. However, the aryl group represented by R 3 does not have a condensed ring and may have an alkyl group or a cyano group. When R 3 there are a plurality, the plurality of R 3 may be the same or different.
  • m 3 is the number of cyano groups substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 14 or less.
  • n 3 is the number of R 3 substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 30 or less.
  • n 3 is an integer of 1 or more and 30 or less.
  • the compound represented by the general formula (3) does not have a benzene ring substituted with 3 or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 3 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  • the alkyl group and aryl group represented by R 3 have the same meanings as the alkyl group and aryl group represented by R 1 described above, and their preferred ranges are also the same.
  • m 3 is the number of cyano groups substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), that is, seven benzene rings linked at the meta position shown as the structural formula in the general formula (3). Yes, and represents an integer from 0 to 14.
  • the substitution mentioned here refers to a state in which any one hydrogen atom on the seven benzene rings is replaced with a cyano group, and the benzene ring in the aryl group represented by R 3 described above is substituted.
  • the good cyano group is not included in the number of m 3 . Further, for the same reason as described above, any one of the seven benzene rings is not substituted with three or more cyano groups.
  • m 3 is an integer of 1 or more and 14 or less
  • m 3 is 1 or more and 7 or less an integer, more preferably 1 to 5 integer.
  • n 3 is the number of R 3 substituted in the diphenyl-m-kinkphenyl structure in the general formula (3), that is, seven benzene rings linked at the meta position shown as the structural formula in the general formula (3). Yes, and represents an integer from 0 to 30.
  • n 3 is preferably an integer of 0 or more and 7 or less, more preferably an integer of 0 or more and 4 or less, from the viewpoint of charge transportability and chemical stability.
  • the compound represented by the general formula (3) has at least one cyano group substituted on the benzene ring for the same reason as described above.
  • the cyano group referred to here is not particularly limited as long as it is substituted on the benzene ring, and may be one of the cyano groups counted by m 3 or the benzene ring in the aryl group represented by R 3.
  • a cyano group substituted with may be used.
  • m 3 is 0, a cyano group substituted on the benzene ring is included in R 3
  • m 3 + n 3 is an integer of 1 to 30.
  • m 3 + n 3 is preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, and further preferably an integer of 1 or more and 3 or less.
  • the compound represented by the general formula (3) does not have a benzene ring substituted with 3 or more cyano groups for the same reason as described above. That is, in the compound represented by the general formula (3), the number of cyano groups substituted on one benzene ring is 2 or less, and 0 or 1 is preferable from the viewpoint of chemical stability.
  • the sum of the number of benzene rings in the compound represented by the general formula (3) and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less for the same reason as described above.
  • the compound represented by the general formula (3) has a cyano group and R 3 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring falls within the above-mentioned range.
  • a preferable range of the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is the same as the range in the general formula (1).
  • the benzene ring should be linked at the meta position (m-) from the viewpoint of the lowest excited triplet (T 1 ) energy and chemical stability. It is particularly preferable that all benzene rings are linked at the meta position (m-).
  • the number of benzene rings in the compound represented by the general formula (3) is preferably 7 or more and 19 or less, more preferably 7 or more and 13 or less, and still more preferably 7 or more and 10 or less.
  • the number of cyano groups substituted on the benzene ring in the compound represented by the general formula (3) is 1 or more and 12 or less. Preferably, it is 1 or more and 7 or less, more preferably 1 or more and 5 or less.
  • the compound represented by any one of the general formulas (1) to (3) is a compound consisting of only a carbon atom, a hydrogen atom and a nitrogen atom. Thereby, the durability is improved even after the element is stored at a high temperature.
  • the molecular weight of the compound represented by any one of the general formulas (1) to (3) is usually 400 or more and 1500 or less, preferably 450 or more and 1200 or less, more preferably 500 or more and 1100 or less, and 600 More preferably, it is 1000 or less.
  • the molecular weight is 450 or more, it is advantageous for forming a high-quality amorphous thin film, and when the molecular weight is 1200 or less, the solubility and sublimation property are improved, which is advantageous for improving the purity of the compound.
  • the compound represented by any one of the general formulas (1) to (3) is used as a host material for a light emitting layer of an organic electroluminescent device or a charge transport material for a layer adjacent to the light emitting layer,
  • the energy gap the light emitting material is a phosphorescent light emitting material
  • the minimum excited triplet (T 1 ) energy in a thin film state is large, which prevents the light emission from being quenched and is advantageous for improving the efficiency.
  • the energy gap and T 1 energy are not too large.
  • the T 1 energy in the film state of the compound represented by any one of the general formulas (1) to (3) is preferably 2.39 eV (55 kcal / mol) or more and 3.51 eV (80 kcal / mol) or less. 2.52 eV (58 kcal / mol) to 3.25 eV (75 kcal / mol), more preferably 2.65 eV (61 kcal / mol) to 3.04 eV (70 kcal / mol). .
  • the T 1 energy is preferably in the above range.
  • the T 1 energy can be obtained from the short wavelength end of a phosphorescence emission spectrum of a thin film of material. For example, a material is deposited on a cleaned quartz glass substrate to a film thickness of about 50 nm by a vacuum deposition method, and the phosphorescence emission spectrum of the thin film is measured under liquid nitrogen temperature F-7000 Hitachi Spectrofluorimeter (Hitachi High Technologies). Use to measure.
  • the T 1 energy can be obtained by converting the rising wavelength on the short wavelength side of the obtained emission spectrum into energy units.
  • the glass transition temperature (Tg) of the compound represented by any one of the general formulas (1) to (3) is from the viewpoint of stably operating the organic electroluminescence device against heat generated during high temperature driving or during device driving. It is preferably 100 ° C. or higher and 400 ° C. or lower, more preferably 120 ° C. or higher and 400 ° C. or lower, and still more preferably 140 ° C. or higher and 400 ° C. or lower.
  • the purity of the compound represented by any one of the general formulas (1) to (3) is low, impurities work as a charge transport trap or promote deterioration of the device.
  • the purity can be measured by, for example, high performance liquid chromatography (HPLC), and the area ratio of the compound represented by any one of the general formulas (1) to (3) when detected with a light absorption intensity of 254 nm is preferably 95. It is 0% or more, more preferably 97.0% or more, particularly preferably 99.0% or more, and most preferably 99.9% or more.
  • a part or all of the hydrogen atoms of the compound represented by any one of the general formulas (1) to (3) are deuterium atoms.
  • the material substituted with can also be preferably used as a charge transport material.
  • the compounds exemplified as the compounds represented by any one of the above general formulas (1) to (3) can be synthesized by the method described in, for example, JP-A-2007-266598.
  • the compound represented by any one of the general formulas (1) to (3) is not limited in its use, and may be contained in any layer in the organic layer.
  • the compound represented by any one of the general formulas (1) to (3) is adjacent to the light emitting layer between the light emitting layer and the light emitting layer and the cathode.
  • the organic layer (the cathode side layer adjacent to the light emitting layer) and the electron injection layer adjacent to the cathode on the light emitting layer side are preferably contained in the light emitting layer and the cathode side layer adjacent to the light emitting layer. More preferably, it is contained in any one of the above, and it is more preferred that it is contained in the light emitting layer.
  • the compound represented by any one of the general formulas (1) to (3) may be contained in both the light emitting layer and the cathode side layer adjacent to the light emitting layer.
  • the compound represented by any one of the general formulas (1) to (3) of the present invention is the light emitting layer.
  • the content is preferably 0.1 to 99% by mass, more preferably 1 to 97% by mass, and still more preferably 10 to 96% by mass with respect to the total mass.
  • the compound represented by any one of the general formulas (1) to (3) is further contained in a layer other than the light emitting layer, it is contained in an amount of 70 to 100% by mass with respect to the total mass of the layer other than the light emitting layer. And more preferably 85 to 100% by mass.
  • the present invention also relates to a charge transport material represented by the general formula (1).
  • the charge transport material represented by the general formula (1) is preferably a charge transport material represented by the general formula (2) or (3).
  • the compound represented by the general formula (1) and the charge transport material of the present invention are preferably used for organic electronic elements such as electrophotography, organic transistors, organic photoelectric conversion elements (energy conversion applications, sensor applications, etc.), and organic electroluminescence elements. It can be used and is particularly preferably used for an organic electroluminescent device.
  • composition containing the charge transport material of the present invention also relates to a composition comprising the charge transport material.
  • the content of the compound represented by any one of the general formulas (1) to (3) is preferably 30 to 99% by mass with respect to the total solid content in the composition, The content is more preferably 50 to 97% by mass, and further preferably 70 to 96% by mass.
  • Other components that may be contained in the composition of the present invention may be organic or inorganic, and as organic materials, materials described as host materials, fluorescent light emitting materials, phosphorescent light emitting materials, and hydrocarbon materials described later can be applied. A host material, a phosphorescent material, and a hydrocarbon material are preferable.
  • composition of the present invention can form an organic layer of an organic electroluminescence device by a dry film forming method such as a vapor deposition method or a sputtering method, or a wet film forming method such as a transfer method or a printing method.
  • a dry film forming method such as a vapor deposition method or a sputtering method
  • a wet film forming method such as a transfer method or a printing method.
  • the present invention also relates to a thin film containing a charge transport material represented by any one of the general formulas (1) to (3).
  • the thin film of the present invention can be formed by using the composition of the present invention by a dry film forming method such as a vapor deposition method or a sputtering method, or a wet film forming method such as a transfer method or a printing method.
  • the thickness of the thin film may be any thickness depending on the application, but is preferably 0.1 nm to 1 mm, more preferably 0.5 nm to 1 ⁇ m, still more preferably 1 nm to 200 nm, and particularly preferably 1 nm to 100 nm. is there.
  • the organic electroluminescent element of the present invention is an organic electroluminescent device having a pair of electrodes comprising an anode and a cathode and at least one organic layer including a light emitting layer between the electrodes on the substrate, wherein the light emitting layer And at least one of the at least one organic layer contains a compound represented by any one of the general formulas (1) to (3) of the present invention.
  • at least one of the pair of electrodes, the anode and the cathode is preferably transparent or translucent.
  • Examples of the organic layer include a hole injection layer, a hole transport layer, a block layer (such as a hole block layer and an exciton block layer), and an electron transport layer in addition to the light emitting layer.
  • a plurality of these organic layers may be provided, and when a plurality of layers are provided, they may be formed of the same material, or may be formed of different materials for each layer.
  • FIG. 1 an example of a structure of the organic electroluminescent element which concerns on this invention is shown.
  • the organic electroluminescent element 10 of FIG. 1 has an organic layer including a light emitting layer 6 between a pair of electrodes (anode 3 and cathode 9) on a substrate 2.
  • As the organic layer a hole injection layer 4, a hole transport layer 5, a light emitting layer 6, a hole block layer 7 and an electron transport layer 8 are laminated in this order from the anode side 3.
  • Anode / hole transport layer / light emitting layer / electron transport layer / cathode Anode / hole transport layer / light emitting layer / block layer / electron transport layer / cathode, Anode / hole transport layer / light emitting layer / block layer / electron transport layer / electron injection layer / cathode, Anode / hole injection layer / hole transport layer / light emitting layer / block layer / electron transport layer / cathode, Anode / hole injection layer / hole transport layer / light emitting layer / block layer / electron transport layer / cathode, Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode, Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode, Anode / hole injection layer / hole transport layer / light emitting layer / block layer / electron transport
  • the element configuration, the substrate, the cathode, and the anode of the organic electroluminescence element are described in detail in, for example, Japanese Patent Application Laid-Open No. 2008-270736, and the matters described in the publication can be applied to the present invention.
  • the substrate used in the present invention is preferably a substrate that does not scatter or attenuate light emitted from the organic layer.
  • an organic material it is preferable that it is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, and workability.
  • the anode usually only needs to have a function as an electrode for supplying holes to the organic layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials.
  • the anode is usually provided as a transparent anode.
  • the cathode usually has a function as an electrode for injecting electrons into the organic layer, and there is no particular limitation on the shape, structure, size, etc., and it is known depending on the use and purpose of the light emitting device.
  • the electrode material can be selected as appropriate.
  • Organic layer in the present invention will be described.
  • each organic layer is preferably formed by any of dry film forming methods such as vapor deposition and sputtering, and solution coating methods such as transfer, printing, spin coating, and bar coating. Can be formed. It is preferable that at least one of the organic layers is formed by a solution coating method.
  • the light emitting layer receives holes from the anode, hole injection layer or hole transport layer and receives electrons from the cathode, electron injection layer or electron transport layer when an electric field is applied, and provides a field for recombination of holes and electrons. And a layer having a function of emitting light.
  • the light emitting layer in the organic electroluminescent element of the present invention contains at least one phosphorescent material.
  • Luminescent material in addition to at least one phosphorescent light-emitting material contained in the light-emitting layer, a fluorescent light-emitting material or a phosphorescent light-emitting material different from the phosphorescent light-emitting material contained in the light-emitting layer can be used as the light-emitting material. Details of these fluorescent materials and phosphorescent materials are described in, for example, paragraph numbers [0100] to [0164] of JP-A-2008-270736 and paragraph numbers [0088] to [0090] of JP-A-2007-266458. The matters described in these publications can be applied to the present invention.
  • Examples of phosphorescent light-emitting materials that can be used in the present invention include US Pat. / 19373A2, JP-A No. 2001-247859, JP-A No. 2002-302671, JP-A No. 2002-117978, JP-A No. 2003-133074, JP-A No. 2002-1235076, JP-A No. 2003-123984, JP-A No. 2002-170684, EP No. 121157, JP-A No.
  • Examples of such a light emitting material include Ir complex, Pt complex, Cu complex, Re complex, W complex, Rh complex, Ru complex, Pd complex, Os complex, Eu complex, Tb complex, Gd.
  • Examples include phosphorescent metal complex compounds such as complexes, Dy complexes, and Ce complexes.
  • an Ir complex, a Pt complex, or a Re complex among which an Ir complex or a Pt complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond. Or Re complexes are preferred. Furthermore, from the viewpoints of luminous efficiency, driving durability, chromaticity, etc., an Ir complex and a Pt complex are particularly preferable, and an Ir complex is most preferable.
  • These phosphorescent metal complex compounds are preferably contained in the light emitting layer together with the compound represented by any one of the general formulas (1) to (3).
  • an iridium complex represented by the following general formula (E-1) or a platinum complex represented by the following general formula (C-1) is used as the phosphorescent material contained in the light emitting layer in the present invention. It is preferable.
  • Z 1 and Z 2 each independently represent a carbon atom or a nitrogen atom.
  • a 1 represents an atomic group that forms a 5- or 6-membered heterocycle with Z 1 and a nitrogen atom.
  • B 1 represents an atomic group that forms a 5- or 6-membered ring with Z 2 and a carbon atom.
  • (XY) represents a monoanionic bidentate ligand.
  • n E1 represents an integer of 1 to 3.
  • n E1 represents an integer of 1 to 3, preferably 2 or 3.
  • Z 1 and Z 2 each independently represent a carbon atom or a nitrogen atom.
  • Z 1 and Z 2 are preferably carbon atoms.
  • a 1 represents an atomic group that forms a 5- or 6-membered heterocycle with Z 1 and a nitrogen atom.
  • Examples of the 5- or 6-membered heterocycle containing A 1 , Z 1 and a nitrogen atom include a pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, triazole ring, oxadiazole Ring, thiadiazole ring and the like.
  • the 5- or 6-membered heterocycle formed by A 1 , Z 1 and a nitrogen atom is preferably a pyridine ring, a pyrazine ring, an imidazole ring, or a pyrazole.
  • the 5- or 6-membered heterocycle formed by the A 1 , Z 1 and the nitrogen atom may have a substituent, and as the substituent on the carbon atom, the substituent group A is on the nitrogen atom.
  • the substituent group B can be applied as the substituent.
  • Preferred substituents on carbon are alkyl groups, perfluoroalkyl groups, aryl groups, aromatic heterocyclic groups, dialkylamino groups, diarylamino groups, alkoxy groups, cyano groups, and fluorine atoms.
  • the substituent is appropriately selected for controlling the emission wavelength and potential, but in the case of shortening the wavelength, an electron donating group, a fluorine atom, and an aromatic ring group are preferable.
  • an electron donating group, a fluorine atom, and an aromatic ring group are preferable.
  • an alkyl group, a dialkylamino group, an alkoxy group, A fluorine atom, an aryl group, an aromatic heterocyclic group and the like are selected.
  • an electron withdrawing group is preferable, and for example, a cyano group, a perfluoroalkyl group, or the like is selected.
  • the substituent on nitrogen is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, and an alkyl group or an aryl group is preferable from the viewpoint of the stability of the complex.
  • the substituents may be linked to form a condensed ring, and the formed ring includes a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyrazole. Ring, thiophene ring, furan ring and the like. These formed rings may have a substituent, and examples of the substituent include the substituent on the carbon atom and the substituent on the nitrogen atom.
  • B 1 represents a 5- or 6-membered ring containing Z 2 and a carbon atom.
  • Examples of the 5- or 6-membered ring formed by B 1 , Z 2 and a carbon atom include a benzene ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, Examples include a triazole ring, an oxadiazole ring, a thiadiazole ring, a thiophene ring, and a furan ring.
  • a 5- or 6-membered ring formed of B 1 , Z 2 and a carbon atom is preferably a benzene ring, a pyridine ring, a pyrazine ring, an imidazole ring, or a pyrazole.
  • the 5- or 6-membered ring formed of B 1 , Z 2 and a carbon atom may have a substituent, and the substituent group A is a substituent on a nitrogen atom as the substituent on the carbon atom.
  • the substituent group B can be applied.
  • Preferred substituents on carbon are alkyl groups, perfluoroalkyl groups, aryl groups, aromatic heterocyclic groups, dialkylamino groups, diarylamino groups, alkoxy groups, cyano groups, and fluorine atoms.
  • the substituent is appropriately selected for controlling the emission wavelength and potential, but in the case of increasing the wavelength, an electron donating group and an aromatic ring group are preferable, for example, an alkyl group, a dialkylamino group, an alkoxy group, an aryl group, An aromatic heterocyclic group or the like is selected.
  • an electron withdrawing group is preferable, and for example, a fluorine atom, a cyano group, a perfluoroalkyl group, and the like are selected.
  • the substituent on nitrogen is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, and an alkyl group or an aryl group is preferable from the viewpoint of the stability of the complex.
  • the substituents may be linked to form a condensed ring, and the formed ring includes a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyrazole. Ring, thiophene ring, furan ring and the like.
  • These formed rings may have a substituent, and examples of the substituent include the substituent on the carbon atom and the substituent on the nitrogen atom.
  • a 5- or 6-membered heterocyclic substituent formed by A 1 , Z 1 and a nitrogen atom and a 5- or 6-membered substituent formed by B 1 , Z 2 and a carbon atom are linked. Then, the same condensed ring as described above may be formed.
  • (XY) represents a bidentate monoanionic ligand. Examples of bidentate monoanionic ligands are described on pages 89-90 of Lamansky et al., WO 02/15645.
  • the bidentate monoanionic ligand represented by (XY) is preferably a bidentate monoanionic ligand represented by the following general formula (L-1).
  • R L1 and R L2 each independently represent an alkyl group, an aryl group, or a heteroaryl group.
  • R L3 represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
  • the alkyl group represented by R L1 to R L3 may have a substituent, and may be saturated or unsaturated.
  • substituent in the case of having a substituent include the above-described substituent Z ′, and preferred substituent Z ′ includes a phenyl group, an aromatic heterocyclic group, a fluorine atom, a silyl group, an amino group, a cyano group, or these. And a phenyl group, a fluorine atom, and a cyano group are more preferable.
  • the alkyl group represented by R L1 to R L3 is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.
  • the aryl group represented by R L1 to R L3 may be condensed or may have a substituent.
  • substituents include the above-described substituent Z ′, and the substituent Z ′ is preferably an alkyl group or an aryl group, and more preferably an alkyl group.
  • the aryl group represented by R L1 to R L3 is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 18 carbon atoms.
  • the heteroaryl group represented by R L1 to R L3 may be condensed or may have a substituent.
  • substituent Z ′ examples include the above-described substituent Z ′, and the substituent Z ′ is preferably an alkyl group or an aryl group, and more preferably an alkyl group.
  • the heteroaryl group represented by R L1 to R L3 is preferably a heteroaryl group having 4 to 12 carbon atoms, more preferably a heteroaryl group having 4 to 10 carbon atoms.
  • R L1 and R L2 are preferably an alkyl group or an aryl group, more preferably an alkyl group or a phenyl group, and particularly preferably an alkyl group.
  • the alkyl group represented by R L1 and R L2 is preferably an alkyl group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 5 carbon atoms in total, such as a methyl group or an ethyl group N-propyl group, iso-propyl group, iso-butyl group, t-butyl group, n-butyl group, cyclohexyl group and the like, and methyl group, ethyl group, iso-butyl group, or t-butyl group is A methyl group is preferable, and a methyl group is particularly preferable.
  • R L3 is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
  • a preferred embodiment of the Ir complex represented by the general formula (E-1) is an Ir complex material represented by the general formula (E-2). Next, general formula (E-2) will be described.
  • a E1 to A E8 each independently represents a nitrogen atom or C—R E.
  • R E represents a hydrogen atom or a substituent.
  • (XY) represents a monoanionic bidentate ligand.
  • n E2 represents an integer of 1 to 3.
  • a E1 to A E8 each independently represent a nitrogen atom or C—R E.
  • R E represents a hydrogen atom or a substituent, and R E may be connected to each other to form a ring.
  • Examples of the ring formed include the same condensed rings described in the general formula (E-1).
  • Examples of the substituent represented by R E we are the same as those mentioned above substituent group A.
  • a E1 ⁇ A E4 is C-R E, if A E1 ⁇ A E4 is C-R E, preferably a hydrogen atom R E of A E3, alkyl group, aryl group, amino group, An alkoxy group, an aryloxy group, a fluorine atom, or a cyano group, more preferably a hydrogen atom, an alkyl group, an amino group, an alkoxy group, an aryloxy group, or a fluorine atom, and particularly preferably a hydrogen atom or a fluorine atom.
  • R E of A E1 , A E2 and A E4 is preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine atom or a cyano group, more preferably a hydrogen atom, An alkyl group, an amino group, an alkoxy group, an aryloxy group, or a fluorine atom, particularly preferably a hydrogen atom.
  • a E5 to A E8 are preferably C—R E , and when A E5 to A E8 are C—R E , R E is preferably a hydrogen atom, alkyl group, perfluoroalkyl group, aryl group, aromatic A heterocyclic group, a dialkylamino group, a diarylamino group, an alkyloxy group, a cyano group, or a fluorine atom, more preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group, a dialkylamino group, a cyano group, Or a fluorine atom, and more preferably a hydrogen atom, an alkyl group, a trifluoromethyl group, or a fluorine atom.
  • a E6 is preferably a nitrogen atom.
  • (X-Y) and n E2 of the general formula in (E1) (X-Y) , and has the same meaning as n E1 preferable ranges are also the same.
  • a more preferred form of the compound represented by the general formula (E-2) is a compound represented by the following general formula (E-3).
  • R T1 , R T2 , R T3 , R T4 , R T5 , R T6 and R T7 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, —CN, a perfluoroalkyl group, a trifluorovinyl group, —CO 2 R, —C (O) R, —NR 2 , —NO 2 , —OR, a halogen atom, an aryl group or a heteroaryl group, and further a substituent Z may be included.
  • Each R independently represents a hydrogen atom, an alkyl group, a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
  • A represents CR ′ or a nitrogen atom
  • R ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, —CN, a perfluoroalkyl group, a trifluorovinyl group, —CO 2 R, —C (O ) R, —NR 2 , —NO 2 , —OR, a halogen atom, an aryl group or a heteroaryl group, which may further have a substituent Z.
  • Each R independently represents a hydrogen atom, an alkyl group, a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
  • R T1 to R T7 and R ′ may be bonded to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring is cycloalkyl, aryl or heteroaryl.
  • the condensed 4- to 7-membered ring may further have a substituent Z.
  • a case where a ring is condensed with R T1 and R T7 , or R T5 and R T6 to form a benzene ring is preferable, and a case where a ring is condensed with R T5 and R T6 to form a benzene ring is particularly preferable.
  • Z is each independently a halogen atom, —R ′′, —OR ′′, —N (R ′′) 2 , —SR ′′, —C (O) R ′′, —C (O) OR ′′, —C (O) N (R ") 2, -CN , -NO 2, -SO 2, -SOR", - SO 2 R “, or -SO 3 R” represents, R "are each independently a hydrogen atom, an alkyl group, A perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group is represented.
  • (XY) represents a monoanionic bidentate ligand.
  • n E3 represents an integer of 1 to 3.
  • the alkyl group may have a substituent, may be saturated or unsaturated, and examples of the group that may be substituted include the above-described substituent Z.
  • the alkyl group represented by R T1 to R T7 and R ′ is preferably an alkyl group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 6 carbon atoms in total, such as methyl Group, ethyl group, i-propyl group, cyclohexyl group, t-butyl group and the like.
  • the cycloalkyl group may have a substituent, may be saturated or unsaturated, and examples of the group that may be substituted include the above-described substituent Z.
  • the cycloalkyl group represented by R T1 to R T7 and R ′ is preferably a cycloalkyl group having 4 to 7 ring members, more preferably a cycloalkyl group having 5 to 6 carbon atoms in total, A cyclopentyl group, a cyclohexyl group, etc. are mentioned.
  • the alkenyl group represented by R T1 to R T7 and R ′ preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms.
  • vinyl, allyl Examples include 1-propenyl, 1-isopropenyl, 1-butenyl, 2-butenyl, 3-pentenyl and the like.
  • the alkynyl group represented by R T1 to R T7 and R ′ preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms.
  • R T1 to R T7 and R ′ preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms.
  • Examples of the perfluoroalkyl group represented by R T1 to R T7 and R ′ include those in which all hydrogen atoms of the aforementioned alkyl group are replaced with fluorine atoms.
  • the aryl group represented by R T1 to R T7 and R ′ is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a tolyl group, or a naphthyl group.
  • the heteroaryl group represented by R T1 to R T7 and R ′ is preferably a heteroaryl group having 5 to 8 carbon atoms, more preferably a 5- or 6-membered substituted or unsubstituted heteroaryl group.
  • Groups such as pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, cinnolinyl, phthalazinyl, quinoxalinyl, pyrrolyl, indolyl, furyl, benzofuryl , Thienyl group, benzothienyl group, pyrazolyl group, imidazolyl group, benzimidazolyl group, triazolyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, isothiazolyl group, benzis
  • R T1 to R T7 and R ′ are preferably a hydrogen atom, an alkyl group, a cyano group, a trifluoromethyl group, a perfluoroalkyl group, a dialkylamino group, a fluoro group, an aryl group or a heteroaryl group, more preferably A hydrogen atom, an alkyl group, a cyano group, a trifluoromethyl group, a fluoro group, and an aryl group are preferable, and a hydrogen atom, an alkyl group, and an aryl group are more preferable.
  • substituent Z an alkyl group, an alkoxy group, a fluoro group, a cyano group, and a dialkylamino group are preferable, and a hydrogen atom is more preferable.
  • R T1 to R T7 and R ′ may be bonded to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring is cycloalkyl, aryl, or heteroaryl;
  • the condensed 4- to 7-membered ring may further have a substituent Z.
  • the definition and preferred range of cycloalkyl, aryl and heteroaryl formed are the same as the cycloalkyl group, aryl group and heteroaryl group defined by R T1 to R T7 and R ′.
  • A represents CR ′, and among R T1 to R T7 , and R ′, 0 to 2 are alkyl groups or phenyl groups, and the rest are all hydrogen atoms, and R T1 to R T7 , And R ′ are particularly preferably a case where 0 to 2 are alkyl groups and the rest are all hydrogen atoms.
  • n E3 is preferably 2 or 3.
  • the type of ligand in the complex is preferably composed of 1 to 2 types, more preferably 1 type.
  • the ligand consists of two types from the viewpoint of ease of synthesis.
  • (XY) has the same meaning as (XY) in formula (E-1), and the preferred range is also the same.
  • One preferred form of the compound represented by the general formula (E-3) is a compound represented by the following general formula (E-4).
  • R T1 to R T4 , A, (XY) and n E4 in the general formula (E-4) are R T1 to R T4 , A, (XY) and n E3 in the general formula (E-3).
  • the preferred range is also the same.
  • R 1 ′ to R 5 ′ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, —CN, perfluoroalkyl group, trifluorovinyl group, —CO 2 R, —C (O) R.
  • Each R independently represents a hydrogen atom, an alkyl group, a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
  • R 1 ′ to R 5 ′ may be bonded to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring is cycloalkyl, aryl, or heteroaryl;
  • the condensed 4- to 7-membered ring may further have a substituent Z.
  • Z is each independently a halogen atom, —R ′′, —OR ′′, —N (R ′′) 2 , —SR ′′, —C (O) R ′′, —C (O) OR ′′, —C (O) N (R ") 2, -CN , -NO 2, -SO 2, -SOR", - SO 2 R “, or -SO 3 R” represents, R "are each independently a hydrogen atom, an alkyl group, A perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group is represented.
  • R 1 ′ to R 5 ′ are the same as R T1 to R T7 and R ′ in formula (E-3). Further, it is particularly preferable that A represents CR ′, and 0 to 2 of R T1 to R T4 , R ′, and R 1 ′ to R 5 ′ are alkyl groups or phenyl groups, and the rest are all hydrogen atoms. More preferably, 0 to 2 of R T1 to R T4 , R ′, and R 1 ′ to R 5 ′ are alkyl groups and the rest are all hydrogen atoms.
  • Another preferred embodiment of the compound represented by the general formula (E-3) is a compound represented by the following general formula (E-5).
  • R T2 to R T6 , A, (XY) and n E5 in the general formula (E-5) are R T2 to R T6 , A, (XY) and n E3 in the general formula (E-3).
  • the preferred range is also the same.
  • R 6 ′ to R 8 ′ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, —CN, perfluoroalkyl group, trifluorovinyl group, —CO 2 R, —C (O) R , —NR 2 , —NO 2 , —OR, a halogen atom, an aryl group or a heteroaryl group, and optionally having a substituent Z.
  • Each R independently represents a hydrogen atom, an alkyl group, a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
  • R T5 , R T6 , R 6 ′ to R 8 ′ may be combined with each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring is cycloalkyl, aryl or It is a heteroaryl, and the condensed 4- to 7-membered ring may further have a substituent Z.
  • Z is each independently a halogen atom, —R ′′, —OR ′′, —N (R ′′) 2 , —SR ′′, —C (O) R ′′, —C (O) OR ′′, —C (O) N (R ") 2, -CN , -NO 2, -SO 2, -SOR", - SO 2 R “, or -SO 3 R” represents, R "are each independently a hydrogen atom, an alkyl group, A perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group is represented.
  • R 6 ′ to R 8 ′ are the same as R T1 to R T7 and R ′ in formula (E-3).
  • A represents CR ′, and among R T2 to R T6 , R ′, and R 6 ′ to R 8 ′, 0 to 2 are alkyl groups or phenyl groups, and the rest are all hydrogen atoms.
  • R T2 to R T6 , R ′, and R 6 ′ to R 8 ′ are more preferably a case where 0 to 2 are alkyl groups and the rest are all hydrogen atoms.
  • Another preferred embodiment of the compound represented by the general formula (E-1) is a case represented by the following general formula (E-6).
  • R 1a to R 1k each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, —CN, a perfluoroalkyl group, a trifluorovinyl group, —CO 2 R, —C (O) R, —NR 2 , —NO 2 , —OR, a halogen atom, an aryl group, or a heteroaryl group, which may further have a substituent Z.
  • Each R independently represents a hydrogen atom, an alkyl group, a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group. Any two of R 1a to R 1k may be bonded to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring is cycloalkyl, aryl, or heteroaryl; The 7-membered ring may further have a substituent Z. Of these, the case where R 1j and R 1k are linked to form a single bond is particularly preferred.
  • Z is each independently a halogen atom, —R ′′, —OR ′′, —N (R ′′) 2 , —SR ′′, —C (O) R ′′, —C (O) OR ′′, —C (O) N (R ") 2, -CN , -NO 2, -SO 2, -SOR", - SO 2 R “, or -SO 3 R” represents, R "are each independently a hydrogen atom, an alkyl group, A perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group is represented.
  • (XY) represents a monoanionic bidentate ligand.
  • n E6 represents an integer of 1 to 3.
  • R 1a to R 1k are the same as those in R T1 to R T7 and R ′ in the general formula (E-3). Further, it is particularly preferable that 0 to 2 of R 1a to R 1k are alkyl groups or phenyl groups and the rest are all hydrogen atoms, and 0 to 2 of R 1a to R 1k are alkyl groups and the rest are all hydrogen atoms. More preferably, it is an atom.
  • the preferred range of (XY) and n E6 is the same as (XY) and n E3 in general formula (E-3).
  • a more preferable form of the compound represented by the general formula (E-6) is a case represented by the following general formula (E-7).
  • R 1a ⁇ R 1i definition and preferable ranges of R 1a ⁇ R 1i are the same as R 1a ⁇ R 1i in the formula (E-6). Further, it is particularly preferable that 0 to 2 of R 1a to R 1i are alkyl groups or aryl groups and the rest are all hydrogen atoms.
  • the definitions and preferred ranges of (XY) and n E7 are the same as (XY) and n E3 in general formula (E-3).
  • the compounds exemplified as the compound represented by the general formula (E-1) can be synthesized by the method described in JP2009-99783A, various methods described in US Pat. No. 7,279,232 and the like. After synthesis, it is preferable to purify by sublimation purification after purification by column chromatography, recrystallization or the like. By sublimation purification, not only can organic impurities be separated, but inorganic salts and residual solvents can be effectively removed.
  • the compound represented by the general formula (E-1) is contained in the light emitting layer, but its use is not limited and may be further contained in any layer in the organic layer.
  • the compound represented by the general formula (E-1) in the light emitting layer is contained in an amount of 0.1% by mass to 50% by mass with respect to the total mass of the compound generally forming the light emitting layer in the light emitting layer.
  • the content is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 40% by mass.
  • the thickness of the light emitting layer is not particularly limited, but is usually preferably 2 nm to 500 nm, and more preferably 3 nm to 200 nm, and more preferably 5 nm to 100 nm from the viewpoint of external quantum efficiency. More preferably.
  • the light emitting layer in the element of the present invention may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material.
  • the kind of the light emitting material may be one kind or two or more kinds.
  • the host material is preferably a charge transport material.
  • the host material may be one kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed.
  • the light emitting layer may contain a material that does not have charge transporting properties and does not emit light.
  • the light emitting layer may be a single layer or a multilayer of two or more layers, and each layer may contain the same light emitting material or host material, or each layer may contain a different material. When there are a plurality of light emitting layers, each of the light emitting layers may emit light with different emission colors.
  • Q 1 , Q 2 , Q 3 and Q 4 each independently represent a ligand coordinated to Pt.
  • L 1 , L 2 and L 3 are each independently Represents a single bond or a divalent linking group.
  • Q 1 , Q 2 , Q 3 and Q 4 each independently represent a ligand coordinated to Pt.
  • the bond between Q 1 , Q 2 , Q 3 and Q 4 and Pt may be any of a covalent bond, an ionic bond, a coordinate bond, and the like.
  • a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom are preferable, and in Q ⁇ 1 >, Q ⁇ 2 >, Q ⁇ 3 > and Q ⁇ 4 >
  • a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom are preferable, and in Q ⁇ 1 >, Q ⁇ 2 >, Q ⁇ 3 > and Q ⁇ 4 >
  • at least one is preferably a carbon atom, more preferably two are carbon atoms, and particularly preferably two are carbon atoms and two are nitrogen atoms.
  • Q 1 , Q 2 , Q 3 and Q 4 bonded to Pt by a carbon atom may be an anionic ligand or a neutral ligand, and the anionic ligand is a vinyl ligand, Aromatic hydrocarbon ring ligand (eg benzene ligand, naphthalene ligand, anthracene ligand, phenanthrene ligand etc.), heterocyclic ligand (eg furan ligand, thiophene ligand, pyridine) Ligand, pyrazine ligand, pyrimidine ligand, pyridazine ligand, triazine ligand, thiazole ligand, oxazole ligand, pyrrole ligand, imidazole ligand, pyrazole ligand, triazole And a condensed ring containing them (for example, quinoline ligand, benzothiazole ligand, etc.).
  • Q 1 , Q 2 , Q 3 and Q 4 bonded to Pt with a nitrogen atom may be neutral ligands or anionic ligands, and as neutral ligands, nitrogen-containing aromatic hetero Ring ligand (pyridine ligand, pyrazine ligand, pyrimidine ligand, pyridazine ligand, triazine ligand, imidazole ligand, pyrazole ligand, triazole ligand, oxazole ligand, Examples include thiazole ligands and condensed rings containing them (for example, quinoline ligands, benzimidazole ligands), amine ligands, nitrile ligands, and imine ligands.
  • nitrogen-containing aromatic hetero Ring ligand pyridine ligand, pyrazine ligand, pyrimidine ligand, pyridazine ligand, triazine ligand, imidazole
  • anionic ligands include amino ligands, imino ligands, nitrogen-containing aromatic heterocyclic ligands (pyrrole ligands, imidazole ligands, triazole ligands and condensed rings containing them) (For example, indole ligand, benzimidazole ligand, etc.)).
  • Q 1 , Q 2 , Q 3 and Q 4 bonded to Pt with an oxygen atom may be neutral ligands or anionic ligands, and neutral ligands are ether ligands, Examples include ketone ligands, ester ligands, amide ligands, oxygen-containing heterocyclic ligands (furan ligands, oxazole ligands and condensed rings containing them (benzoxazole ligands, etc.)). It is done.
  • the anionic ligand include an alkoxy ligand, an aryloxy ligand, a heteroaryloxy ligand, an acyloxy ligand, a silyloxy ligand, and the like.
  • Q 1 , Q 2 , Q 3 and Q 4 bonded to Pt with a sulfur atom may be neutral ligands or anionic ligands, and neutral ligands include thioether ligands, Examples include thioketone ligands, thioester ligands, thioamide ligands, sulfur-containing heterocyclic ligands (thiophene ligands, thiazole ligands and condensed rings containing them (such as benzothiazole ligands)). It is done.
  • the anionic ligand include an alkyl mercapto ligand, an aryl mercapto ligand, and a heteroaryl mercapto ligand.
  • Q 1 , Q 2 , Q 3 and Q 4 bonded to Pt with a phosphorus atom may be neutral ligands or anionic ligands, and neutral ligands include phosphine ligands, Examples include phosphate ester ligands, phosphite ester ligands, and phosphorus-containing heterocyclic ligands (phosphinin ligands, etc.).
  • Anionic ligands include phosphino ligands and phosphinyl ligands. And phosphoryl ligands.
  • the groups represented by Q 1 , Q 2 , Q 3, and Q 4 may have a substituent, and those listed as the substituent group A can be appropriately applied as the substituent. Moreover, substituents may be connected to each other (when Q 3 and Q 4 are connected, a Pt complex of a cyclic tetradentate ligand is formed).
  • the group represented by Q 1 , Q 2 , Q 3 and Q 4 is preferably an aromatic hydrocarbon ring ligand bonded to Pt with a carbon atom, and an aromatic heterocyclic ligand bonded to Pt with a carbon atom.
  • L 1 , L 2 and L 3 represent a single bond or a divalent linking group.
  • Divalent linking groups represented by L 1 , L 2 and L 3 include alkylene groups (methylene, ethylene, propylene, etc.), arylene groups (phenylene, naphthalenediyl), heteroarylene groups (pyridinediyl, thiophenediyl, etc.) ), Imino group (—NR L —) (such as phenylimino group), oxy group (—O—), thio group (—S—), phosphinidene group (—PR L —) (such as phenylphosphinidene group), silylene (-SiR L R L '-) ( dimethylsilylene group, a diphenylsilylene group), or the like combinations thereof.
  • examples of R L and R L ′ include an alkyl group and an aryl group. These linking groups may further have a substituent. As the substituent, those exemplified as the substituent group A can be appropriately applied. From the viewpoint of the stability of the complex and the emission quantum yield, L 1 , L 2 and L 3 are preferably a single bond, an alkylene group, an arylene group, a heteroarylene group, an imino group, an oxy group, a thio group or a silylene group.
  • a single bond, an alkylene group, an arylene group or an imino group still more preferably a single bond, an alkylene group or an arylene group, still more preferably a single bond, a methylene group or a phenylene group, still more preferably.
  • Single bond, disubstituted methylene group more preferably single bond, dimethylmethylene group, diethylmethylene group, diisobutylmethylene group, dibenzylmethylene group, ethylmethylmethylene group, methylpropylmethylene group, isobutylmethylmethylene group, diphenyl Methylene, methylphenylmethylene, cyclohexanediyl, cycl A lopentanediyl group, a fluorenediyl group, and a fluoromethylmethylene group, particularly preferably a single bond, a dimethylmethylene group, a diphenylmethylene group, and a cyclohexanediyl group.
  • platinum complexes represented by the general formula (C-1) a platinum complex represented by the following general formula (C-2) is more preferable.
  • L 21 represents a single bond or a divalent linking group.
  • a 21 and A 22 each independently represent a carbon atom or a nitrogen atom.
  • Z 21 and Z 22 each independently represent a nitrogen-containing aromatic heterocycle.
  • Z 23 and Z 24 each independently represent a benzene ring or an aromatic heterocycle.
  • L 21 has the same meaning as L 1 in formula (C-1), and the preferred range is also the same.
  • a 21 and A 22 each independently represent a carbon atom or a nitrogen atom. Of A 21, A 22, Preferably, at least one is a carbon atom, it A 21, A 22 are both carbon atoms are preferred from the standpoint of emission quantum yield stability aspects and complexes of the complex .
  • Z 21 and Z 22 each independently represent a nitrogen-containing aromatic heterocycle.
  • the nitrogen-containing aromatic heterocycle represented by Z 21 and Z 22 include a pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, triazole ring, oxadiazole ring, Examples include thiadiazole rings.
  • the ring represented by Z 21 and Z 22 is preferably a pyridine ring, a pyrazine ring, an imidazole ring or a pyrazole ring, more preferably a pyridine ring.
  • the nitrogen-containing aromatic heterocycle represented by Z 21 and Z 22 may have a substituent, and the substituent group A is a substituent on a carbon atom, and the substituent on a nitrogen atom is The substituent group B can be applied.
  • the substituent on carbon is preferably an alkyl group, a perfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diarylamino group, an alkoxy group, a cyano group, or a halogen atom.
  • the substituent is appropriately selected for controlling the emission wavelength and potential, but in the case of shortening the wavelength, an electron donating group, a fluorine atom, and an aromatic ring group are preferable.
  • an alkyl group, a dialkylamino group, an alkoxy group, A fluorine atom, an aryl group, an aromatic heterocyclic group and the like are selected.
  • an electron withdrawing group is preferable, and for example, a cyano group, a perfluoroalkyl group, or the like is selected.
  • the substituent on the nitrogen atom is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, and an alkyl group or an aryl group is preferable from the viewpoint of the stability of the complex.
  • the substituents may be linked to form a condensed ring, and the formed ring includes a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyrazole. Ring, thiophene ring, furan ring and the like.
  • Z 23 and Z 24 each independently represent a benzene ring or an aromatic heterocycle.
  • the nitrogen-containing aromatic heterocycle represented by Z 23 and Z 24 include a pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, triazole ring, oxadi Examples include an azole ring, a thiadiazole ring, a thiophene ring, and a furan ring.
  • the ring represented by Z 23 and Z 24 is preferably a benzene ring, a pyridine ring, a pyrazine ring, an imidazole ring, a pyrazole ring, or a thiophene ring, More preferred are a benzene ring, a pyridine ring and a pyrazole ring, and still more preferred are a benzene ring and a pyridine ring.
  • the benzene ring and nitrogen-containing aromatic heterocycle represented by Z 23 and Z 24 may have a substituent.
  • the substituent group A is substituted on the nitrogen atom.
  • the substituent group B can be applied as the group.
  • the substituent on carbon is preferably an alkyl group, a perfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diarylamino group, an alkoxy group, a cyano group, or a halogen atom.
  • the substituent is appropriately selected for controlling the emission wavelength and potential, but in the case of increasing the wavelength, an electron donating group and an aromatic ring group are preferable, for example, an alkyl group, a dialkylamino group, an alkoxy group, an aryl group, An aromatic heterocyclic group or the like is selected.
  • an electron withdrawing group is preferable, and for example, a fluorine atom, a cyano group, a perfluoroalkyl group, and the like are selected.
  • the substituent on the nitrogen atom is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, and an alkyl group or an aryl group is preferable from the viewpoint of the stability of the complex.
  • the substituents may be linked to form a condensed ring, and the formed ring includes a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyrazole. Ring, thiophene ring, furan ring and the like.
  • platinum complexes represented by the general formula (C-2) one of more preferred embodiments is a platinum complex represented by the following general formula (C-3).
  • a 301 to A 313 each independently represent C—R or a nitrogen atom.
  • R represents a hydrogen atom or a substituent.
  • L 31 represents a single bond or a divalent linking group.
  • L 31 has the same meaning as L 21 in formula (C-2), and the preferred range is also the same.
  • a 301 to A 306 each independently represents C—R or a nitrogen atom.
  • R represents a hydrogen atom or a substituent.
  • substituent represented by R those exemplified as the substituent group A can be applied.
  • a 301 to A 306 are preferably C—R, and Rs may be connected to each other to form a ring.
  • R in A 302 and A 305 is preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine atom, or a cyano group. More preferably a hydrogen atom, an amino group, an alkoxy group, an aryloxy group, or a fluorine atom, particularly preferably a hydrogen atom or a fluorine atom, and R as A 301 , A 303 , A 304 , or A 306 is preferably a hydrogen atom.
  • a 307 , A 308 , A 309 and A 310 each independently represent C—R or a nitrogen atom.
  • R represents a hydrogen atom or a substituent. As the substituent represented by R, those exemplified as the substituent group A can be applied.
  • R is preferably a hydrogen atom, alkyl group, perfluoroalkyl group, aryl group, aromatic heterocyclic group, dialkylamino group, diarylamino Group, alkyloxy group, cyano group, halogen atom, more preferably hydrogen atom, alkyl group, perfluoroalkyl group, aryl group, dialkylamino group, cyano group, fluorine atom, more preferably hydrogen atom, alkyl group. , A trifluoromethyl group and a fluorine atom. If possible, the substituents may be linked to form a condensed ring structure.
  • a 308 is preferably a nitrogen atom.
  • the 6-membered ring formed from two carbon atoms and A 307 , A 308 , A 309 and A 310 includes a pyridine ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring. And a triazine ring, more preferably a pyridine ring, a pyrazine ring, a pyrimidine ring and a pyridazine ring, and particularly preferably a pyridine ring.
  • the 6-membered ring is a pyridine ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring (particularly preferably a pyridine ring), a hydrogen atom present at a position where a metal-carbon bond is formed as compared with a benzene ring. Since the acidity is improved, a metal complex is more easily formed, which is advantageous.
  • a 311 , A 312 and A 313 each independently represent C—R or a nitrogen atom.
  • R represents a hydrogen atom or a substituent.
  • substituent represented by R those exemplified as the substituent group A can be applied.
  • R is preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diarylamino group, an alkyl An oxy group, a cyano group, and a halogen atom, more preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group, a dialkylamino group, a cyano group, and a fluorine atom, and more preferably a hydrogen atom, an alkyl group, and trifluoro A methyl group and a fluorine atom.
  • the substituents may be linked to form a condensed ring structure.
  • the 5-membered ring formed by A 311 , A 312 and A 313 and one nitrogen atom and one carbon atom include a pyrrole ring, a pyrazole ring, an imidazole ring, a furan ring, and a thiophene ring, and more preferable.
  • the 5-membered ring is a pyrrole ring, a pyrazole ring, or an imidazole ring (more preferably, a pyrrole ring or a pyrazole ring), it is advantageous because the stability of the metal complex is improved.
  • platinum complexes represented by the general formula (C-2) one of the more preferred embodiments is a platinum complex represented by the following general formula (C-4).
  • a 401 to A 414 each independently represents C—R or a nitrogen atom.
  • R represents a hydrogen atom or a substituent.
  • L 41 represents a single bond or a divalent linking group.
  • a 401 to A 414 each independently represents C—R or a nitrogen atom.
  • R represents a hydrogen atom or a substituent.
  • a 401 to A 406 and L 41 have the same meanings as A 301 to A 306 and L 31 in formula (C-3), and preferred ranges thereof are also the same.
  • the number of nitrogen atoms is preferably 0 to 2, and more preferably 0 to 1.
  • a 408 and A 412 are preferably nitrogen atoms, and both A 408 and A 412 are more preferably nitrogen atoms.
  • R in A 408 and A 412 is preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine atom, A cyano group, more preferably a hydrogen atom, a perfluoroalkyl group, an alkyl group, an aryl group, a fluorine atom and a cyano group, and particularly preferably a hydrogen atom, a perfluoroalkyl group and a cyano group.
  • R represented by A 407 , A 409 , A 411 and A 413 is preferably a hydrogen atom, alkyl group, perfluoroalkyl group, aryl group, amino group, alkoxy group, aryloxy group, fluorine atom or cyano group, more preferably Is a hydrogen atom, a perfluoroalkyl group, a fluorine atom or a cyano group, particularly preferably a hydrogen atom or a fluorine atom.
  • R represented by A 410 and A 414 is preferably a hydrogen atom or a fluorine atom, and more preferably a hydrogen atom.
  • Rs may be connected to each other to form a ring.
  • platinum complexes represented by the general formula (C-1) another more preferable embodiment is a platinum complex represented by the following general formula (C-5).
  • L 51 represents a single bond or a divalent linking group.
  • a 51 each independently represents a carbon atom or a nitrogen atom.
  • Z 51 and Z 52 each independently represent a nitrogen-containing aromatic heterocycle.
  • Z 53 each independently represents a benzene ring or an aromatic heterocycle.
  • Y is an anionic acyclic ligand that binds to Pt.
  • L 51 has the same meaning as L 1 in formula (C-1), and the preferred range is also the same.
  • a 51 represents a carbon atom or a nitrogen atom. In view of the stability of the complex and the light emission quantum yield of the complex, A 51 is preferably a carbon atom.
  • Z 51 and Z 52 are synonymous with Z 21 and Z 22 in the general formula (C-2), respectively, and preferred ranges thereof are also the same.
  • Z 53 has the same meaning as Z 23 in formula (C-2), and the preferred range is also the same.
  • Y is an anionic acyclic ligand that binds to Pt.
  • An acyclic ligand is one in which atoms bonded to Pt do not form a ring in the form of a ligand.
  • a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom are preferable, a nitrogen atom and an oxygen atom are more preferable, and an oxygen atom is the most preferable.
  • a vinyl ligand is mentioned as Y couple
  • Examples of Y bonded to Pt with an oxygen atom include an alkoxy ligand, an aryloxy ligand, a heteroaryloxy ligand, an acyloxy ligand, a silyloxy ligand, a carboxyl ligand, a phosphate ligand, Examples thereof include sulfonic acid ligands.
  • Examples of Y bonded to Pt with a sulfur atom include alkyl mercapto ligands, aryl mercapto ligands, heteroaryl mercapto ligands, and thiocarboxylic acid ligands.
  • the ligand represented by Y may have a substituent, and those exemplified as the substituent group A can be appropriately applied as the substituent. Moreover, substituents may be connected to each other.
  • the ligand represented by Y is preferably a ligand bonded to Pt with an oxygen atom, more preferably an acyloxy ligand, an alkyloxy ligand, an aryloxy ligand, a heteroaryloxy ligand. , A silyloxy ligand, and more preferably an acyloxy ligand.
  • platinum complexes represented by the general formula (C-5) one of more preferred embodiments is a platinum complex represented by the following general formula (C-6).
  • a 601 to A 610 each independently represents C—R or a nitrogen atom.
  • R represents a hydrogen atom or a substituent.
  • L 61 represents a single bond or a divalent linking group.
  • Y is an anionic acyclic ligand that binds to Pt.
  • L 61 has the same meaning as L 51 in formula (C-5), and the preferred range is also the same.
  • a 601 to A 610 have the same meanings as A 301 to A 310 in formula (C-3), and preferred ranges are also the same.
  • Y has the same meaning as that in formula (C-5), and the preferred range is also the same.
  • platinum complex represented by the general formula (C-1) include paragraph numbers [0143] to [0152], [0157] to [0158], [0162] to [0162] to [0162] of [2005-310733].
  • 0168 compounds described in JP-A-2006-256999, paragraphs [0065] to [0083], compounds described in JP-A-2006-93542, paragraphs [0065]-[0090] , Compounds described in paragraph numbers [0063] to [0071] of JP-A No. 2007-73891, compounds described in paragraph numbers [0079] to [0083] of JP-A No. 2007-324309, and JP-A 2006-93542 Compounds described in paragraph Nos.
  • Examples of the platinum complex compound represented by the general formula (C-1) include Journal of Organic Chemistry 53,786, (1988), G.S. R. Newkome et al. ), Page 789, method described in left column 53 to right column 7, line 790, method described in left column 18 to 38, method 790, method described in right column 19 to 30 and The combination, Chemische Berichte 113, 2749 (1980), H.C. Lexy et al.), Page 2752, lines 26 to 35, and the like.
  • a ligand or a dissociated product thereof and a metal compound are mixed with a solvent (for example, a halogen solvent, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, a nitrile solvent, an amide solvent, a sulfone solvent,
  • a solvent for example, a halogen solvent, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, a nitrile solvent, an amide solvent, a sulfone solvent
  • a base inorganic or organic various bases such as sodium methoxide, t-butoxypotassium, triethylamine, potassium carbonate, etc.
  • a base inorganic or organic various bases such as sodium methoxide, t-butoxypotassium, triethylamine, potassium carbonate, etc.
  • a base inorganic or organic various bases such as sodium methoxide, t-butoxypotassium, triethylamine
  • the content of the compound represented by formula (C-1) in the light emitting layer of the present invention is preferably 1 to 30% by mass, more preferably 3 to 25% by mass in the light emitting layer. More preferably, it is 20 mass%.
  • the host material is a compound mainly responsible for charge injection and transport in the light emitting layer, and itself is a compound that does not substantially emit light.
  • “substantially does not emit light” means that the amount of light emitted from the compound that does not substantially emit light is preferably 5% or less, more preferably 3% or less of the total amount of light emitted from the entire device. Preferably it says 1% or less.
  • the host material a compound represented by any one of the general formulas (1) to (3) of the present invention can be used.
  • Examples of other host materials that can be used in the present invention include the following compounds. Pyrrole, indole, carbazole, azaindole, azacarbazole, triazole, oxazole, oxadiazole, pyrazole, imidazole, thiophene, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone, hydrazone , Stilbene, silazane, aromatic tertiary amine compounds, styrylamine compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole), aniline copolymers, thiophene oligomers, polythiophene and other conductive polymer oligomers , Organic silane, carbon film, pyridine, pyrimidine, triazine, imidazole,
  • the host material that can be used in combination may be a hole transporting host material or an electron transporting host material, but a hole transporting host material can be used.
  • the light emitting layer preferably contains a host material.
  • the host material is preferably a compound represented by the following general formula (4-1) or (4-2). In the present invention, it is more preferable that the light emitting layer contains at least one compound represented by the general formula (4-1) or (4-2).
  • the compound represented by the general formula (4-1) or (4-2) when the compound represented by the general formula (4-1) or (4-2) is contained in the light emitting layer, the compound represented by the general formula (4-1) or (4-2) is
  • the light emitting layer preferably contains 30 to 100% by mass, more preferably 40 to 100% by mass, and particularly preferably 50 to 100% by mass.
  • each layer when the compound represented by the general formula (4-1) or (4-2) is used in a plurality of organic layers, it is preferable that each layer contains the above-mentioned range.
  • the compound represented by the general formula (4-1) or (4-2) may contain only one kind in any organic layer, and a plurality of general formulas (4-1) or (4) The compound represented by -2) may be contained in combination at any ratio.
  • R ′ 8 is Each independently represents a substituent, and when d, e and f are 2 or more, R ′ 8 may be different or the same, and at least one of R ′ 8 is represented by the following general formula (5). Represents a carbazole group.
  • R ′ 9 each independently represents a substituent.
  • G represents an integer of 0 to 8.
  • R ′ 8 independently represents a substituent, specifically, a halogen atom, an alkoxy group, a cyano group, a nitro group, an alkyl group, an aryl group, a heterocyclic group, or a substituent represented by the general formula (5) It is.
  • R ′ 8 does not represent the general formula (5), it is preferably an alkyl group having 10 or less carbon atoms, a substituted or unsubstituted aryl group having 10 or less carbon atoms, and more preferably an alkyl group having 6 or less carbon atoms. It is.
  • R ′ 9 each independently represents a substituent, specifically a halogen atom, an alkoxy group, a cyano group, a nitro group, an alkyl group, an aryl group, or a heterocyclic group, preferably an alkyl group having 10 or less carbon atoms, A substituted or unsubstituted aryl group having 10 or less carbon atoms, more preferably an alkyl group having 6 or less carbon atoms.
  • g represents an integer of 0 to 8 and is preferably 0 to 4 from the viewpoint of not shielding too much the carbazole skeleton responsible for charge transport. From the viewpoint of ease of synthesis, when carbazole has a substituent, those having a substituent so as to be symmetric with respect to the nitrogen atom are preferable.
  • the sum of d and e is preferably 2 or more from the viewpoint of maintaining the charge transport ability.
  • R ′ 8 is preferably substituted with meta for the other benzene ring. The reason for this is that in ortho substitution, the steric hindrance between adjacent substituents is large, so that the bond is easily cleaved, and the durability is lowered.
  • the molecular shape approaches a rigid rod shape and is easily crystallized, so that element degradation is likely to occur under high temperature conditions.
  • a compound represented by the following structure is preferable.
  • f is preferably 2 or more from the viewpoint of maintaining the charge transport ability.
  • R ′ 8 is substituted with meta from the same viewpoint.
  • a compound represented by the following structure is preferable.
  • an isotope of hydrogen such as a deuterium atom
  • all hydrogen atoms in the compound may be replaced with hydrogen isotopes, or a mixture in which a part is a compound containing hydrogen isotopes may be used.
  • R ′ 9 in the general formula (5) is substituted with deuterium, and the following structures are particularly preferable.
  • the atoms constituting the substituents also include their isotopes.
  • the compounds represented by the general formulas (4-1) and (4-2) can be synthesized by combining various known synthesis methods.
  • carbazole compounds are synthesized by dehydroaromatization after the Athercorp rearrangement reaction of a condensate of an aryl hydrazine and a cyclohexane derivative (LF Tieze, by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
  • LF Tieze by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
  • LF Tieze by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
  • LF Tieze by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
  • the compounds represented by the general formulas (4-1) and (4-2) preferably form a thin layer by a vacuum deposition process, but a wet process such as solution coating is also preferably used. I can do it.
  • the molecular weight of the compound is preferably 2000 or less, more preferably 1200 or less, and particularly preferably 800 or less from the viewpoints of deposition suitability and solubility. Also, from the viewpoint of vapor deposition suitability, if the molecular weight is too small, the vapor pressure becomes small, the change from the gas phase to the solid phase does not occur, and it is difficult to form an organic layer. Particularly preferred.
  • the general formulas (4-1) and (4-2) are preferably compounds represented by the following structures or compounds in which one or more hydrogen atoms are substituted with deuterium atoms.
  • R in the structure shown below '9, R in the formula (5)' is synonymous with 9.
  • the triplet lowest excitation energy (T 1 energy) of the host material is preferably higher than the T 1 energy of the phosphorescent light emitting material in terms of color purity, light emission efficiency, and driving durability. It is preferable T 1 is greater 0.1eV higher than the T 1 of the phosphorescent material of the host material, more preferably at least 0.2eV higher, and further preferably more than 0.3eV large. T 1 of the host material is a large T 1 is obtained from the phosphorescent material to the host material for thereby quench T 1 is less than the light emission of the phosphorescent material.
  • the content of the host compound in the present invention is not particularly limited, but from the viewpoint of light emission efficiency and driving voltage, it is 15% by mass to 95% by mass with respect to the total compound mass forming the light emitting layer. Preferably there is.
  • the light emitting layer contains a plurality of types of host compounds including the compound represented by any one of the general formulas (1) to (3), the compound represented by any one of the general formulas (1) to (3) is It is preferable that it is 50 to 99 mass% in all the host compounds.
  • the pair of electrodes include an anode, and at least one organic layer is included between the light emitting layer and the anode, and at least one of the following general formulas ( It is preferable to contain a compound represented by M-1).
  • the compound represented by the general formula (M-1) is more preferably contained in an organic layer adjacent to the light emitting layer between the light emitting layer and the anode, but its use is not limited, and It may be further contained in any of these layers.
  • a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an exciton block layer, a charge block It can be contained in any or a plurality of layers.
  • the organic layer adjacent to the light emitting layer between the light emitting layer and the anode and containing the compound represented by formula (M-1) is more preferably a hole transport layer.
  • Ar 1 and Ar 2 are each independently one or more selected from alkyl, aryl, heteroaryl, arylamino, alkylamino, morpholino, thiomorpholino, N, O, and S It represents a 5- or 6-membered heterocycloalkyl or cycloalkyl containing a hetero atom, and may further have a substituent Z.
  • Ar 1 and Ar 2 may be bonded to each other by a single bond, alkylene, or alkenylene (with or without a condensed ring) to form a condensed 5- to 9-membered ring.
  • Ar 3 represents alkyl, aryl, heteroaryl, or arylamino, and may further have a substituent Z.
  • Z is each independently a halogen atom, —R ′′, —OR ′′, —N (R ′′) 2 , —SR ′′, —C (O) R ′′, —C (O) OR ′′, —C (O) N (R ") 2, -CN , -NO 2, -SO 2, -SOR", - SO 2 R “, or -SO 3 R” represents, R "are each independently a hydrogen atom, an alkyl group, A perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group is represented.
  • p is an integer of 1 to 4, and when p is 2 or more, Ar 1 and Ar 2 may be the same or different.
  • Another preferred embodiment of the compound represented by the general formula (M-1) is a case represented by the following general formula (M-2).
  • R M1 represents an alkyl group, an aryl group, or a heteroaryl group.
  • R M2 to R M23 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, an amino group, a silyl group, a cyano group, a nitro group, or a fluorine atom.
  • R M1 represents an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms), or a heteroaryl group (preferably having 4 to 12 carbon atoms). Which may have the aforementioned substituent Z.
  • R M1 is preferably an aryl group or a heteroaryl group, and more preferably an aryl group. Preferred substituents when the aryl group of R M1 has a substituent include an alkyl group, a halogen atom, a cyano group, an aryl group, and an alkoxy group, and an alkyl group, a halogen atom, a cyano group, and an aryl group are more preferable.
  • the aryl group of R M1 is preferably a phenyl group that may have a substituent Z, and more preferably a phenyl group that may have an alkyl group or a cyano group.
  • R M2 to R M23 are each independently a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms), a heteroaryl group (preferably having 4 to 12 carbon atoms), Alkoxy group (preferably having 1 to 8 carbon atoms), aryloxy group (preferably having 6 to 30 carbon atoms), amino group (preferably having 0 to 24 carbon atoms), silyl group (preferably having 0 to 18 carbon atoms), cyano Represents a group, a nitro group, or a fluorine atom, and these may have the aforementioned substituent Z.
  • R M2 , R M7 , R M8 , R M15 , R M16 and R M23 are preferably a hydrogen atom or an alkyl group or an aryl group which may have a substituent Z, more preferably a hydrogen atom.
  • R M4 , R M5 , R M11 , R M12 , R M19, and R M20 are preferably a hydrogen atom, an alkyl or aryl group optionally having substituent Z, or a fluorine atom, more preferably a hydrogen atom. Is an atom.
  • R M3 , R M6 , R M9 , R M14 , R M17 and R M22 are preferably a hydrogen atom, an alkyl or aryl group optionally having substituent Z, a fluorine atom, or a cyano group, and more A hydrogen atom or an alkyl group which may have a substituent Z is preferable, and a hydrogen atom is more preferable.
  • R M10 , R M13 , R M18 and R M21 are preferably a hydrogen atom, an alkyl group optionally having a substituent Z, an aryl group, a heteroaryl group or an amino group, a nitro group, a fluorine atom, or a cyano group More preferably a hydrogen atom, an alkyl or aryl group optionally having a substituent Z, a nitro group, a fluorine atom, or a cyano group, still more preferably a hydrogen atom or a substituent Z. It is an alkyl group that may be present.
  • the substituent is preferably a fluorine atom
  • the alkyl group which may have the substituent Z preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. is there.
  • Another preferred embodiment of the compound represented by the general formula (M-1) is a case represented by the following general formula (M-3).
  • R S1 to R S5 are each independently an alkyl group, cycloalkyl group, alkenyl group, alkynyl group, —CN, perfluoroalkyl group, trifluorovinyl group, —CO 2 R, —C (O) represents R, —NR 2 , —NO 2 , —OR, a halogen atom, an aryl group or a heteroaryl group, and may further have a substituent Z.
  • Each R independently represents a hydrogen atom, an alkyl group, a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
  • R S1 to R S5 When a plurality of R S1 to R S5 are present, they may be bonded to each other to form a ring, and may further have a substituent Z.
  • a represents an integer of 0 to 4, and when a plurality of R S1 are present, they may be the same or different and may be bonded to each other to form a ring.
  • b to e each independently represent an integer of 0 to 5, and when there are a plurality of R S2 to R S5 , they may be the same or different, and any two may combine to form a ring.
  • q is an integer of 1 to 5, and when q is 2 or more, a plurality of R S1 may be the same or different, and may be bonded to each other to form a ring.
  • the alkyl group may have a substituent, may be saturated or unsaturated, and examples of the group that may be substituted include the above-described substituent Z.
  • the alkyl group represented by R S1 to R S5 is preferably an alkyl group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 6 carbon atoms in total, such as a methyl group or an ethyl group. , I-propyl group, cyclohexyl group, t-butyl group and the like.
  • the cycloalkyl group may have a substituent, may be saturated or unsaturated, and examples of the group that may be substituted include the above-described substituent Z.
  • the cycloalkyl group represented by R S1 to R S5 is preferably a cycloalkyl group having 4 to 7 ring members, more preferably a cycloalkyl group having 5 to 6 carbon atoms in total, such as a cyclopentyl group and cyclohexyl group. Groups and the like.
  • the alkenyl group represented by R S1 to R S5 preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms.
  • vinyl, allyl, 1-propenyl Examples include 1-isopropenyl, 1-butenyl, 2-butenyl, 3-pentenyl and the like.
  • the alkynyl group represented by R S1 to R S5 preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms.
  • Examples of the perfluoroalkyl group represented by R S1 to R S5 include those in which all hydrogen atoms of the aforementioned alkyl group are replaced with fluorine atoms.
  • the aryl group represented by R S1 to R S5 is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a tolyl group, a biphenyl group, and a terphenyl group.
  • the heteroaryl group represented by R S1 to R S5 is preferably a heteroaryl group having 5 to 8 carbon atoms, more preferably a 5- or 6-membered substituted or unsubstituted heteroaryl group,
  • R S1 to R S5 are preferably a hydrogen atom, an alkyl group, a cyano group, a trifluoromethyl group, a perfluoroalkyl group, a dialkylamino group, a fluoro group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group.
  • Group, cyano group, trifluoromethyl group, fluoro group and aryl group more preferably a hydrogen atom, an alkyl group and an aryl group.
  • substituent Z an alkyl group, an alkoxy group, a fluoro group, a cyano group, and a dialkylamino group are preferable, and a hydrogen atom and an alkyl group are more preferable.
  • R S1 to R S5 may be bonded to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring is cycloalkyl, aryl, or heteroaryl;
  • the 7-membered ring may further have a substituent Z.
  • the definition and preferred range of cycloalkyl, aryl, and heteroaryl formed are the same as the cycloalkyl group, aryl group, and heteroaryl group defined by R S1 to R S5 .
  • the compound represented by the general formula (M-1) is preferably contained in an amount of 50 to 100% by mass, The content is preferably 100% by mass, and particularly preferably 95 to 100% by mass.
  • each layer contains the above-mentioned range.
  • the compound represented by the general formula (M-1) may contain only one kind in any organic layer, and the compound represented by the plurality of general formulas (M-1) You may contain in combination.
  • the thickness of the hole transport layer containing the compound represented by the general formula (M-1) is preferably 1 nm to 500 nm, more preferably 3 nm to 200 nm, and more preferably 5 nm to 100 nm. Further preferred.
  • the hole transport layer is preferably provided in contact with the light emitting layer.
  • the hole transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
  • the lowest excited triplet (T 1 ) energy in the film state of the compound represented by the general formula (M-1) is preferably 2.52 eV (58 kcal / mol) or more and 3.47 eV (80 kcal / mol) or less. It is more preferably 2.60 eV (60 kcal / mol) or more and 3.25 eV (75 kcal / mol) or less, and further preferably 2.69 eV (62 kcal / mol) or more and 3.04 eV (70 kcal / mol) or less.
  • the hydrogen atom constituting the general formula (M-1) includes hydrogen isotopes (such as deuterium atoms). In this case, all hydrogen atoms in the compound may be replaced with hydrogen isotopes, or a mixture in which a part is a compound containing hydrogen isotopes may be used.
  • the compound represented by the general formula (M-1) can be synthesized by combining various known synthesis methods.
  • carbazole compounds are synthesized by dehydroaromatization after the Athercorp rearrangement reaction of a condensate of an aryl hydrazine and a cyclohexane derivative (LF Tieze, by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
  • LF Tieze by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
  • LF Tieze by Th. Eicher
  • Takano, Ogasawara, Precision organic synthesis page 339 (published by Nankodo).
  • Tetrahedron Letters 39: 617 (1998), 39: 2367 (1998) and 40: 6393 (1999) and the like Tetrahedron Letters 39: 617 (1998), 39: 2367 (1998) and 40
  • the compound represented by the general formula (M-1) of the present invention is preferably formed into a thin layer by a vacuum deposition process, but a wet process such as solution coating can also be suitably used.
  • the molecular weight of the compound is preferably 2000 or less, more preferably 1200 or less, and particularly preferably 800 or less from the viewpoints of deposition suitability and solubility. Also, from the viewpoint of vapor deposition suitability, if the molecular weight is too small, the vapor pressure becomes small, the change from the gas phase to the solid phase does not occur, and it is difficult to form an organic layer. Particularly preferred. *
  • the pair of electrodes preferably includes a cathode, and preferably includes at least one organic layer between the light emitting layer and the cathode, and the organic layer includes an aromatic hydrocarbon compound. It is preferable to do.
  • the aromatic hydrocarbon compound is more preferably contained in an organic layer adjacent to the light emitting layer between the light emitting layer and the cathode, but its use is not limited, and any of the organic layers may be further added. It may be contained.
  • any one or more of a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an exciton block layer, and a charge block layer are used. It can contain.
  • the organic layer adjacent to the light emitting layer between the light emitting layer and the cathode and containing the aromatic hydrocarbon compound is preferably a charge blocking layer or an electron transporting layer, and more preferably an electron transporting layer.
  • the aromatic hydrocarbon compound preferably comprises only carbon atoms and hydrogen atoms from the viewpoint of ease of synthesis.
  • the aromatic hydrocarbon compound is contained in a layer other than the light emitting layer, it is preferably contained in an amount of 70 to 100% by mass, more preferably 85 to 100% by mass.
  • the aromatic hydrocarbon compound is contained in the light emitting layer, it is preferably contained in an amount of 0.1 to 99% by weight, more preferably 1 to 95% by weight, based on the total weight of the light emitting layer. It is more preferable to include the mass%.
  • the condensed polycyclic skeleton having 13 to 22 carbon atoms is preferably any one of fluorene, anthracene, phenanthrene, tetracene, chrysene, pentacene, pyrene, perylene, and triphenylene.
  • fluorene, triphenylene, phenanthrene Is more preferable, and triphenylene is more preferable from the viewpoint of stability of the compound and charge injection / transport properties, and a compound represented by the general formula (Tp-1) is particularly preferable.
  • the hydrocarbon compound represented by the general formula (Tp-1) preferably has a molecular weight in the range of 400 to 1200, more preferably 400 to 1000, and still more preferably 400 to 800. If the molecular weight is 400 or more, a high-quality amorphous thin film can be formed, and if the molecular weight is 1200 or less, it is preferable in terms of solubility in a solvent, sublimation, and appropriate deposition.
  • hydrocarbon compound represented by the general formula (Tp-1) is not limited, and it may be further contained not only in the organic layer adjacent to the light emitting layer but also in any layer within the organic layer.
  • R 12 to R 23 are each independently a hydrogen atom, an alkyl group or an alkyl group, a phenyl group optionally substituted with a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group, Represents a fluorenyl group, a naphthyl group, or a triphenylenyl group, provided that R 12 to R 23 are not all hydrogen atoms.
  • Examples of the alkyl group represented by R 12 to R 23 are substituted or unsubstituted, for example, methyl group, ethyl group, isopropyl group, n-butyl group, tert-butyl group, n-octyl group, n-decyl group, and an n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like, preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a cyclohexyl group, more preferably a methyl group, an ethyl group, or A tert-butyl group.
  • R 12 to R 23 are preferably an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (these are further an alkyl group, a phenyl group, a fluorenyl group). More preferably a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group, which may be substituted with a group, a naphthyl group, or a triphenylenyl group.
  • a benzene ring that may be substituted with a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (which may be further substituted with an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group); It is particularly preferred.
  • the total number of aryl rings is preferably 2 to 8, and preferably 3 to 5. By setting it as this range, a high-quality amorphous thin film can be formed, and solubility in a solvent, sublimation, and deposition suitability are improved.
  • R 12 to R 23 each independently preferably has a total carbon number of 20 to 50, more preferably a total carbon number of 20 to 36. By setting it as this range, a high-quality amorphous thin film can be formed, and solubility in a solvent, sublimation, and deposition suitability are improved.
  • the hydrocarbon compound represented by the general formula (Tp-1) is preferably a hydrocarbon compound represented by the following general formula (Tp-2).
  • a plurality of Ar 1 are the same, and a phenyl group, a fluorenyl group, a naphthyl group, which may be substituted with an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group, Or represents a triphenylenyl group.
  • An alkyl group and an alkyl group represented by Ar 1 , a phenyl group, a fluorenyl group, a naphthyl group, or a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group that may be substituted with a triphenylenyl group include R 12 to R 23 . It is synonymous with what was mentioned, and a preferable thing is also the same.
  • the hydrocarbon compound represented by the general formula (Tp-1) is preferably a hydrocarbon compound represented by the following general formula (Tp-3).
  • L represents an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a phenyl group, a fluorenyl group, a naphthyl group, a triphenylenyl group which may be substituted with a triphenylenyl group, or a combination thereof.
  • n represents an integer of 1 to 6.
  • the alkyl group, phenyl group, fluorenyl group, naphthyl group, or triphenylenyl group that forms the n-valent linking group represented by L has the same meaning as that described for R 12 to R 23 .
  • L is preferably an alkyl group or an n-valent linking group formed by combining a benzene ring, a fluorene ring, or a combination thereof, which may be substituted with a benzene ring.
  • L is bonded to the triphenylene ring by *.
  • N is preferably 1 to 5, and more preferably 1 to 4.
  • the hydrocarbon compound represented by the general formula (Tp-1) is preferably a hydrocarbon compound represented by the following general formula (Tp-4).
  • Ar 2 in the case where a plurality of Ar 2 are present is the same, and Ar 2 represents a group formed by substitution with an alkyl group, phenyl group, naphthyl group, or triphenylenyl group, or a combination thereof.
  • Ar 2 represents a group formed by substitution with an alkyl group, phenyl group, naphthyl group, or triphenylenyl group, or a combination thereof.
  • And q each independently represent 0 or 1, but p and q are not simultaneously 0.
  • Ar 2 represents a hydrogen atom.
  • Ar 2 is preferably a group formed by combining an alkyl group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, or a triphenylenyl group, and more preferably a combination of a methyl group, a t-butyl group, a phenyl group, or a triphenylenyl group. It is a group consisting of Ar 2 is particularly preferably a benzene ring substituted with an alkyl group having 1 to 4 carbon atoms at the meta position, a phenyl group, a naphthyl group, a triphenylenyl group, or a combination thereof.
  • the hydrocarbon compound according to the present invention is used as a host material of a light emitting layer of an organic electroluminescent device or a charge transport material of a layer adjacent to the light emitting layer, an energy gap in a thin film state than the light emitting material (the light emitting material is a phosphorescent light emitting material)
  • the light emitting material is a phosphorescent light emitting material
  • the energy gap and T 1 energy are not too large.
  • the T 1 energy in the film state of the hydrocarbon compound represented by the general formula (Tp-1) is preferably 52 kcal / mol or more and 80 kcal / mol or less, and 55 kcal / mol or more and 68 kcal / mol or less. Is more preferable, and it is still more preferable that they are 58 kcal / mol or more and 63 kcal / mol or less. In particular, when a phosphorescent light emitting material is used as the light emitting material, the T 1 energy is preferably in the above range.
  • the T 1 energy can be obtained by a method similar to the method in the description of the general formula (1) described above.
  • the glass transition temperature (Tg) of the hydrocarbon compound according to the present invention is 80 ° C. or more and 400 ° C. or less from the viewpoint of stably operating the organic electroluminescence device against heat generation during high temperature driving or during device driving.
  • the temperature is preferably 100 ° C. or higher and 400 ° C. or lower, more preferably 120 ° C. or higher and 400 ° C. or lower.
  • the compounds exemplified as the hydrocarbon compounds according to the present invention include those described in International Publication No. 05/013388, International Publication No. 06/130598, International Publication No. 09/021107, US2009 / 0009065, International Publication No. 09 / It can be synthesized by the methods described in the 008311 pamphlet and the international publication 04/018587 pamphlet. After synthesis, it is preferable to purify by sublimation purification after purification by column chromatography, recrystallization or the like. By sublimation purification, not only can organic impurities be separated, but inorganic salts and residual solvents can be effectively removed.
  • the light emitting device of the present invention preferably contains at least one organic layer between the light emitting layer and the cathode, and the organic layer contains at least one compound represented by the following general formula (O-1). Is preferable from the viewpoints of element efficiency and driving voltage.
  • the general formula (O-1) will be described below.
  • R O1 represents an alkyl group, an aryl group, or each independently .A O1 ⁇ A O4 representing the heteroaryl group, the C-R A or .R A representing the nitrogen atom Represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R A may be the same or different, and L O1 represents a divalent to hexavalent linking group comprising an aryl ring or a heteroaryl ring.
  • N O1 represents an integer of 2 to 6.
  • R O1 represents an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms), or a heteroaryl group (preferably having 4 to 12 carbon atoms).
  • Z ′ may be included.
  • R O1 is preferably an aryl group or a heteroaryl group, more preferably an aryl group.
  • an alkyl group, an aryl group or a cyano group can be mentioned, an alkyl group or an aryl group is more preferable, and an aryl group is still more preferable.
  • the aryl group of R O1 When the aryl group of R O1 has a plurality of substituents, the plurality of substituents may be bonded to each other to form a 5- or 6-membered ring.
  • the aryl group of R O1 is preferably a phenyl group which may have a substituent Z ′, more preferably a phenyl group which may be substituted with an alkyl group or an aryl group, still more preferably unsubstituted.
  • a O1 to A O4 each independently represent C—R A or a nitrogen atom.
  • 0 to 2 are preferably nitrogen atoms, and 0 or 1 is more preferably a nitrogen atom.
  • all of A O1 ⁇ A O4 is C-R A, or A O1 be a nitrogen atom, is preferably A O2 ⁇ A O4 is C-R A, A O1 be a nitrogen atom, A O2 ⁇ More preferably, A O4 is C—R A , more preferably A O1 is a nitrogen atom, A O2 to A O4 are C—R A , and R A is all a hydrogen atom.
  • R A represents a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms), or a heteroaryl group (preferably having 4 to 12 carbon atoms). It may have a substituent Z ′.
  • the plurality of RA may be the same or different.
  • R A is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
  • L O1 represents a divalent to hexavalent linking group composed of an aryl ring (preferably having 6 to 30 carbon atoms) or a heteroaryl ring (preferably having 4 to 12 carbon atoms).
  • L O1 is preferably an arylene group, heteroarylene group, aryltriyl group, or heteroaryltriyl group, more preferably a phenylene group, a biphenylene group, or a benzenetriyl group, still more preferably a biphenylene group, Or it is a benzenetriyl group.
  • L O1 may have the above-described substituent Z ′, and when it has a substituent, the substituent is preferably an alkyl group, an aryl group, or a cyano group. Specific examples of L O1 include the following.
  • n O1 represents an integer of 2 to 6, preferably an integer of 2 to 4, more preferably 2 or 3. n O1 is most preferably 3 from the viewpoint of device efficiency, and most preferably 2 from the viewpoint of device durability.
  • the compound represented by the general formula (O-1) is more preferably a compound represented by the following general formula (O-2).
  • R O1 represents an alkyl group, an aryl group, or a heteroaryl group.
  • R O2 to R O4 each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
  • a O1 to A O4 each independently represent C—R A or a nitrogen atom, R A represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R A may be the same or different. May be.
  • R O1 and A O1 ⁇ A O4 the general formula (O1) in the same meaning as R O1 and A O1 ⁇ A O4 of, also the same preferable ranges thereof.
  • R 02 to R 04 are each independently a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms), or a heteroaryl group (preferably having 4 to 12 carbon atoms). Which may have the aforementioned substituent Z ′.
  • R 02 to R 04 are preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an aryl group, and most preferably a hydrogen atom.
  • the compound represented by the general formula (O-1) has a glass transition temperature (Tg) of 100 ° C. from the viewpoint of stable operation at high temperature storage, stable operation against high temperature driving, and heat generation during driving. It is preferably from ⁇ 300 ° C., more preferably from 120 ° C. to 300 ° C., further preferably from 130 ° C. to 300 ° C., and still more preferably from 140 ° C. to 300 ° C.
  • the compound represented by the general formula (O-1) can be synthesized by the method described in JP-A No. 2001-335776. After synthesis, purification by column chromatography, recrystallization, reprecipitation, etc., followed by purification by sublimation is preferred. Not only can organic impurities be separated by sublimation purification, but inorganic salts, residual solvents, moisture, and the like can be effectively removed.
  • the compound represented by the general formula (O-1) is contained in an organic layer between the light emitting layer and the cathode, but is contained in a layer on the cathode side adjacent to the light emitting layer. Is preferred.
  • the charge transport layer refers to a layer in which charge transfer occurs when a voltage is applied to the organic electroluminescent element. Specific examples include a hole injection layer, a hole transport layer, an electron block layer, a light emitting layer, a hole block layer, an electron transport layer, and an electron injection layer. A hole injection layer, a hole transport layer, an electron blocking layer, or a light emitting layer is preferable. If the charge transport layer formed by the coating method is a hole injection layer, a hole transport layer, an electron block layer, or a light emitting layer, it is possible to produce an organic electroluminescent element with low cost and high efficiency.
  • the charge transport layer is more preferably a hole injection layer, a hole transport layer, or an electron block layer.
  • the hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side.
  • the hole injection layer and the hole transport layer the matters described in paragraph numbers [0165] to [0167] of JP-A-2008-270736 can be applied to the present invention.
  • the hole injection layer preferably contains an electron accepting dopant.
  • an electron-accepting dopant may be any organic material or inorganic material as long as it can extract electrons from the doped material and generate radical cations, for example, tetracyanoquinodimethane. (TCNQ), tetrafluorotetracyanoquinodimethane (F 4 -TCNQ), molybdenum oxide, and the like.
  • the electron-accepting dopant in the hole injection layer is preferably contained in an amount of 0.01% by mass to 50% by mass, and preferably 0.1% by mass to 40% by mass with respect to the total mass of the compound forming the hole injection layer. %, More preferably 0.2% by mass to 30% by mass.
  • the electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side.
  • the electron injection material and the electron transport material used for these layers may be a low molecular compound or a high molecular compound.
  • As the electron transport material a compound represented by any one of the general formulas (1) to (3) of the present invention can be used.
  • Other materials include pyridine derivatives, quinoline derivatives, pyrimidine derivatives, pyrazine derivatives, phthalazine derivatives, phenanthroline derivatives, triazine derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, Metal complexes of anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthalene, perylene, and other aromatic ring tetracarboxylic anhydrides, phthalocyanine derivatives, 8-quinolinol derivatives And metal phthalocyanines, various metal complexes represented by metal complexes with benzoxazole and benzothiazole ligands, It is preferable that a layer
  • the thicknesses of the electron injection layer and the electron transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
  • the thickness of the electron transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
  • the thickness of the electron injection layer is preferably from 0.1 nm to 200 nm, more preferably from 0.2 nm to 100 nm, and even more preferably from 0.5 nm to 50 nm.
  • the electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
  • the electron injection layer preferably contains an electron donating dopant.
  • an electron donating dopant may be any organic material or inorganic material as long as it can give electrons to the doped material and generate radical anions.
  • TTF tetrathiafulvalene
  • TTT dithiaimidazole compounds
  • TTT tetrathianaphthacene
  • bis- [1,3 diethyl-2-methyl-1,2-dihydrobenzimidazolyl] lithium and cesium.
  • the electron donating dopant in the electron injection layer is preferably contained in an amount of 0.01% by mass to 50% by mass, and 0.1% by mass to 40% by mass with respect to the total mass of the compound forming the electron injection layer. More preferably, the content is 0.5 to 30% by mass.
  • the hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side.
  • a hole blocking layer can be provided as an organic layer adjacent to the light emitting layer on the cathode side.
  • organic compounds constituting the hole blocking layer include aluminum (III) bis (2-methyl-8-quinolinolato) 4-phenylphenolate (Aluminum (III) bis (2-methyl-8-quinolinato) 4- aluminum complexes such as phenylphenolate (abbreviated as Balq)), triazole derivatives, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (2,9-dimethyl-4,7-diphenyl-1,10-) phenanthroline derivatives such as phenanthroline (abbreviated as BCP)) and the like.
  • BCP phenanthroline
  • the thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
  • the hole blocking layer may have a single layer structure made of one or more of the materials described above, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions.
  • the electron blocking layer is a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side.
  • an electron blocking layer can be provided as an organic layer adjacent to the light emitting layer on the anode side.
  • the thickness of the electron blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
  • the electron blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
  • the entire organic EL element may be protected by a protective layer.
  • the protective layer the matters described in JP-A-2008-270736, paragraphs [0169] to [0170] can be applied to the present invention.
  • the element of this invention may seal the whole element using a sealing container.
  • the sealing container the matters described in paragraph [0171] of JP-A-2008-270736 can be applied to the present invention.
  • the organic electroluminescence device of the present invention emits light by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode.
  • a direct current which may include an alternating current component as necessary
  • the driving method of the organic electroluminescence device of the present invention is described in JP-A-2-148687, JP-A-6-301355, JP-A-5-290080, JP-A-7-134558, JP-A-8-234585, and JP-A-8-2441047.
  • the driving methods described in each publication, Japanese Patent No. 2784615, US Pat. Nos. 5,828,429 and 6,023,308 can be applied.
  • the external quantum efficiency of the organic electroluminescent element of the present invention is preferably 7% or more, more preferably 10% or more, and further preferably 12% or more.
  • the value of the external quantum efficiency should be the maximum value of the external quantum efficiency when the device is driven at 20 ° C., or the value of the external quantum efficiency around 300 to 400 cd / m 2 when the device is driven at 20 ° C. Can do.
  • the internal quantum efficiency of the organic electroluminescence device of the present invention is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more.
  • the internal quantum efficiency of the device is calculated by dividing the external quantum efficiency by the light extraction efficiency. In a normal organic EL element, the light extraction efficiency is about 20%.
  • the element of the present invention can be suitably used for a display element, a display, a backlight, electrophotography, an illumination light source, a recording light source, an exposure light source, a reading light source, a sign, a signboard, an interior, or optical communication.
  • a device driven in a region having a high light emission luminance such as a lighting device and a display device.
  • FIG. 2 is a cross-sectional view schematically showing an example of the light emitting device of the present invention.
  • the light-emitting device 20 of FIG. 2 is comprised by the board
  • FIG. 1 is a cross-sectional view schematically showing an example of the light emitting device of the present invention.
  • the light-emitting device 20 of FIG. 2 is comprised by the board
  • the organic electroluminescent device 10 is configured by sequentially laminating an anode (first electrode) 3, an organic layer 11, and a cathode (second electrode) 9 on a substrate 2.
  • a protective layer 12 is laminated on the cathode 9, and a sealing container 16 is provided on the protective layer 12 with an adhesive layer 14 interposed therebetween.
  • a part of each electrode 3 and 9, a partition, an insulating layer, etc. are abbreviate
  • the adhesive layer 14 a photocurable adhesive such as an epoxy resin or a thermosetting adhesive can be used, and for example, a thermosetting adhesive sheet can also be used.
  • the use of the light-emitting device of the present invention is not particularly limited, and for example, it can be a display device such as a television, a personal computer, a mobile phone, and electronic paper in addition to a lighting device.
  • FIG. 3 is a cross-sectional view schematically showing an example of the illumination device of the present invention.
  • the illumination device 40 of the present invention includes the organic EL element 10 and the light scattering member 30 described above. More specifically, the lighting device 40 is configured such that the substrate 2 of the organic EL element 10 and the light scattering member 30 are in contact with each other.
  • the light scattering member 30 is not particularly limited as long as it can scatter light.
  • the light scattering member 30 is a member in which fine particles 32 are dispersed on a transparent substrate 31.
  • the transparent substrate 31 for example, a glass substrate can be preferably cited.
  • transparent resin fine particles can be preferably exemplified.
  • the glass substrate and the transparent resin fine particles known ones can be used.
  • the incident light is scattered by the light scattering member 30, and the scattered light is emitted from the light emitting surface 30B. It is emitted as illumination light.
  • Synthesis Examples 2 to 11 Synthesis of Compounds 1, 2, 4 to 11 Compounds 1, 2, 4 to 11 were synthesized according to the scheme shown below. Reaction conditions and purification operations are the same as in Synthesis Example 1.
  • Example 1 Green ETL, EIL
  • a glass substrate having a thickness of 0.5 mm and a 2.5 cm square ITO film (manufactured by Geomat Co., Ltd., surface resistance 10 ⁇ / ⁇ ) is placed in a cleaning container, subjected to ultrasonic cleaning in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes. Went.
  • the following organic layers were sequentially deposited on the transparent anode (ITO film) by vacuum deposition.
  • First layer GD-1: film thickness 10 nm
  • 0.1 nm of lithium fluoride and 100 nm of metallic aluminum were vapor-deposited in this order to form a cathode. This is put in a glove box substituted with nitrogen gas without being exposed to the atmosphere, and sealed using a glass sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.).
  • a comparative element 1-1 was obtained.
  • the elements 1-1 to 1- 10 Comparative elements 1-2 to 1-9 were obtained.
  • Table 1 shows the results of evaluating these elements by the following methods from the viewpoints of efficiency, driving voltage, efficiency change after high temperature storage, chromaticity change after high temperature storage, and durability after high temperature storage.
  • (C) Change in efficiency after high-temperature storage Each element is stored in a thermostat at 100 ° C. for 24 hours, and then light is emitted by applying a DC voltage so that the luminance becomes 1000 cd / m 2 at room temperature.
  • the external quantum efficiency ⁇ 100 at this time was compared with the external quantum efficiency ⁇ RT when light was emitted at room temperature, and the ratio between the two ( ⁇ 100 / ⁇ RT ) was used as an index of the efficiency change during high-luminance driving. A larger value is more preferable.
  • (D) Change in chromaticity after high-temperature storage Each element is stored in a thermostat at 100 ° C.
  • Example 2 Green ETL
  • Example 2 A device was fabricated in the same manner as in Example 1 except that the layer configuration was changed to the one shown below, and the results of performing the same evaluation as in Example 1 for the items described in Table 2 are shown in Table 2.
  • Fourth layer H-1 and GD-2 (mass ratio 85:15): film thickness 30 nm
  • Fifth layer Materials listed in Table 2: Film thickness 5 nm
  • Example 3 (Blue ETL) A device was fabricated in the same manner as in Example 1 except that the layer configuration was changed to the one shown below, and the results of the same evaluation as in Example 1 for the items shown in Table 3 are shown in Table 3.
  • Example 4 (Blue ETL) A device was fabricated in the same manner as in Example 1 except that the layer configuration was changed to the one shown below, and the results of the same evaluation as in Example 1 for the items shown in Table 4 are shown in Table 4.
  • Fourth layer H-3 and BD-2 (mass ratio 85:15): film thickness 30 nm
  • Fifth layer Materials listed in Table 4: Film thickness 5 nm
  • Example 5 shows the results of fabricating the device in the same manner as in Example 1 except that the layer configuration was changed to the following, and performing the same evaluation as in Example 1.
  • the charge transport material of the present invention is excellent in electron injection and transport properties, stability to excitons and electrons, and heat resistance, when used as an electron transport material, high efficiency, low voltage, and efficiency after high-temperature storage, It was found that an element excellent in chromaticity and durability can be obtained.
  • Example 6 Green Host, ETL A device was produced in the same manner as in Example 1 except that the layer configuration was changed to the one shown below, and the results of evaluating the items described in Table 6 by the same method as in Example 1 are shown in Table 6.
  • Fifth layer Materials listed in Table 6: Film thickness 5 nm
  • Example 7 Light blue host, ETL
  • ETL Light blue host
  • Example 8 (Red host, ETL) A device was fabricated in the same manner as in Example 1 except that the layer configuration was changed to the one shown below, and the results of evaluating the items described in Table 8 by the same method as in Example 1 are shown in Table 8.
  • Fifth layer Materials listed in Table 8: Film thickness 5 nm
  • the charge transport material of the present invention is excellent in electron injection and transport properties, exciton and electron stability, and heat resistance, it is highly efficient when used as a host material, and efficiency, chromaticity and durability after storage at high temperatures. A device excellent in the above can be obtained.
  • Example 9 Coating, green host
  • a glass substrate having a thickness of 0.5 mm and a 2.5 cm square ITO film (manufactured by Geomat Co., Ltd., surface resistance 10 ⁇ / ⁇ ) is placed in a cleaning container, subjected to ultrasonic cleaning in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes. Went.
  • a hole transporting buffer layer having a film thickness of about 50 nm was formed.
  • a toluene solution containing 1% by mass of Compound 1 as a host material and 0.05% by mass of GD-1 was spin-coated (2000 rpm, 60 seconds) on the previous buffer layer, and a light-emitting layer having a thickness of about 50 nm Formed.
  • ET-3 was deposited to 50 nm by vacuum deposition to form an electron transport layer, and further, 0.1 nm of lithium fluoride and 100 nm of metallic aluminum were deposited in this order to form a cathode.
  • the charge transport material of the present invention can provide a film having a good film quality even when formed by a wet film formation method, and an element having a good performance.
  • the device of the present invention using the compound represented by any one of the general formulas (1) to (3) of the present invention has an efficiency after high temperature storage as compared with the device of the comparative example. It can be seen that the change in color and the change in chromaticity are small and the durability after high temperature storage is excellent. *
  • the light emitting element of the present invention is designed to increase the light emission efficiency in such a case. Therefore, it can be used advantageously.
  • the element of the present invention is excellent in luminous efficiency and durability even when used in a high temperature environment such as in-vehicle use, and is suitable for a light emitting device, a display device, and a lighting device.
  • an organic electroluminescent device that satisfies all of the suppression of a decrease in luminous efficiency after storage of the device at a high temperature, the suppression of chromaticity change, and the improvement of durability at a high level.

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Abstract

Disclosed is an organic electroluminescent element that satisfies at a high level the minimization of a decrease in luminous efficiency after high temperature storage of the element, the minimization of changes in chromaticity; and improvement in durability. The organic electroluminescent element comprises a pair of electrodes comprising an anode and a cathode, and at least one organic layer containing a luminous layer between said electrodes, on a substrate. The luminous layer contains at least one type of phosphorescent material, and, of the at least one organic layer, at least one layer contains a compound having a specific m-Quinquephenyl structure.

Description

有機電界発光素子、並びにｍ－キンクフェニル構造を有する電荷輸送材料及び化合物Organic electroluminescent device, charge transport material and compound having m-kinkphenyl structure
　本発明は有機電界発光素子、並びにｍ－キンクフェニル構造を有する電荷輸送材料及び化合物に関する。 The present invention relates to an organic electroluminescence device, and a charge transport material and compound having an m-kinkphenyl structure.
　有機電界発光素子（以下、「素子」、「有機ＥＬ素子」ともいう）は、低電圧駆動で高輝度の発光が得られることから活発に研究開発が行われている。有機電界発光素子は、一対の電極間に有機層を有し、陰極から注入された電子と陽極から注入された正孔とが有機層において再結合し、生成した励起子のエネルギーを発光に利用するものである。 Organic electroluminescent elements (hereinafter also referred to as “elements” and “organic EL elements”) are actively researched and developed because they can emit light with high luminance when driven at a low voltage. An organic electroluminescent element has an organic layer between a pair of electrodes, and electrons injected from the cathode and holes injected from the anode recombine in the organic layer, and the generated exciton energy is used for light emission. To do.
　近年、燐光発光材料を用いることにより、素子の高効率化が進んでいる。更なる素子の発光効率の向上及び駆動電圧の低減のため、オルト位に置換基を有するベンゾニトリル系電荷輸送材料の使用が特許文献１に記載されている。また特定構造の芳香族化合物を電荷輸送材料として用いた有機電界発光素子が特許文献２～４に記載されている。 In recent years, the use of phosphorescent light-emitting materials has advanced the efficiency of devices. Patent Document 1 discloses the use of a benzonitrile-based charge transport material having a substituent at the ortho position for further improving the light emission efficiency of the device and reducing the driving voltage. Patent Documents 2 to 4 describe organic electroluminescent devices using an aromatic compound having a specific structure as a charge transport material.
　また本発明のｍ－キンクフェニル構造を有する化合物としては、非特許文献１に非線形光学材料として分子計算された分子モデルが記載されるが、実際の化合物の合成例の記載はなく、また当該分子モデルの化合物を、電荷輸送材料や有機電界発光素子へ適用する記述や示唆もない。 As the compound having an m-kinkphenyl structure of the present invention, Non-patent Document 1 describes a molecular model calculated as a nonlinear optical material, but there is no description of an actual compound synthesis example, and the molecule There is no description or suggestion of applying the model compounds to charge transport materials or organic electroluminescent devices.
日本国特開２００７－２６６５９８号公報Japanese Unexamined Patent Publication No. 2007-266598 日本国特開２００６－１３５１６０号公報Japanese Unexamined Patent Publication No. 2006-135160 日本国特開２００６－１３５１８４号公報Japanese Unexamined Patent Publication No. 2006-135184 日本国特開２００６－１９０７１８号公報Japanese Unexamined Patent Publication No. 2006-190718
　本発明者らの検討により、特許文献１～４に記載の従来の素子では、高温で保管した際に発光効率が低下し、大きく色度が変化し、また耐久性が悪化するという問題があることが本発明者らの検討により新たに明らかになり、その改良が求められていた。特に、車載用途など、高温保管後にもその特性が変化しない素子が求められている。これまでに報告されている化合物である、後述の実施例で示される比較化合物１～１１などを使用した素子は、いずれも１００℃で２４時間保管後に駆動すると効率が低下し、色度が大きく変化し、また耐久性が低い等の問題点があった。従来の素子が有するこれらの問題に対し、本発明者らは、本発明のｍ－キンクフェニル構造を有する電荷輸送材料を用いることにより、素子の高温保管後の発光効率の低下の抑制、色度変化の抑制、及び耐久性の向上の全てを、高い水準で満足する有機電界発光素子が提供されることを見出した。 As a result of investigations by the present inventors, the conventional devices described in Patent Documents 1 to 4 have problems that the luminous efficiency decreases when stored at high temperatures, the chromaticity changes greatly, and the durability deteriorates. This has been newly clarified by the study by the present inventors, and an improvement has been demanded. In particular, there is a demand for an element whose characteristics do not change even after high-temperature storage, such as in-vehicle use. The devices using the comparative compounds 1 to 11 shown in the examples to be described later, which have been reported so far, all have low efficiency and large chromaticity when driven after storage at 100 ° C. for 24 hours. There were problems such as changes and low durability. In order to solve these problems of the conventional device, the present inventors use the charge transport material having the m-kinkphenyl structure of the present invention to suppress the decrease in luminous efficiency after storage of the device at a high temperature, and the chromaticity. It has been found that an organic electroluminescence device satisfying all of the suppression of change and the improvement of durability at a high level is provided.
　すなわち、本発明の目的は、素子の高温保管後の発光効率の低下の抑制、色度変化の抑制、及び耐久性の向上の全てを、高い水準で満足する有機電界発光素子を提供することである。
　また、本発明の別の目的は、上述の有機電界発光素子に有用な化合物及び電荷輸送材料を提供することである。更に、本発明の別の目的は、本発明の有機電界発光素子を含む発光装置、表示装置及び照明装置を提供することである。 That is, an object of the present invention is to provide an organic electroluminescent device that satisfies all of the suppression of a decrease in luminous efficiency after storage of the device at a high temperature, the suppression of chromaticity change, and the improvement of durability at a high level. is there.
Another object of the present invention is to provide a compound and a charge transport material useful for the organic electroluminescence device described above. Furthermore, another object of the present invention is to provide a light emitting device, a display device, and a lighting device including the organic electroluminescent element of the present invention.
　本発明者らの検討によると、特定のｍ－キンクフェニル構造を有する電荷輸送材料を用いることで、素子の高温保管後の発光効率の低下の抑制、色度変化の抑制、及び耐久性の向上の全てを、高い水準で満足する有機電界発光素子が提供されることを見出した。 According to the study by the present inventors, by using a charge transport material having a specific m-kinkphenyl structure, it is possible to suppress a decrease in luminous efficiency after storage of the device at a high temperature, suppress a change in chromaticity, and improve durability. It was found that an organic electroluminescent device satisfying all of the above conditions at a high level is provided.
　すなわち、本発明は下記の手段により達成することができる。
　〔１〕基板上に、陽極及び陰極からなる一対の電極と、該電極間に発光層を含む少なくとも一層の有機層とを有する有機電界発光素子であって、
　前記発光層に燐光発光材料を少なくとも一種含み、かつ、前記少なくとも一層の有機層のいずれか少なくとも一層に下記一般式（１）で表される、ｍ－キンクフェニル構造を有する化合物を含む有機電界発光素子。 That is, the present invention can be achieved by the following means.
[1] An organic electroluminescent device having a pair of electrodes consisting of an anode and a cathode on a substrate, and at least one organic layer including a light emitting layer between the electrodes,
Organic electroluminescence comprising at least one phosphorescent material in the light emitting layer, and at least one of the at least one organic layer comprising a compound having an m-kinkphenyl structure represented by the following general formula (1) element.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　一般式（１）中、Ｒ１はアルキル基又はアリール基を表す。但し、Ｒ１で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ１が複数存在する時、複数のＲ１は同一でも異なってもよい。
　ｍ１は、一般式（１）中のｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１０以下の整数を表す。
　ｎ１は、一般式（１）中のｍ－キンクフェニル構造に置換したＲ１の数であり、０以上２２以下の整数を表す。ここで、ｍ１＋ｎ１は１以上２２以下の整数である。
　但し、一般式（１）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ１を有する。 In general formula (1), R 1 represents an alkyl group or an aryl group. However, the aryl group represented by R 1 does not have a condensed ring and may have an alkyl group or a cyano group. When R 1 there are a plurality, the plurality of R 1 may be the same or different.
m 1 is the number of cyano groups substituted in the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 10 or less.
n 1 is the number of R 1 substituted with the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 22 or less. Here, m 1 + n 1 is an integer of 1 or more and 22 or less.
However, the compound represented by the general formula (1) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 1 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
　〔２〕前記一般式（１）で表される化合物が下記一般式（２）で表される、上記〔１〕に記載の有機電界発光素子。 [2] The organic electroluminescent element according to the above [1], wherein the compound represented by the general formula (1) is represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　一般式（２）中、Ｒ２はアルキル基又はアリール基を表す。但し、Ｒ２で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ２が複数存在する時、複数のＲ２は同一でも異なってもよい。
　ｍ２は、一般式（２）中のビフェニル－ｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１４以下の整数を表す。
　ｎ２は、一般式（２）中のビフェニル－ｍ－キンクフェニル構造に置換したＲ２の数であり、０以上３０以下の整数を表す。ここで、ｍ２＋ｎ２は１以上３０以下の整数である。
　但し、一般式（２）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ２を有する。 In general formula (2), R 2 represents an alkyl group or an aryl group. However, the aryl group represented by R 2 does not have a condensed ring and may have an alkyl group or a cyano group. When R 2 there are a plurality, the plurality of R 2 may be the same or different.
m 2 is the number of cyano groups substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 14 or less.
n 2 is the number of R 2 substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 30 or less. Here, m 2 + n 2 is 1 to 30 integer.
However, the compound represented by the general formula (2) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 2 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
　〔３〕前記一般式（１）で表される化合物が下記一般式（３）で表される、上記〔１〕に記載の有機電界発光素子。 [3] The organic electroluminescent element according to the above [1], wherein the compound represented by the general formula (1) is represented by the following general formula (3).
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　一般式（３）中、Ｒ３はアルキル基又はアリール基を表す。但し、Ｒ３で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ３が複数存在する時、複数のＲ３は同一でも異なってもよい。
　ｍ３は、一般式（３）中のジフェニル－ｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１４以下の整数を表す。
　ｎ３は、一般式（３）中のジフェニル－ｍ－キンクフェニル構造に置換したＲ３の数であり、０以上３０以下の整数を表す。ここで、ｍ３＋ｎ３は１以上３０以下の整数である。
　但し、一般式（３）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ３を有する。 In general formula (3), R 3 represents an alkyl group or an aryl group. However, the aryl group represented by R 3 does not have a condensed ring and may have an alkyl group or a cyano group. When R 3 there are a plurality, the plurality of R 3 may be the same or different.
m 3 is the number of cyano groups substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 14 or less.
n 3 is the number of R 3 substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 30 or less. Here, m 3 + n 3 is an integer of 1 or more and 30 or less.
However, the compound represented by the general formula (3) does not have a benzene ring substituted with 3 or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 3 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
　〔４〕前記燐光発光材料が、下記一般式（Ｅ－１）で表されるイリジウム錯体である、上記〔１〕～〔３〕のいずれか一項に記載の有機電界発光素子。 [4] The organic electroluminescent element according to any one of [1] to [3], wherein the phosphorescent material is an iridium complex represented by the following general formula (E-1).
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　一般式（Ｅ－１）中、Ｚ１及びＺ２はそれぞれ独立に、炭素原子又は窒素原子を表す。
　Ａ１はＺ１と窒素原子と共に５又は６員のヘテロ環を形成する原子群を表す。
　Ｂ１はＺ２と炭素原子と共に５又は６員環を形成する原子群を表す。
　（Ｘ－Ｙ）はモノアニオン性の二座配位子を表す。
　ｎＥ１は１～３の整数を表す。
　〔５〕前記一般式（Ｅ－１）で表されるイリジウム錯体が下記一般式（Ｅ－２）で表される、上記〔４〕に記載の有機電界発光素子。 In general formula (E-1), Z 1 and Z 2 each independently represent a carbon atom or a nitrogen atom.
A 1 represents an atomic group that forms a 5- or 6-membered heterocycle with Z 1 and a nitrogen atom.
B 1 represents an atomic group that forms a 5- or 6-membered ring with Z 2 and a carbon atom.
(XY) represents a monoanionic bidentate ligand.
n E1 represents an integer of 1 to 3.
[5] The organic electroluminescence device as described in [4] above, wherein the iridium complex represented by the general formula (E-1) is represented by the following general formula (E-2).
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　一般式（Ｅ－２）中、ＡＥ１～ＡＥ８はそれぞれ独立に、窒素原子又はＣ－ＲＥを表す。
　ＲＥは水素原子又は置換基を表す。
　（Ｘ－Ｙ）はモノアニオン性の二座配位子を表す。
　ｎＥ２は１～３の整数を表す。
　〔６〕前記一般式（Ｅ－１）で表されるイリジウム錯体が下記一般式（Ｅ－６）で表される、上記〔４〕に記載の有機電界発光素子。 In general formula (E-2), A E1 to A E8 each independently represents a nitrogen atom or C—R E.
R E represents a hydrogen atom or a substituent.
(XY) represents a monoanionic bidentate ligand.
n E2 represents an integer of 1 to 3.
[6] The organic electroluminescence device as described in [4] above, wherein the iridium complex represented by the general formula (E-1) is represented by the following general formula (E-6).
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　一般式（Ｅ－６）中、Ｒ１ａ～Ｒ１ｋは、それぞれ独立に水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、－ＣＮ、ペルフルオロアルキル基、トリフルオロビニル基、－ＣＯ２Ｒ、－Ｃ（Ｏ）Ｒ、－ＮＲ２、－ＮＯ２、－ＯＲ、ハロゲン原子、アリール基又はヘテロアリール基を表し、更に置換基Ｚを有していてもよい。Ｒはそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。
　Ｒ１ａ～Ｒ１ｋは、任意の２つが互いに結合して縮合４～７員環を形成してもよく、該縮合４～７員環は更に置換基Ｚを有していてもよい。
　Ｚはそれぞれ独立に、ハロゲン原子、－Ｒ”、－ＯＲ”、－Ｎ（Ｒ”）２、－ＳＲ”、－Ｃ（Ｏ）Ｒ”、－Ｃ（Ｏ）ＯＲ”、－Ｃ（Ｏ）Ｎ（Ｒ”）２、－ＣＮ、－ＮＯ２、－ＳＯ２、－ＳＯＲ”、－ＳＯ２Ｒ”、又は－ＳＯ３Ｒ”を表し、Ｒ”はそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。
　（Ｘ－Ｙ）は、モノアニオン性の二座配位子を表す。
　ｎＥ６は１～３の整数を表す。 In general formula (E-6), R 1a to R 1k each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, —CN, a perfluoroalkyl group, a trifluorovinyl group, —CO 2 R, —C (O) R, —NR 2 , —NO 2 , —OR, a halogen atom, an aryl group, or a heteroaryl group, which may further have a substituent Z. Each R independently represents a hydrogen atom, an alkyl group, a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
Any two of R 1a to R 1k may be bonded to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring may further have a substituent Z.
Z is each independently a halogen atom, —R ″, —OR ″, —N (R ″) 2 , —SR ″, —C (O) R ″, —C (O) OR ″, —C (O) N (R ") 2, -CN , -NO 2, -SO 2, -SOR", - SO 2 R ", or -SO 3 R" represents, R "are each independently a hydrogen atom, an alkyl group, A perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group is represented.
(XY) represents a monoanionic bidentate ligand.
n E6 represents an integer of 1 to 3.
　〔７〕前記発光層と陰極との間に、前記発光層に隣接する有機層を有し、該有機層が前記一般式（１）～（３）のいずれかで表される化合物を含有する、上記〔１〕～〔６〕のいずれか一項に記載の有機電界発光素子。
　〔８〕前記発光層が前記一般式（１）～（３）のいずれかで表される化合物を含有する、上記〔１〕～〔７〕のいずれか一項に記載の有機電界発光素子。
　〔９〕前記一対の電極間に、前記陰極に隣接する電子注入層を有し、該電子注入層が前記一般式（１）～（３）のいずれかで表される化合物を含有する、上記〔１〕～〔８〕のいずれか一項に記載の有機電界発光素子。
　〔１０〕前記電子注入層が、更に電子供与性ドーパントを含有する、上記〔９〕に記載の有機電界発光素子。
　〔１１〕前記一対の電極間にある有機層の少なくとも一層が、溶液塗布法により形成されることを特徴とする上記〔１〕～〔１０〕のいずれか一項に記載の有機電界発光素子。
　〔１２〕上記〔１〕～〔１１〕のいずれか一項に記載の有機電界発光素子を用いた発光装置。
　〔１３〕上記〔１〕～〔１１〕のいずれか一項に記載の有機電界発光素子を用いた表示装置。
　〔１４〕上記〔１〕～〔１１〕のいずれか一項に記載の有機電界発光素子を用いた照明装置。 [7] An organic layer adjacent to the light emitting layer is provided between the light emitting layer and the cathode, and the organic layer contains a compound represented by any one of the general formulas (1) to (3). The organic electroluminescent device according to any one of [1] to [6] above.
[8] The organic electroluminescent element according to any one of [1] to [7], wherein the light emitting layer contains a compound represented by any one of the general formulas (1) to (3).
[9] The electron injection layer adjacent to the cathode between the pair of electrodes, the electron injection layer containing the compound represented by any one of the general formulas (1) to (3) [1] The organic electroluminescence device as described in any one of [8].
[10] The organic electroluminescent element as described in [9] above, wherein the electron injection layer further contains an electron donating dopant.
[11] The organic electroluminescent element as described in any one of [1] to [10] above, wherein at least one organic layer between the pair of electrodes is formed by a solution coating method.
[12] A light emitting device using the organic electroluminescent element as described in any one of [1] to [11].
[13] A display device using the organic electroluminescent element as described in any one of [1] to [11].
[14] An illumination device using the organic electroluminescent element as described in any one of [1] to [11].
　〔１５〕下記一般式（１）で表される電荷輸送材料。 [15] A charge transport material represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　一般式（１）中、Ｒ１はアルキル基又はアリール基を表す。但し、Ｒ１で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ１が複数存在する時、複数のＲ１は同一でも異なってもよい。
　ｍ１は、一般式（１）中のｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１０以下の整数を表す。
　ｎ１は、一般式（１）中のｍ－キンクフェニル構造に置換したＲ１の数であり、０以上２２以下の整数を表す。ここで、ｍ１＋ｎ１は１以上２２以下の整数である。
　但し、一般式（１）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ１を有する。 In general formula (1), R 1 represents an alkyl group or an aryl group. However, the aryl group represented by R 1 does not have a condensed ring and may have an alkyl group or a cyano group. When R 1 there are a plurality, the plurality of R 1 may be the same or different.
m 1 is the number of cyano groups substituted in the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 10 or less.
n 1 is the number of R 1 substituted with the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 22 or less. Here, m 1 + n 1 is an integer of 1 or more and 22 or less.
However, the compound represented by the general formula (1) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 1 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
　〔１６〕下記一般式（２）で表される、上記〔１５〕に記載の電荷輸送材料。 [16] The charge transport material according to [15], which is represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　一般式（２）中、Ｒ２はアルキル基又はアリール基を表す。但し、Ｒ２で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ２が複数存在する時、複数のＲ２は同一でも異なってもよい。
　ｍ２は、一般式（２）中のビフェニル－ｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１４以下の整数を表す。
　ｎ２は、一般式（２）中のビフェニル－ｍ－キンクフェニル構造に置換したＲ２の数であり、０以上３０以下の整数を表す。ここで、ｍ２＋ｎ２は１以上３０以下の整数である。
　但し、一般式（２）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ２を有する。 In general formula (2), R 2 represents an alkyl group or an aryl group. However, the aryl group represented by R 2 does not have a condensed ring and may have an alkyl group or a cyano group. When R 2 there are a plurality, the plurality of R 2 may be the same or different.
m 2 is the number of cyano groups substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 14 or less.
n 2 is the number of R 2 substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 30 or less. Here, m 2 + n 2 is 1 to 30 integer.
However, the compound represented by the general formula (2) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 2 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
　〔１７〕下記一般式（３）で表される、上記〔１５〕に記載の電荷輸送材料。 [17] The charge transport material according to [15], which is represented by the following general formula (3).
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　一般式（３）中、Ｒ３はアルキル基又はアリール基を表す。但し、Ｒ３で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ３が複数存在する時、複数のＲ３は同一でも異なってもよい。
　ｍ３は、一般式（３）中のジフェニル－ｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１４以下の整数を表す。
　ｎ３は、一般式（３）中のジフェニル－ｍ－キンクフェニル構造に置換したＲ３の数であり、０以上３０以下の整数を表す。ここで、ｍ３＋ｎ３は１以上３０以下の整数である。
　但し、一般式（３）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ３を有する。 In general formula (3), R 3 represents an alkyl group or an aryl group. However, the aryl group represented by R 3 does not have a condensed ring and may have an alkyl group or a cyano group. When R 3 there are a plurality, the plurality of R 3 may be the same or different.
m 3 is the number of cyano groups substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 14 or less.
n 3 is the number of R 3 substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 30 or less. Here, m 3 + n 3 is an integer of 1 or more and 30 or less.
However, the compound represented by the general formula (3) does not have a benzene ring substituted with 3 or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 3 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
　〔１８〕上記〔１５〕～〔１７〕のいずれか一項に記載の電荷輸送材料を含む組成物。
　〔１９〕上記〔１５〕～〔１７〕のいずれか一項に記載の電荷輸送材料を含む薄膜。 [18] A composition comprising the charge transport material according to any one of [15] to [17].
[19] A thin film comprising the charge transport material according to any one of [15] to [17].
　〔２０〕下記一般式（１）で表される化合物。 [20] A compound represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　一般式（１）中、Ｒ１はアルキル基又はアリール基を表す。但し、Ｒ１で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ１が複数存在する時、複数のＲ１は同一でも異なってもよい。
　ｍ１は、一般式（１）中のｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１０以下の整数を表す。
　ｎ１は、一般式（１）中のｍ－キンクフェニル構造に置換したＲ１の数であり、０以上２２以下の整数を表す。ここで、ｍ１＋ｎ１は１以上２２以下の整数である。
　但し、一般式（１）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ１を有する。 In general formula (1), R 1 represents an alkyl group or an aryl group. However, the aryl group represented by R 1 does not have a condensed ring and may have an alkyl group or a cyano group. When R 1 there are a plurality, the plurality of R 1 may be the same or different.
m 1 is the number of cyano groups substituted in the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 10 or less.
n 1 is the number of R 1 substituted with the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 22 or less. Here, m 1 + n 1 is an integer of 1 or more and 22 or less.
However, the compound represented by the general formula (1) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 1 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
　〔２１〕下記一般式（２）で表される、上記〔２０〕に記載の化合物。 [21] The compound according to [20], which is represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　一般式（２）中、Ｒ２はアルキル基又はアリール基を表す。但し、Ｒ２で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ２が複数存在する時、複数のＲ２は同一でも異なってもよい。
　ｍ２は、一般式（２）中のビフェニル－ｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１４以下の整数を表す。
　ｎ２は、一般式（２）中のビフェニル－ｍ－キンクフェニル構造に置換したＲ２の数であり、０以上３０以下の整数を表す。ここで、ｍ２＋ｎ２は１以上３０以下の整数である。
　但し、一般式（２）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ２を有する。 In general formula (2), R 2 represents an alkyl group or an aryl group. However, the aryl group represented by R 2 does not have a condensed ring and may have an alkyl group or a cyano group. When R 2 there are a plurality, the plurality of R 2 may be the same or different.
m 2 is the number of cyano groups substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 14 or less.
n 2 is the number of R 2 substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 30 or less. Here, m 2 + n 2 is 1 to 30 integer.
However, the compound represented by the general formula (2) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 2 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
　〔２２〕下記一般式（３）で表される、上記〔２０〕に記載の化合物。 [22] The compound according to [20], which is represented by the following general formula (3).
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　一般式（３）中、Ｒ３はアルキル基又はアリール基を表す。但し、Ｒ３で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ３が複数存在する時、複数のＲ３は同一でも異なってもよい。
　ｍ３は、一般式（３）中のジフェニル－ｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１４以下の整数を表す。
　ｎ３は、一般式（３）中のジフェニル－ｍ－キンクフェニル構造に置換したＲ３の数であり、０以上３０以下の整数を表す。ここで、ｍ３＋ｎ３は１以上３０以下の整数である。
　但し、一般式（３）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ３を有する。 In general formula (3), R 3 represents an alkyl group or an aryl group. However, the aryl group represented by R 3 does not have a condensed ring and may have an alkyl group or a cyano group. When R 3 there are a plurality, the plurality of R 3 may be the same or different.
m 3 is the number of cyano groups substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 14 or less.
n 3 is the number of R 3 substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 30 or less. Here, m 3 + n 3 is an integer of 1 or more and 30 or less.
However, the compound represented by the general formula (3) does not have a benzene ring substituted with 3 or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 3 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
　本発明によれば、素子の高温保管後の発光効率の低下の抑制、色度変化の抑制、及び耐久性の向上の全てを、高い水準で満足する有機電界発光素子を提供することができる。 According to the present invention, it is possible to provide an organic electroluminescent device that satisfies all of the suppression of a decrease in luminous efficiency after storage of the device at a high temperature, the suppression of chromaticity change, and the improvement of durability at a high level.
本発明に係る有機電界発光素子の構成の一例を示す概略図である。It is the schematic which shows an example of a structure of the organic electroluminescent element which concerns on this invention. 本発明に係る発光装置の一例を示す概略図である。It is the schematic which shows an example of the light-emitting device which concerns on this invention. 本発明に係る照明装置の一例を示す概略図である。It is the schematic which shows an example of the illuminating device which concerns on this invention.
　下記一般式（１）～（３）の説明における水素原子は同位体（重水素原子等）も含み、また更に置換基を構成する原子は、その同位体も含んでいることを表す。
　本発明において、「置換基」というとき、その置換基は置換されていてもよい。例えば、本発明で「アルキル基」と言う時、フッ素原子で置換されたアルキル基（例えばトリフルオロメチル基）やアリール基で置換されたアルキル基（例えばトリフェニルメチル基）なども含むが、「炭素数１～６のアルキル基」と言うとき、置換されたものも含めた全ての基として炭素数が１～６であることを示す。 In the description of the following general formulas (1) to (3), a hydrogen atom includes an isotope (deuterium atom and the like), and an atom constituting a substituent further includes the isotope.
In the present invention, when the term “substituent” is used, the substituent may be substituted. For example, the term “alkyl group” in the present invention includes an alkyl group substituted with a fluorine atom (for example, trifluoromethyl group) and an alkyl group substituted with an aryl group (for example, triphenylmethyl group). When the term “alkyl group having 1 to 6 carbon atoms” is used, it means that all groups including substituted ones have 1 to 6 carbon atoms.
　本発明において、置換基群Ａ、置換基群Ｂ及び置換基Ｚ’を以下のように定義する。
（置換基群Ａ）
　アルキル基（好ましくは炭素数１～３０、より好ましくは炭素数１～２０、特に好ましくは炭素数１～１０であり、例えばメチル、エチル、イソプロピル、ｔｅｒｔ－ブチル、ｎ－オクチル、ｎ－デシル、ｎ－ヘキサデシル、シクロプロピル、シクロペンチル、シクロヘキシルなどが挙げられる。）、アルケニル基（好ましくは炭素数２～３０、より好ましくは炭素数２～２０、特に好ましくは炭素数２～１０であり、例えばビニル、アリル、２－ブテニル、３－ペンテニルなどが挙げられる。）、アルキニル基（好ましくは炭素数２～３０、より好ましくは炭素数２～２０、特に好ましくは炭素数２～１０であり、例えばプロパルギル、３－ペンチニルなどが挙げられる。）、アリール基（好ましくは炭素数６～３０、より好ましくは炭素数６～２０、特に好ましくは炭素数６～１２であり、例えばフェニル、ｐ－メチルフェニル、ナフチル、アントリルなどが挙げられる。）、アミノ基（好ましくは炭素数０～３０、より好ましくは炭素数０～２０、特に好ましくは炭素数０～１０であり、例えばアミノ、メチルアミノ、ジメチルアミノ、ジエチルアミノ、ジベンジルアミノ、ジフェニルアミノ、ジトリルアミノなどが挙げられる。）、アルコキシ基（好ましくは炭素数１～３０、より好ましくは炭素数１～２０、特に好ましくは炭素数１～１０であり、例えばメトキシ、エトキシ、ブトキシ、２－エチルヘキシロキシなどが挙げられる。）、アリールオキシ基（好ましくは炭素数６～３０、より好ましくは炭素数６～２０、特に好ましくは炭素数６～１２であり、例えばフェニルオキシ、１－ナフチルオキシ、２－ナフチルオキシなどが挙げられる。）、ヘテロ環オキシ基（好ましくは炭素数１～３０、より好ましくは炭素数１～２０、特に好ましくは炭素数１～１２であり、例えばピリジルオキシ、ピラジルオキシ、ピリミジルオキシ、キノリルオキシなどが挙げられる。）、アシル基（好ましくは炭素数２～３０、より好ましくは炭素数２～２０、特に好ましくは炭素数２～１２であり、例えばアセチル、ベンゾイル、ホルミル、ピバロイルなどが挙げられる。）、アルコキシカルボニル基（好ましくは炭素数２～３０、より好ましくは炭素数２～２０、特に好ましくは炭素数２～１２であり、例えばメトキシカルボニル、エトキシカルボニルなどが挙げられる。）、アリールオキシカルボニル基（好ましくは炭素数７～３０、より好ましくは炭素数７～２０、特に好ましくは炭素数７～１２であり、例えばフェニルオキシカルボニルなどが挙げられる。）、アシルオキシ基（好ましくは炭素数２～３０、より好ましくは炭素数２～２０、特に好ましくは炭素数２～１０であり、例えばアセトキシ、ベンゾイルオキシなどが挙げられる。）、アシルアミノ基（好ましくは炭素数２～３０、より好ましくは炭素数２～２０、特に好ましくは炭素数２～１０であり、例えばアセチルアミノ、ベンゾイルアミノなどが挙げられる。）、アルコキシカルボニルアミノ基（好ましくは炭素数２～３０、より好ましくは炭素数２～２０、特に好ましくは炭素数２～１２であり、例えばメトキシカルボニルアミノなどが挙げられる。）、アリールオキシカルボニルアミノ基（好ましくは炭素数７～３０、より好ましくは炭素数７～２０、特に好ましくは炭素数７～１２であり、例えばフェニルオキシカルボニルアミノなどが挙げられる。）、スルホニルアミノ基（好ましくは炭素数１～３０、より好ましくは炭素数１～２０、特に好ましくは炭素数１～１２であり、例えばメタンスルホニルアミノ、ベンゼンスルホニルアミノなどが挙げられる。）、スルファモイル基（好ましくは炭素数０～３０、より好ましくは炭素数０～２０、特に好ましくは炭素数０～１２であり、例えばスルファモイル、メチルスルファモイル、ジメチルスルファモイル、フェニルスルファモイルなどが挙げられる。）、カルバモイル基（好ましくは炭素数１～３０、より好ましくは炭素数１～２０、特に好ましくは炭素数１～１２であり、例えばカルバモイル、メチルカルバモイル、ジエチルカルバモイル、フェニルカルバモイルなどが挙げられる。）、アルキルチオ基（好ましくは炭素数１～３０、より好ましくは炭素数１～２０、特に好ましくは炭素数１～１２であり、例えばメチルチオ、エチルチオなどが挙げられる。）、アリールチオ基（好ましくは炭素数６～３０、より好ましくは炭素数６～２０、特に好ましくは炭素数６～１２であり、例えばフェニルチオなどが挙げられる。）、ヘテロ環チオ基（好ましくは炭素数１～３０、より好ましくは炭素数１～２０、特に好ましくは炭素数１～１２であり、例えばピリジルチオ、２－ベンズイミダゾリルチオ、２－ベンズオキサゾリルチオ、２－ベンズチアゾリルチオなどが挙げられる。）、スルホニル基（好ましくは炭素数１～３０、より好ましくは炭素数１～２０、特に好ましくは炭素数１～１２であり、例えばメシル、トシルなどが挙げられる。）、スルフィニル基（好ましくは炭素数１～３０、より好ましくは炭素数１～２０、特に好ましくは炭素数１～１２であり、例えばメタンスルフィニル、ベンゼンスルフィニルなどが挙げられる。）、ウレイド基（好ましくは炭素数１～３０、より好ましくは炭素数１～２０、特に好ましくは炭素数１～１２であり、例えばウレイド、メチルウレイド、フェニルウレイドなどが挙げられる。）、リン酸アミド基（好ましくは炭素数１～３０、より好ましくは炭素数１～２０、特に好ましくは炭素数１～１２であり、例えばジエチルリン酸アミド、フェニルリン酸アミドなどが挙げられる。）、ヒドロキシ基、メルカプト基、ハロゲン原子（例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子）、シアノ基、スルホ基、カルボキシル基、ニトロ基、ヒドロキサム酸基、スルフィノ基、ヒドラジノ基、イミノ基、ヘテロ環基（芳香族ヘテロ環基も包含し、好ましくは炭素数１～３０、より好ましくは炭素数１～１２であり、ヘテロ原子としては、例えば窒素原子、酸素原子、硫黄原子、リン原子、ケイ素原子、セレン原子、テルル原子であり、具体的にはピリジル、ピラジニル、ピリミジル、ピリダジニル、ピロリル、ピラゾリル、トリアゾリル、イミダゾリル、オキサゾリル、チアゾリル、イソキサゾリル、イソチアゾリル、キノリル、フリル、チエニル、セレノフェニル、テルロフェニル、ピペリジル、ピペリジノ、モルホリノ、ピロリジル、ピロリジノ、ベンゾオキサゾリル、ベンゾイミダゾリル、ベンゾチアゾリル、カルバゾリル基、アゼピニル基、シロリル基などが挙げられる。）、シリル基（好ましくは炭素数３～４０、より好ましくは炭素数３～３０、特に好ましくは炭素数３～２４であり、例えばトリメチルシリル、トリフェニルシリルなどが挙げられる。）、シリルオキシ基（好ましくは炭素数３～４０、より好ましくは炭素数３～３０、特に好ましくは炭素数３～２４であり、例えばトリメチルシリルオキシ、トリフェニルシリルオキシなどが挙げられる。）、ホスホリル基（例えばジフェニルホスホリル基、ジメチルホスホリル基などが挙げられる。）が挙げられる。これらの置換基は更に置換されてもよく、更なる置換基としては、以上に説明した置換基群Ａから選択される基を挙げることができる。 In the present invention, the substituent group A, the substituent group B, and the substituent Z ′ are defined as follows.
(Substituent group A)
An alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as vinyl , Allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as propargyl , 3-pentynyl, etc.), aryl groups (preferably having 6 to 30 carbon atoms, more preferably carbon 6 to 20, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, anthryl, etc.), amino group (preferably 0 to 30 carbon atoms, more preferably 0 carbon atoms) To 20 and particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, and ditolylamino), alkoxy groups (preferably having 1 to 30 carbon atoms). More preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.), an aryloxy group (preferably 6 to 6 carbon atoms). 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms. And a heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms). For example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy and the like), an acyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms). , Benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxy Carbonyl, etc.), aryloxycarbonyl group (preferably carbon The number of primes is 7 to 30, more preferably 7 to 20, and particularly preferably 7 to 12, and examples thereof include phenyloxycarbonyl. ), An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy, benzoyloxy, etc.), an acylamino group (preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably 2-10 carbon atoms, and examples thereof include acetylamino, benzoylamino and the like, and alkoxycarbonylamino groups (preferably having 2-2 carbon atoms). 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, etc.), an aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl And sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino). ), A sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenyl Sulfamoyl, etc.), carbamoyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, Phenylcarbamoyl etc.), alkylthio group ( Preferably, it has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio, ethylthio, etc.), an arylthio group (preferably 6 to 30 carbon atoms). More preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 to carbon atoms). 20, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio, etc.), a sulfonyl group (preferably having 1 carbon atom) To 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl). A sulfinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl. ), A ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid An amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenyl phosphoric acid amide), a hydroxy group , Mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group ( An aromatic heterocyclic group is also included, preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms. Is, for example, a nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom, selenium atom, tellurium atom, specifically pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, pyrrolyl, pyrazolyl, triazolyl, imidazolyl, oxazolyl, thiazolyl, And isoxazolyl, isothiazolyl, quinolyl, furyl, thienyl, selenophenyl, tellurophenyl, piperidyl, piperidino, morpholino, pyrrolidyl, pyrrolidino, benzoxazolyl, benzoimidazolyl, benzothiazolyl, carbazolyl group, azepinyl group, silolyl group and the like. A silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl). A aryloxy group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyloxy, triphenylsilyloxy, etc.), phosphoryl group (for example, A diphenylphosphoryl group, a dimethylphosphoryl group, etc.). These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group A described above.
（置換基群Ｂ）
　アルキル基（好ましくは炭素数１～３０、より好ましくは炭素数１～２０、特に好ましくは炭素数１～１０であり、例えばメチル、エチル、イソプロピル、ｔｅｒｔ－ブチル、ｎ－オクチル、ｎ－デシル、ｎ－ヘキサデシル、シクロプロピル、シクロペンチル、シクロヘキシルなどが挙げられる。）、アルケニル基（好ましくは炭素数２～３０、より好ましくは炭素数２～２０、特に好ましくは炭素数２～１０であり、例えばビニル、アリル、２－ブテニル、３－ペンテニルなどが挙げられる。）、アルキニル基（好ましくは炭素数２～３０、より好ましくは炭素数２～２０、特に好ましくは炭素数２～１０であり、例えばプロパルギル、３－ペンチニルなどが挙げられる。）、アリール基（好ましくは炭素数６～３０、より好ましくは炭素数６～２０、特に好ましくは炭素数６～１２であり、例えばフェニル、ｐ－メチルフェニル、ナフチル、アントリルなどが挙げられる。）、シアノ基、ヘテロ環基（芳香族ヘテロ環基も包含し、好ましくは炭素数１～３０、より好ましくは炭素数１～１２であり、ヘテロ原子としては、例えば窒素原子、酸素原子、硫黄原子、リン原子、ケイ素原子、セレン原子、テルル原子であり、具体的にはピリジル、ピラジニル、ピリミジル、ピリダジニル、ピロリル、ピラゾリル、トリアゾリル、イミダゾリル、オキサゾリル、チアゾリル、イソキサゾリル、イソチアゾリル、キノリル、フリル、チエニル、セレノフェニル、テルロフェニル、ピペリジル、ピペリジノ、モルホリノ、ピロリジル、ピロリジノ、ベンゾオキサゾリル、ベンゾイミダゾリル、ベンゾチアゾリル、カルバゾリル基、アゼピニル基、シロリル基などが挙げられる。）が挙げられる。これらの置換基は更に置換されてもよく、更なる置換基としては、以上に説明した置換基群Ｂから選択される基を挙げることができる。 (Substituent group B)
An alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as vinyl , Allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as propargyl , 3-pentynyl, etc.), aryl groups (preferably having 6 to 30 carbon atoms, more preferably carbon 6 to 20, particularly preferably 6 to 12 carbon atoms, including, for example, phenyl, p-methylphenyl, naphthyl, anthryl, etc.), cyano group, heterocyclic group (including aromatic heterocyclic group, Has 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom, a selenium atom, and a tellurium atom. Is pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, pyrrolyl, pyrazolyl, triazolyl, imidazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, quinolyl, furyl, thienyl, selenophenyl, tellurophenyl, piperidyl, piperidino, morpholino, pyrrolidyl, pyrrolidino, benzoxazolid Le, benzimidazoli , Benzothiazolyl, carbazolyl, azepinyl group,. Etc. Shiroriru group) can be mentioned. These substituents may be further substituted, and examples of the further substituent include groups selected from the substituent group B described above.
＜置換基Ｚ’＞
　アルキル基（好ましくは炭素数１～１０、より好ましくは炭素数１～６、更に好ましくは炭素数１～４であり、例えばメチル、エチル、イソプロピル、ｎ－プロピル、ｔｅｒｔ－ブチル、イソブチル、ｎ－ブチル、ネオペンチル、ｎ－ペンチル、ｎ－ヘキシル、シクロプロピル、シクロペンチル、シクロヘキシルなどが挙げられる）、アルケニル基（好ましくは炭素数２～８、より好ましくは炭素数２～５であり、例えばビニル等が挙げられる）、アリール基（炭素数６～３０、より好ましくは炭素数６～２０であり、例えばフェニル基、ナフチル基、アントラセニル基、テトラセニル基、ピレニル基、ペリレニル基、トリフェニレニル基、クリセニル基が挙げられる）、ヘテロアリール基（好ましくは炭素数４～３０、より好ましくは炭素数４～２０であり、例えばピリジン、ピラジン、ピリミジン、ピリダジン、トリアジン、チオフェン、フラン、オキサゾール、チアゾール、イミダゾール、ピラゾール、トリアゾール、オキサジアゾール、チアジアゾール等が挙げられる）、アルコキシ基（好ましくは炭素数１～８、より好ましくは炭素数１～５であり、例えばメトキシ基、エトキシ基、ｎ－プロピルオキシ基、ｉｓｏ－プロピルオキシ基等が挙げられる）、フェノキシ基、ハロゲン原子（好ましくはフッ素原子）、シリル基（好ましくは炭素数４～３０、より好ましくは炭素数４～２０であり、トリメチルシリル基、トリエチルシリル基、トリフェニルシリル基などが挙げられる）、アミノ基（好ましくは炭素数２～６０、より好ましくは炭素数２～４０であり、ジメチルアミノ基、ジエチルアミノ基、ジフェニルアミノ基等が挙げられる）、シアノ基又はこれらを組み合わせて成る基を表し、複数の置換基Ｚ’は互いに結合してアリール環を形成しても良い。複数の置換基Ｚ’が互いに結合して形成するアリール環としては、フェニル環、ピリジン環等が挙げられ、フェニル環が好ましい。 <Substituent Z '>
An alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, such as methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, n- Butyl, neopentyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl group (preferably having 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms, such as vinyl) Aryl group (having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, such as phenyl group, naphthyl group, anthracenyl group, tetracenyl group, pyrenyl group, perylenyl group, triphenylenyl group, chrysenyl group) Heteroaryl group (preferably having 4 to 30 carbon atoms, more preferably carbon 4 to 20, for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiophene, furan, oxazole, thiazole, imidazole, pyrazole, triazole, oxadiazole, thiadiazole and the like, alkoxy group (preferably having 1 carbon atom) To 8, more preferably 1 to 5 carbon atoms, such as methoxy, ethoxy, n-propyloxy, iso-propyloxy, etc.), phenoxy, halogen (preferably fluorine), A silyl group (preferably having 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, such as trimethylsilyl group, triethylsilyl group, triphenylsilyl group), an amino group (preferably having 2 to 60 carbon atoms, More preferably, it has 2 to 40 carbon atoms, and dimethyl Amino group, a diethylamino group, and a diphenylamino group), a cyano group or a group formed by combining these groups, a plurality of substituents Z 'may form an aryl ring bonded to each other. Examples of the aryl ring formed by bonding a plurality of substituents Z ′ to each other include a phenyl ring and a pyridine ring, and a phenyl ring is preferable.
　本発明の有機電界発光素子は、基板上に、陽極及び陰極からなる一対の電極と、該電極間に発光層を含む少なくとも一層の有機層とを有する有機電界発光素子であって、前記発光層に燐光発光材料を少なくとも一種含み、かつ、前記少なくとも一層の有機層のいずれか少なくとも一層に後述の一般式（１）で表される、ｍ－キンクフェニル構造を有する化合物を含有する。
　なお本発明は、一般式（１）で表される化合物にも関する。一般式（１）で表される化合物は、好ましくは後述の一般式（２）又は（３）で表される化合物である。 The organic electroluminescent device of the present invention is an organic electroluminescent device having a pair of electrodes comprising an anode and a cathode and at least one organic layer including a light emitting layer between the electrodes on the substrate, wherein the light emitting layer And at least one of the at least one organic layer contains a compound having an m-kinkphenyl structure represented by the following general formula (1).
In addition, this invention relates also to the compound represented by General formula (1). The compound represented by the general formula (1) is preferably a compound represented by the following general formula (2) or (3).
〔一般式（１）で表される化合物〕
　以下、一般式（１）で表される化合物について説明する。 [Compound represented by the general formula (1)]
Hereinafter, the compound represented by the general formula (1) will be described.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　一般式（１）中、Ｒ１はアルキル基又はアリール基を表す。但し、Ｒ１で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ１が複数存在する時、複数のＲ１は同一でも異なってもよい。
　ｍ１は、一般式（１）中のｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１０以下の整数を表す。
　ｎ１は、一般式（１）中のｍ－キンクフェニル構造に置換したＲ１の数であり、０以上２２以下の整数を表す。ここで、ｍ１＋ｎ１は１以上２２以下の整数である。
　但し、一般式（１）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ１を有する。 In general formula (1), R 1 represents an alkyl group or an aryl group. However, the aryl group represented by R 1 does not have a condensed ring and may have an alkyl group or a cyano group. When R 1 there are a plurality, the plurality of R 1 may be the same or different.
m 1 is the number of cyano groups substituted in the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 10 or less.
n 1 is the number of R 1 substituted with the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 22 or less. Here, m 1 + n 1 is an integer of 1 or more and 22 or less.
However, the compound represented by the general formula (1) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 1 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
　Ｒ１で表されるアルキル基は、直鎖、分岐鎖、又は環状のアルキル基であり、フッ素原子、シアノ基等の置換基は有さない。すなわち、Ｒ１で表されるアルキル基は無置換のアルキル基である。Ｒ１で表されるアルキル基は、好ましくは炭素数１～１８のアルキル基であり、より好ましくは炭素数１～１２のアルキル基であり、更に好ましくは炭素数１～６のアルキル基である。Ｒ１で表されるアルキル基は、特に好ましくはメチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｔ－ブチル基、ｉ－ブチル基、ｎ－ペンチル基、ネオペンチル基、ｔ－アミル基、ｓ－イソアミル基、シクロペンチル基、ｎ－ヘキシル基、及びシクロヘキシル基のいずれかであり、最も好ましくはメチル基、ｉ－プロピル基、ｎ－ブチル基、及びｔ－ブチル基のいずれかである。 The alkyl group represented by R 1 is a linear, branched, or cyclic alkyl group and does not have a substituent such as a fluorine atom or a cyano group. That is, the alkyl group represented by R 1 is an unsubstituted alkyl group. The alkyl group represented by R 1 is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and still more preferably an alkyl group having 1 to 6 carbon atoms. . The alkyl group represented by R 1 is particularly preferably a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, i-butyl group, n-pentyl group, neopentyl group. Group, t-amyl group, s-isoamyl group, cyclopentyl group, n-hexyl group and cyclohexyl group, most preferably methyl group, i-propyl group, n-butyl group and t-butyl group One of them.
　Ｒ１で表されるアリール基は、ナフタレン環やアントラセン環等の縮合環を有さないアリール基である。またＲ１で表されるアリール基には、窒素原子、硫黄原子、酸素原子等のヘテロ原子を含むヘテロアリール基は含まれない。すなわち、Ｒ１で表されるアリール基はヘテロ環を有さない。Ｒ１で表されるアリール基は、典型的には、一つの単環の芳香族炭化水素、又は複数の単環の芳香族炭化水素が互いに単結合で連結した芳香族炭化水素の環炭素原子から、一個の水素原子を除去してなる一価の基であり、芳香環を１～５個含むことが好ましく、１～３個含むことがより好ましい。またＲ１で表されるアリール基に含まれる芳香環は、ベンゼン環であることが好ましい。Ｒ１で表されるアリール基には、前述のアルキル基又はシアノ基が置換していてもよい。Ｒ１で表されるアリール基は、好ましくはアルキル基若しくはシアノ基が置換していてもよい、フェニル基、ビフェニル基、ターフェニル基、クォーターフェニル基、又はキンクフェニル基であり、より好ましくはアルキル基若しくはシアノ基が置換していてもよい、フェニル基、ビフェニル基、又はターフェニル基である。Ｒ１で表されるアリール基に複数のベンゼン環が含まれる場合、該複数のベンゼン環はメタ位（ｍ－）で連結していることが好ましい。Ｒ１で表されるアリール基に置換していてもよいアルキル基の好ましい範囲は、前述のＲ１で表されるアルキル基の好ましい範囲と同様である。 The aryl group represented by R 1 is an aryl group having no condensed ring such as a naphthalene ring or an anthracene ring. The aryl group represented by R 1 does not include a heteroaryl group containing a hetero atom such as a nitrogen atom, a sulfur atom, or an oxygen atom. That is, the aryl group represented by R 1 does not have a heterocycle. The aryl group represented by R 1 is typically an aromatic hydrocarbon ring carbon atom in which one monocyclic aromatic hydrocarbon or a plurality of monocyclic aromatic hydrocarbons are connected to each other by a single bond. Thus, it is a monovalent group formed by removing one hydrogen atom, and preferably contains 1 to 5 aromatic rings, more preferably 1 to 3 aromatic rings. The aromatic ring contained in the aryl group represented by R 1 is preferably a benzene ring. The aryl group represented by R 1 may be substituted with the aforementioned alkyl group or cyano group. The aryl group represented by R 1 is preferably a phenyl group, a biphenyl group, a terphenyl group, a quarterphenyl group, or a kinkphenyl group, which may be substituted with an alkyl group or a cyano group, and more preferably an alkyl group. A phenyl group, a biphenyl group, or a terphenyl group, which may be substituted with a group or a cyano group. When the aryl group represented by R 1 includes a plurality of benzene rings, the plurality of benzene rings are preferably linked at the meta position (m-). The preferred range of the alkyl group that may be substituted on the aryl group represented by R 1 is the same as the preferred range of the alkyl group represented by R 1 described above.
　ｍ１は、一般式（１）中のｍ－キンクフェニル構造、すなわち一般式（１）中で構造式として示されるメタ位で連結した５つのベンゼン環、に置換したシアノ基の数であり、０以上１０以下の整数を表す。ここで言う置換とは、前記５つのベンゼン環上の任意の一つの水素原子がシアノ基に置き換えられた状態をいい、前述のＲ１で表されるアリール基に置換していてもよいシアノ基はｍ１の数に含まれない。また後述するように、前記５つのベンゼン環のいずれか１つのベンゼン環に、３個以上のシアノ基が置換することは無い。
　本発明においては、電荷輸送性及び化学的安定性の観点から一般式（１）中のｍ－キンクフェニル構造に置換したシアノ基が少なくとも１個存在すること（すなわち、ｍ１は１以上１０以下の整数であること）が好ましく、より好ましくはｍ１が１以上５以下の整数であり、更に好ましくは１以上３以下の整数である。 m 1 is the number of cyano groups substituted in the m-kinkphenyl structure in the general formula (1), that is, five benzene rings linked at the meta position shown as the structural formula in the general formula (1), Represents an integer of 0 to 10. The substitution referred to here means a state in which any one hydrogen atom on the five benzene rings is replaced by a cyano group, and the cyano group optionally substituted by the aryl group represented by R 1 described above. Is not included in the number of m 1 . Further, as will be described later, three or more cyano groups are not substituted on any one of the five benzene rings.
In the present invention, at least one cyano group substituted on the m-kinkphenyl structure in the general formula (1) is present from the viewpoint of charge transportability and chemical stability (that is, m 1 is 1 or more and 10 or less. preferably of an integer that) is, more preferably m 1 is 1 to 5 integer, more preferably from 1 to 3 of an integer.
　ｎ１は、一般式（１）中のｍ－キンクフェニル構造、すなわち一般式（１）中で構造式として示されるメタ位で連結した５つのベンゼン環、に置換したＲ１の数であり、０以上２２以下の整数を表す。ｎ１は、電荷輸送性及び化学的安定性の観点から好ましくは１以上５以下の整数であり、より好ましくは１以上３以下の整数である。 n 1 is the number of R 1 substituted in the m-kinkphenyl structure in the general formula (1), that is, five benzene rings linked at the meta position shown as the structural formula in the general formula (1), An integer from 0 to 22 is represented. n 1 is preferably an integer of 1 to 5 and more preferably an integer of 1 to 3 from the viewpoint of charge transportability and chemical stability.
　一般式（１）で表される化合物は、ベンゼン環に置換したシアノ基を少なくとも１個有する。ここで言うシアノ基はベンゼン環に置換していれば特に制限されず、前記ｍ１で数えられるシアノ基の一つであってもよいし、前記Ｒ１で表されるアリール基中のベンゼン環に置換したシアノ基であってもよい。電子求引性基として化学的に安定なシアノ基をベンゼン環に有することにより、電子輸送材料として使用した際の電子の移動がより円滑になる。
　ｍ１が０の場合、ベンゼン環に置換したシアノ基はＲ１に含まれることになるので、ｍ１＋ｎ１は１以上２２以下の整数となる。ｍ１＋ｎ１は、好ましくは２以上８以下の整数であり、より好ましくは３以上６以下の整数である。 The compound represented by the general formula (1) has at least one cyano group substituted on the benzene ring. The cyano group referred to here is not particularly limited as long as it is substituted on the benzene ring, and may be one of the cyano groups counted by m 1 or the benzene ring in the aryl group represented by R 1. A cyano group substituted with may be used. By having a chemically stable cyano group as an electron withdrawing group in the benzene ring, the movement of electrons when used as an electron transporting material becomes smoother.
When m 1 is 0, a cyano group substituted on the benzene ring is included in R 1, and therefore m 1 + n 1 is an integer of 1 or more and 22 or less. m 1 + n 1 is preferably an integer of 2 to 8, more preferably an integer of 3 to 6.
　また一般式（１）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無い。一つのベンゼン環に３個以上シアノ基が置換すると、化合物の化学的安定性が著しく低下し、素子を高温で保存した際の性能の低下の原因の一つとなるためである。すなわち、一般式（１）で表される化合物において、一つのベンゼン環に置換するシアノ基の数は２個以下であり、０又は１個であることが化学的安定性の観点で好ましい。 Further, the compound represented by the general formula (1) does not have a benzene ring substituted with 3 or more cyano groups. This is because if three or more cyano groups are substituted on one benzene ring, the chemical stability of the compound is remarkably lowered, and this is one of the causes of deterioration in performance when the device is stored at high temperature. That is, in the compound represented by the general formula (1), the number of cyano groups substituted on one benzene ring is 2 or less, and 0 or 1 is preferable from the viewpoint of chemical stability.
　本発明において、一般式（１）で表される化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和は９以上２０以下である。一般式（１）で表される化合物は、ベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が前述の範囲となるようにシアノ基及びＲ１を有する。ベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和は、９以上１７以下であることがより好ましく、９以上１４以下であることが更に好ましい。ベンゼン環やシアノ基を化合物に導入することで、該化合物を素子に用いたときの素子の耐熱性が向上するが、ベンゼン環やシアノ基の個数が多すぎると昇華性、蒸着成膜適性、塗布成膜適性が低下する傾向がある。ベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和を前述の範囲とすることで、耐熱性と昇華・成膜適性を両立することが可能となる。 In the present invention, the sum of the number of benzene rings in the compound represented by the general formula (1) and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less. The compound represented by the general formula (1) has a cyano group and R 1 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring falls within the above range. The sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is preferably 9 or more and 17 or less, and more preferably 9 or more and 14 or less. By introducing a benzene ring or a cyano group into the compound, the heat resistance of the device when the compound is used in the device is improved. However, if the number of benzene rings or cyano groups is too large, sublimation property, vapor deposition film forming property, There is a tendency that the suitability for coating film formation decreases. By making the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring within the above range, both heat resistance and suitability for sublimation / film formation can be achieved.
　一般式（１）で表される化合物中の、ベンゼン環の連結様式としては、最低励起三重項（Ｔ１）エネルギーや化学的安定性の観点からメタ位（ｍ－）で連結されていることが好ましく、全てのベンゼン環がメタ位（ｍ－）で連結されていることが特に好ましい。
　一般式（１）で表される化合物中のベンゼン環の数は５以上１９以下であることが好ましく、６以上１３以下であることがより好ましく、６以上１０以下であることが更に好ましい。
　一般式（１）で表される化合物中の、ベンゼン環に置換したシアノ基の数（すなわちｍ１と、Ｒ１に含まれるシアノ基の数との和）は１以上１２以下であることが好ましく、１以上７以下であることがより好ましく、１以上５以下であることが更に好ましい。 In the compound represented by the general formula (1), the benzene ring is connected at the meta position (m-) from the viewpoint of the lowest excited triplet (T 1 ) energy and chemical stability. It is particularly preferable that all benzene rings are linked at the meta position (m-).
The number of benzene rings in the compound represented by the general formula (1) is preferably 5 or more and 19 or less, more preferably 6 or more and 13 or less, and still more preferably 6 or more and 10 or less.
The number of cyano groups substituted on the benzene ring in the compound represented by the general formula (1) (that is, the sum of m 1 and the number of cyano groups contained in R 1 ) is 1 or more and 12 or less. Preferably, it is 1 or more and 7 or less, more preferably 1 or more and 5 or less.
　前記一般式（１）で表される化合物は、電荷輸送性及び化学的安定性の観点から下記一般式（２）で表される化合物であることが好ましい。 The compound represented by the general formula (1) is preferably a compound represented by the following general formula (2) from the viewpoint of charge transportability and chemical stability.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　一般式（２）中、Ｒ２はアルキル基又はアリール基を表す。但し、Ｒ２で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ２が複数存在する時、複数のＲ２は同一でも異なってもよい。
　ｍ２は、一般式（２）中のビフェニル－ｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１４以下の整数を表す。
　ｎ２は、一般式（２）中のビフェニル－ｍ－キンクフェニル構造に置換したＲ２の数であり、０以上３０以下の整数を表す。ここで、ｍ２＋ｎ２は１以上３０以下の整数である。
　但し、一般式（２）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ２を有する。 In general formula (2), R 2 represents an alkyl group or an aryl group. However, the aryl group represented by R 2 does not have a condensed ring and may have an alkyl group or a cyano group. When R 2 there are a plurality, the plurality of R 2 may be the same or different.
m 2 is the number of cyano groups substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 14 or less.
n 2 is the number of R 2 substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 30 or less. Here, m 2 + n 2 is 1 to 30 integer.
However, the compound represented by the general formula (2) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 2 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
　Ｒ２で表されるアルキル基及びアリール基は、前述のＲ１で表されるアルキル基及びアリール基と同義であり、それらの好ましい範囲も同様である。 The alkyl group and aryl group represented by R 2 have the same meanings as the alkyl group and aryl group represented by R 1 described above, and their preferred ranges are also the same.
　ｍ２は、一般式（２）中のビフェニル－ｍ－キンクフェニル構造、すなわち一般式（２）中で構造式として示されるメタ位で連結した７つのベンゼン環、に置換したシアノ基の数であり、０以上１４以下の整数を表す。ここで言う置換とは、前記７つのベンゼン環上の任意の一つの水素原子がシアノ基に置き換えられた状態をいい、前述のＲ２で表されるアリール基中のベンゼン環に置換していてもよいシアノ基はｍ２の数に含まれない。また前述と同様の理由で、前記７つのベンゼン環のいずれか１つのベンゼン環に、３個以上のシアノ基が置換することは無い。
　本発明においては、電荷輸送性及び化学的安定性の観点から、一般式（２）中のビフェニル－ｍ－キンクフェニル構造に置換したシアノ基が少なくとも１個存在すること（すなわち、ｍ２は１以上１４以下の整数であること）が好ましく、より好ましくはｍ２が１以上７以下の整数であり、更に好ましくは１以上５以下の整数である。 m 2 is the number of cyano groups substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), that is, the seven benzene rings linked at the meta position shown as the structural formula in the general formula (2). Yes, and represents an integer from 0 to 14. The substitution mentioned here refers to a state in which any one hydrogen atom on the seven benzene rings is replaced with a cyano group, and the benzene ring in the aryl group represented by R 2 described above is substituted. The good cyano group is not included in the number of m 2 . Further, for the same reason as described above, any one of the seven benzene rings is not substituted with three or more cyano groups.
In the present invention, from the viewpoint of charge transportability and chemical stability, at least one cyano group substituted on the biphenyl-m-kinkphenyl structure in the general formula (2) is present (that is, m 2 is 1). It is preferably an integer of 14 or less, and more preferably m 2 is an integer of 1 to 7, more preferably an integer of 1 to 5.
　ｎ２は、一般式（２）中のビフェニル－ｍ－キンクフェニル構造、すなわち一般式（２）中で構造式として示されるメタ位で連結した７つのベンゼン環、に置換したＲ２の数であり、０以上３０以下の整数を表す。ｎ２は、電荷輸送性及び化学的安定性の観点から、好ましくは０以上７以下の整数であり、より好ましくは０以上４以下の整数である。 n 2 is the number of R 2 substituted in the biphenyl-m-kinkphenyl structure in the general formula (2), that is, seven benzene rings linked at the meta position shown as the structural formula in the general formula (2). Yes, and represents an integer of 0 to 30. n 2 is preferably an integer of 0 to 7, more preferably an integer of 0 to 4, from the viewpoint of charge transportability and chemical stability.
　一般式（２）で表される化合物は、前述と同様の理由により、ベンゼン環に置換したシアノ基を少なくとも１個有する。ここで言うシアノ基はベンゼン環に置換していれば特に制限されず、前記ｍ２で数えられるシアノ基の一つであってもよいし、前記Ｒ２で表されるアリール基中のベンゼン環に置換したシアノ基であってもよい。
　ｍ２が０の場合、ベンゼン環に置換したシアノ基はＲ２に含まれることになるので、ｍ２＋ｎ２は１以上３０以下の整数となる。ｍ２＋ｎ２は、好ましくは１以上８以下の整数であり、より好ましくは１以上５以下の整数であり、更に好ましくは１以上３以下の整数である。 The compound represented by the general formula (2) has at least one cyano group substituted on the benzene ring for the same reason as described above. The cyano group referred to here is not particularly limited as long as it is substituted on the benzene ring, and may be one of the cyano groups counted by m 2 or the benzene ring in the aryl group represented by R 2. A cyano group substituted with may be used.
When m 2 is 0, a cyano group substituted on the benzene ring is included in R 2 , and m 2 + n 2 is an integer of 1 or more and 30 or less. m 2 + n 2 is preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and even more preferably an integer of 1 to 3.
　また一般式（２）で表される化合物は、前述と同様の理由により、シアノ基が３個以上置換したベンゼン環を有することは無い。すなわち、一般式（２）で表される化合物において、一つのベンゼン環に置換するシアノ基の数は２個以下であり、０又は１個であることが化学的安定性の観点で好ましい。 Further, the compound represented by the general formula (2) does not have a benzene ring substituted with 3 or more cyano groups for the same reason as described above. That is, in the compound represented by the general formula (2), the number of cyano groups substituted on one benzene ring is 2 or less, and 0 or 1 is preferable from the viewpoint of chemical stability.
　本発明において、一般式（２）で表される化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和は、前述と同様の理由により、９以上２０以下である。一般式（２）で表される化合物は、ベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が前述の範囲となるようにシアノ基及びＲ２を有する。ベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和の好ましい範囲は、前述の一般式（１）における範囲と同様である。 In the present invention, the sum of the number of benzene rings in the compound represented by the general formula (2) and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less for the same reason as described above. The compound represented by the general formula (2) has a cyano group and R 2 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring falls within the above-mentioned range. A preferable range of the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is the same as the range in the general formula (1).
　一般式（２）で表される化合物中の、ベンゼン環の連結様式としては、最低励起三重項（Ｔ１）エネルギーや化学的安定性の観点からメタ位（ｍ－）で連結されていることが好ましく、全てのベンゼン環がメタ位（ｍ－）で連結されていることが特に好ましい。
　一般式（２）で表される化合物中のベンゼン環の数は７以上１９以下であることが好ましく、７以上１３以下であることがより好ましく、７以上１０以下であることが更に好ましい。
　一般式（２）で表される化合物中の、ベンゼン環に置換したシアノ基の数（すなわちｍ２と、Ｒ２に含まれるシアノ基の数との和）は１以上１２以下であることが好ましく、１以上７以下であることがより好ましく、１以上５以下であることが更に好ましい。 In the compound represented by the general formula (2), the benzene ring should be linked at the meta position (m-) from the viewpoint of the lowest excited triplet (T 1 ) energy and chemical stability. It is particularly preferred that all benzene rings are linked at the meta position (m-).
The number of benzene rings in the compound represented by the general formula (2) is preferably 7 or more and 19 or less, more preferably 7 or more and 13 or less, and still more preferably 7 or more and 10 or less.
The number of cyano groups substituted on the benzene ring in the compound represented by the general formula (2) (that is, the sum of m 2 and the number of cyano groups contained in R 2 ) is 1 or more and 12 or less. Preferably, it is 1 or more and 7 or less, more preferably 1 or more and 5 or less.
　前記一般式（１）で表される化合物は、電荷輸送性及び化学的安定性の観点から、下記一般式（３）で表される化合物であることも好ましい。 The compound represented by the general formula (1) is preferably a compound represented by the following general formula (3) from the viewpoint of charge transportability and chemical stability.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　一般式（３）中、Ｒ３はアルキル基又はアリール基を表す。但し、Ｒ３で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ３が複数存在する時、複数のＲ３は同一でも異なってもよい。
　ｍ３は、一般式（３）中のジフェニル－ｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１４以下の整数を表す。
　ｎ３は、一般式（３）中のジフェニル－ｍ－キンクフェニル構造に置換したＲ３の数であり、０以上３０以下の整数を表す。ここで、ｍ３＋ｎ３は１以上３０以下の整数である。
　但し、一般式（３）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ３を有する。 In general formula (3), R 3 represents an alkyl group or an aryl group. However, the aryl group represented by R 3 does not have a condensed ring and may have an alkyl group or a cyano group. When R 3 there are a plurality, the plurality of R 3 may be the same or different.
m 3 is the number of cyano groups substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 14 or less.
n 3 is the number of R 3 substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 30 or less. Here, m 3 + n 3 is an integer of 1 or more and 30 or less.
However, the compound represented by the general formula (3) does not have a benzene ring substituted with 3 or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 3 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
　Ｒ３で表されるアルキル基及びアリール基は、前述のＲ１で表されるアルキル基及びアリール基と同義であり、それらの好ましい範囲も同様である。 The alkyl group and aryl group represented by R 3 have the same meanings as the alkyl group and aryl group represented by R 1 described above, and their preferred ranges are also the same.
　ｍ３は、一般式（３）中のジフェニル－ｍ－キンクフェニル構造、すなわち一般式（３）中で構造式として示されるメタ位で連結した７つのベンゼン環、に置換したシアノ基の数であり、０以上１４以下の整数を表す。ここで言う置換とは、前記７つのベンゼン環上の任意の一つの水素原子がシアノ基に置き換えられた状態をいい、前述のＲ３で表されるアリール基中のベンゼン環に置換していてもよいシアノ基はｍ３の数に含まれない。また前述と同様の理由で、前記７つのベンゼン環のいずれか１つのベンゼン環に、３個以上のシアノ基が置換することは無い。
　本発明においては、一般式（３）中のジフェニル－ｍ－キンクフェニル構造に置換したシアノ基が少なくとも１個存在すること（すなわち、ｍ３は１以上１４以下の整数であること）が好ましく、より好ましくはｍ３が１以上７以下の整数であり、更に好ましくは１以上５以下の整数である。 m 3 is the number of cyano groups substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), that is, seven benzene rings linked at the meta position shown as the structural formula in the general formula (3). Yes, and represents an integer from 0 to 14. The substitution mentioned here refers to a state in which any one hydrogen atom on the seven benzene rings is replaced with a cyano group, and the benzene ring in the aryl group represented by R 3 described above is substituted. The good cyano group is not included in the number of m 3 . Further, for the same reason as described above, any one of the seven benzene rings is not substituted with three or more cyano groups.
In the present invention, it is preferable that at least one cyano group substituted on the diphenyl-m-kinkphenyl structure in the general formula (3) is present (that is, m 3 is an integer of 1 or more and 14 or less), more preferably m 3 is 1 or more and 7 or less an integer, more preferably 1 to 5 integer.
　ｎ３は、一般式（３）中のジフェニル－ｍ－キンクフェニル構造、すなわち一般式（３）中で構造式として示されるメタ位で連結した７つのベンゼン環、に置換したＲ３の数であり、０以上３０以下の整数を表す。ｎ３は、電荷輸送性及び化学的安定性の観点から、好ましくは０以上７以下の整数であり、より好ましくは０以上４以下の整数である。 n 3 is the number of R 3 substituted in the diphenyl-m-kinkphenyl structure in the general formula (3), that is, seven benzene rings linked at the meta position shown as the structural formula in the general formula (3). Yes, and represents an integer from 0 to 30. n 3 is preferably an integer of 0 or more and 7 or less, more preferably an integer of 0 or more and 4 or less, from the viewpoint of charge transportability and chemical stability.
　一般式（３）で表される化合物は、前述と同様の理由により、ベンゼン環に置換したシアノ基を少なくとも１個有する。ここで言うシアノ基はベンゼン環に置換していれば特に制限されず、前記ｍ３で数えられるシアノ基の一つであってもよいし、前記Ｒ３で表されるアリール基中のベンゼン環に置換したシアノ基であってもよい。
　ｍ３が０の場合、ベンゼン環に置換したシアノ基はＲ３に含まれることになるので、ｍ３＋ｎ３は１以上３０以下の整数となる。ｍ３＋ｎ３は、好ましくは１以上８以下の整数であり、より好ましくは１以上５以下の整数であり、更に好ましくは１以上３以下の整数である。 The compound represented by the general formula (3) has at least one cyano group substituted on the benzene ring for the same reason as described above. The cyano group referred to here is not particularly limited as long as it is substituted on the benzene ring, and may be one of the cyano groups counted by m 3 or the benzene ring in the aryl group represented by R 3. A cyano group substituted with may be used.
When m 3 is 0, a cyano group substituted on the benzene ring is included in R 3 , and m 3 + n 3 is an integer of 1 to 30. m 3 + n 3 is preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, and further preferably an integer of 1 or more and 3 or less.
　また一般式（３）で表される化合物は、前述と同様の理由により、シアノ基が３個以上置換したベンゼン環を有することは無い。すなわち、一般式（３）で表される化合物において、一つのベンゼン環に置換するシアノ基の数は２個以下であり、０又は１個であることが化学的安定性の観点で好ましい。 Further, the compound represented by the general formula (3) does not have a benzene ring substituted with 3 or more cyano groups for the same reason as described above. That is, in the compound represented by the general formula (3), the number of cyano groups substituted on one benzene ring is 2 or less, and 0 or 1 is preferable from the viewpoint of chemical stability.
　本発明において、一般式（３）で表される化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和は、前述と同様の理由により、９以上２０以下である。一般式（３）で表される化合物は、ベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が前述の範囲となるようにシアノ基及びＲ３を有する。ベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和の好ましい範囲は、前述の一般式（１）における範囲と同様である。 In the present invention, the sum of the number of benzene rings in the compound represented by the general formula (3) and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less for the same reason as described above. The compound represented by the general formula (3) has a cyano group and R 3 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring falls within the above-mentioned range. A preferable range of the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is the same as the range in the general formula (1).
　一般式（３）で表される化合物中の、ベンゼン環の連結様式としては、最低励起三重項（Ｔ１）エネルギーや化学的安定性の観点からメタ位（ｍ－）で連結されていることが好ましく、全てのベンゼン環がメタ位（ｍ－）で連結されていることが特に好ましい。
　一般式（３）で表される化合物中のベンゼン環の数は７以上１９以下であることが好ましく、７以上１３以下であることがより好ましく、７以上１０以下であることが更に好ましい。
　一般式（３）で表される化合物中の、ベンゼン環に置換したシアノ基の数（すなわちｍ３と、Ｒ３に含まれるシアノ基の数との和）は１以上１２以下であることが好ましく、１以上７以下であることがより好ましく、１以上５以下であることが更に好ましい。 In the compound represented by the general formula (3), the benzene ring should be linked at the meta position (m-) from the viewpoint of the lowest excited triplet (T 1 ) energy and chemical stability. It is particularly preferable that all benzene rings are linked at the meta position (m-).
The number of benzene rings in the compound represented by the general formula (3) is preferably 7 or more and 19 or less, more preferably 7 or more and 13 or less, and still more preferably 7 or more and 10 or less.
The number of cyano groups substituted on the benzene ring in the compound represented by the general formula (3) (that is, the sum of m 3 and the number of cyano groups contained in R 3 ) is 1 or more and 12 or less. Preferably, it is 1 or more and 7 or less, more preferably 1 or more and 5 or less.
　一般式（１）～（３）のいずれかで表される化合物は、炭素原子、水素原子及び窒素原子のみからなる化合物である。これにより素子の高温保管後においても、耐久性の向上がもたらされる。 The compound represented by any one of the general formulas (1) to (3) is a compound consisting of only a carbon atom, a hydrogen atom and a nitrogen atom. Thereby, the durability is improved even after the element is stored at a high temperature.
　一般式（１）～（３）のいずれかで表される化合物の分子量は通常４００以上１５００以下であり、４５０以上１２００以下であることが好ましく、５００以上１１００以下であることがより好ましく、６００以上１０００以下であることが更に好ましい。分子量が４５０以上であると良質なアモルファス薄膜形成に有利であり、分子量が１２００以下であると溶解性や昇華性が向上し、化合物の純度向上に有利である。 The molecular weight of the compound represented by any one of the general formulas (1) to (3) is usually 400 or more and 1500 or less, preferably 450 or more and 1200 or less, more preferably 500 or more and 1100 or less, and 600 More preferably, it is 1000 or less. When the molecular weight is 450 or more, it is advantageous for forming a high-quality amorphous thin film, and when the molecular weight is 1200 or less, the solubility and sublimation property are improved, which is advantageous for improving the purity of the compound.
　一般式（１）～（３）のいずれかで表される化合物を有機電界発光素子の発光層のホスト材料や発光層に隣接する層の電荷輸送材料として使用する場合、発光材料より薄膜状態でのエネルギーギャップ（発光材料が燐光発光材料の場合には、薄膜状態での最低励起三重項（Ｔ１）エネルギー）が大きいと、発光がクエンチしてしまうことを防ぎ、効率向上に有利である。一方、化合物の化学的安定性の観点からは、エネルギーギャップ及びＴ１エネルギーは大き過ぎない方が好ましい。
　一般式（１）～（３）のいずれかで表される化合物の膜状態でのＴ１エネルギーは、２．３９ｅＶ（５５ｋｃａｌ／ｍｏｌ）以上３．５１ｅＶ（８０ｋｃａｌ／ｍｏｌ）以下であることが好ましく、２．５２ｅＶ（５８ｋｃａｌ／ｍｏｌ）以上３．２５ｅＶ（７５ｋｃａｌ／ｍｏｌ）以下であることがより好ましく、２．６５ｅＶ（６１ｋｃａｌ／ｍｏｌ）以上３．０４ｅＶ（７０ｋｃａｌ／ｍｏｌ）以下であることが更に好ましい。特に、発光材料として燐光発光材料を用いる場合には、Ｔ１エネルギーが上記範囲となることが好ましい。 When the compound represented by any one of the general formulas (1) to (3) is used as a host material for a light emitting layer of an organic electroluminescent device or a charge transport material for a layer adjacent to the light emitting layer, When the energy gap (the light emitting material is a phosphorescent light emitting material) is large, the minimum excited triplet (T 1 ) energy in a thin film state is large, which prevents the light emission from being quenched and is advantageous for improving the efficiency. On the other hand, from the viewpoint of chemical stability of the compound, it is preferable that the energy gap and T 1 energy are not too large.
The T 1 energy in the film state of the compound represented by any one of the general formulas (1) to (3) is preferably 2.39 eV (55 kcal / mol) or more and 3.51 eV (80 kcal / mol) or less. 2.52 eV (58 kcal / mol) to 3.25 eV (75 kcal / mol), more preferably 2.65 eV (61 kcal / mol) to 3.04 eV (70 kcal / mol). . In particular, when a phosphorescent light emitting material is used as the light emitting material, the T 1 energy is preferably in the above range.
　Ｔ１エネルギーは、材料の薄膜の燐光発光スペクトルを測定し、その短波長端から求めることができる。例えば、洗浄した石英ガラス基板上に、材料を真空蒸着法により約５０ｎｍの膜厚に成膜し、薄膜の燐光発光スペクトルを液体窒素温度下でＦ－７０００日立分光蛍光光度計（日立ハイテクノロジーズ）を用いて測定する。得られた発光スペクトルの短波長側の立ち上がり波長をエネルギー単位に換算することによりＴ１エネルギーを求めることができる。 The T 1 energy can be obtained from the short wavelength end of a phosphorescence emission spectrum of a thin film of material. For example, a material is deposited on a cleaned quartz glass substrate to a film thickness of about 50 nm by a vacuum deposition method, and the phosphorescence emission spectrum of the thin film is measured under liquid nitrogen temperature F-7000 Hitachi Spectrofluorimeter (Hitachi High Technologies). Use to measure. The T 1 energy can be obtained by converting the rising wavelength on the short wavelength side of the obtained emission spectrum into energy units.
　有機電界発光素子を高温駆動時や素子駆動中の発熱に対して安定して動作させる観点から、一般式（１）～（３）のいずれかで表される化合物のガラス転移温度（Ｔｇ）は１００℃以上４００℃以下であることが好ましく、１２０℃以上４００℃以下であることがより好ましく、１４０℃以上４００℃以下であることが更に好ましい。 The glass transition temperature (Tg) of the compound represented by any one of the general formulas (1) to (3) is from the viewpoint of stably operating the organic electroluminescence device against heat generated during high temperature driving or during device driving. It is preferably 100 ° C. or higher and 400 ° C. or lower, more preferably 120 ° C. or higher and 400 ° C. or lower, and still more preferably 140 ° C. or higher and 400 ° C. or lower.
　一般式（１）～（３）のいずれかで表される化合物の純度が低いと、不純物が電荷輸送のトラップとして働いたり、素子の劣化を促進させたりするため、一般式（１）～（３）のいずれかで表される化合物の純度は高いほど好ましい。純度は例えば高速液体クロマトグラフィー（ＨＰＬＣ）により測定でき、２５４ｎｍの光吸収強度で検出したときの一般式（１）～（３）のいずれかで表される化合物の面積比は、好ましくは９５．０％以上であり、より好ましくは９７．０％以上であり、特に好ましくは９９．０％以上であり、最も好ましくは９９．９％以上である。 If the purity of the compound represented by any one of the general formulas (1) to (3) is low, impurities work as a charge transport trap or promote deterioration of the device. The higher the purity of the compound represented by any of 3), the better. The purity can be measured by, for example, high performance liquid chromatography (HPLC), and the area ratio of the compound represented by any one of the general formulas (1) to (3) when detected with a light absorption intensity of 254 nm is preferably 95. It is 0% or more, more preferably 97.0% or more, particularly preferably 99.0% or more, and most preferably 99.9% or more.
　国際公開第２００８／１１７８８９号に記載のカルバゾール系材料で知られているように、一般式（１）～（３）のいずれかで表される化合物の水素原子の一部又は全部を重水素原子で置換した材料も好ましく電荷輸送材料として用いることができる。 As known in the carbazole-based material described in WO 2008/117889, a part or all of the hydrogen atoms of the compound represented by any one of the general formulas (1) to (3) are deuterium atoms. The material substituted with can also be preferably used as a charge transport material.
　一般式（１）～（３）のいずれかで表される化合物の具体例を以下に列挙するが、本発明がこれらに限定されることはない。 Specific examples of the compound represented by any one of the general formulas (1) to (3) are listed below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　上記一般式（１）～（３）のいずれかで表される化合物として例示した化合物は、例えば特開２００７－２６６５９８等に記載の方法により、合成できる。 The compounds exemplified as the compounds represented by any one of the above general formulas (1) to (3) can be synthesized by the method described in, for example, JP-A-2007-266598.
　本発明において、一般式（１）～（３）のいずれかで表される化合物は、その用途が限定されることはなく、有機層内のいずれの層に含有されてもよい。一般式（１）～（３）のいずれかで表される化合物の導入層としては、発光層、発光層と陰極との間の層、発光層と陽極との間の層のいずれか、若しくは複数に含有されるのが好ましく、発光層、正孔注入層、正孔輸送層、電子輸送層、電子注入層、励起子ブロック層、電荷ブロック層のいずれか、若しくは複数に含有されるのがより好ましく、発光層、電子輸送層、電子注入層のいずれかに含有されることが更に好ましい。
　本発明では、高温駆動後の色度変化をより抑えるために、一般式（１）～（３）のいずれかで表される化合物を発光層、発光層と陰極との間で発光層に隣接する有機層（発光層に隣接する陰極側の層）、及び発光層側で陰極に隣接する電子注入層のいずれかに含有されることが好ましく、発光層及び発光層に隣接する陰極側の層のいずれかに含有されることがより好ましく、発光層に含有されることが更に好ましい。また、一般式（１）～（３）のいずれかで表される化合物を発光層及び発光層に隣接する陰極側の層の両層に含有させてもよい。
　一般式（１）～（３）のいずれかで表される化合物を発光層中に含有させる場合、本発明の一般式（１）～（３）のいずれかで表される化合物は発光層の全質量に対して０．１～９９質量％含ませることが好ましく、１～９７質量％含ませることがより好ましく、１０～９６質量％含ませることが更に好ましい。一般式（１）～（３）のいずれかで表される化合物を発光層以外の層に更に含有させる場合は、該発光層以外の層の全質量に対して７０～１００質量％含まれることが好ましく、８５～１００質量％含まれることがより好ましい。　 In the present invention, the compound represented by any one of the general formulas (1) to (3) is not limited in its use, and may be contained in any layer in the organic layer. As the introduction layer of the compound represented by any one of the general formulas (1) to (3), any one of a light emitting layer, a layer between the light emitting layer and the cathode, a layer between the light emitting layer and the anode, or It is preferably contained in a plurality, and it is contained in any one or more of the light emitting layer, the hole injection layer, the hole transport layer, the electron transport layer, the electron injection layer, the exciton block layer, and the charge block layer. More preferably, it is more preferably contained in any one of the light emitting layer, the electron transport layer, and the electron injection layer.
In the present invention, in order to further suppress the change in chromaticity after high temperature driving, the compound represented by any one of the general formulas (1) to (3) is adjacent to the light emitting layer between the light emitting layer and the light emitting layer and the cathode. The organic layer (the cathode side layer adjacent to the light emitting layer) and the electron injection layer adjacent to the cathode on the light emitting layer side are preferably contained in the light emitting layer and the cathode side layer adjacent to the light emitting layer. More preferably, it is contained in any one of the above, and it is more preferred that it is contained in the light emitting layer. Further, the compound represented by any one of the general formulas (1) to (3) may be contained in both the light emitting layer and the cathode side layer adjacent to the light emitting layer.
When the compound represented by any one of the general formulas (1) to (3) is contained in the light emitting layer, the compound represented by any one of the general formulas (1) to (3) of the present invention is the light emitting layer. The content is preferably 0.1 to 99% by mass, more preferably 1 to 97% by mass, and still more preferably 10 to 96% by mass with respect to the total mass. When the compound represented by any one of the general formulas (1) to (3) is further contained in a layer other than the light emitting layer, it is contained in an amount of 70 to 100% by mass with respect to the total mass of the layer other than the light emitting layer. And more preferably 85 to 100% by mass.
〔一般式（１）で表される電荷輸送材料〕
　本発明は、上記一般式（１）で表される電荷輸送材料にも関する。上記一般式（１）で表される電荷輸送材料は、好ましくは上記一般式（２）又は（３）で表される電荷輸送材料である。 [Charge Transport Material Represented by General Formula (1)]
The present invention also relates to a charge transport material represented by the general formula (1). The charge transport material represented by the general formula (1) is preferably a charge transport material represented by the general formula (2) or (3).
〔本発明の一般式（１）で表される化合物及び電荷輸送材料の用途〕
　本発明の一般式（１）で表される化合物及び電荷輸送材料は、電子写真、有機トランジスタ、有機光電変換素子（エネルギー変換用途、センサー用途等）、有機電界発光素子等の有機エレクトロニクス素子に好ましく用いることができ、有機電界発光素子に用いるのが特に好ましい。 [Use of compound represented by general formula (1) and charge transport material of the present invention]
The compound represented by the general formula (1) and the charge transport material of the present invention are preferably used for organic electronic elements such as electrophotography, organic transistors, organic photoelectric conversion elements (energy conversion applications, sensor applications, etc.), and organic electroluminescence elements. It can be used and is particularly preferably used for an organic electroluminescent device.
〔本発明の電荷輸送材料を含有する組成物〕
　本発明は前記電荷輸送材料を含む組成物にも関する。本発明の組成物において、一般式（１）～（３）のいずれかで表される化合物の含有量は、組成物中の全固形分に対して３０～９９質量％であることが好ましく、５０～９７質量％であることがより好ましく、７０～９６質量％であることが更に好ましい。本発明の組成物における他に含有しても良い成分としては、有機物でも無機物でもよく、有機物としては、後述するホスト材料、蛍光発光材料、燐光発光材料、炭化水素材料として挙げた材料が適用でき、好ましくはホスト材料、燐光発光材料、炭化水素材料である。
　本発明の組成物は蒸着法やスパッタ法等の乾式製膜法、転写法、印刷法等の湿式製膜法により有機電界発光素子の有機層を形成することができる。 [Composition containing the charge transport material of the present invention]
The present invention also relates to a composition comprising the charge transport material. In the composition of the present invention, the content of the compound represented by any one of the general formulas (1) to (3) is preferably 30 to 99% by mass with respect to the total solid content in the composition, The content is more preferably 50 to 97% by mass, and further preferably 70 to 96% by mass. Other components that may be contained in the composition of the present invention may be organic or inorganic, and as organic materials, materials described as host materials, fluorescent light emitting materials, phosphorescent light emitting materials, and hydrocarbon materials described later can be applied. A host material, a phosphorescent material, and a hydrocarbon material are preferable.
The composition of the present invention can form an organic layer of an organic electroluminescence device by a dry film forming method such as a vapor deposition method or a sputtering method, or a wet film forming method such as a transfer method or a printing method.
〔本発明の電荷輸送材料を含有する薄膜〕
　本発明は一般式（１）～（３）のいずれかで表される電荷輸送材料を含有する薄膜にも関する。本発明の薄膜は、本発明の組成物を用いて蒸着法やスパッタ法等の乾式製膜法、転写法、印刷法等の湿式製膜法により形成することができる。薄膜の膜厚は用途によっていかなる厚みでもよいが、好ましくは０．１ｎｍ～１ｍｍであり、より好ましくは０．５ｎｍ～１μｍであり、更に好ましくは１ｎｍ～２００ｎｍであり、特に好ましくは１ｎｍ～１００ｎｍである。 [Thin Film Containing Charge Transport Material of the Present Invention]
The present invention also relates to a thin film containing a charge transport material represented by any one of the general formulas (1) to (3). The thin film of the present invention can be formed by using the composition of the present invention by a dry film forming method such as a vapor deposition method or a sputtering method, or a wet film forming method such as a transfer method or a printing method. The thickness of the thin film may be any thickness depending on the application, but is preferably 0.1 nm to 1 mm, more preferably 0.5 nm to 1 μm, still more preferably 1 nm to 200 nm, and particularly preferably 1 nm to 100 nm. is there.
〔有機電界発光素子〕
　本発明の有機電界発光素子について詳細に説明する。
　本発明の有機電界発光素子は、基板上に、陽極及び陰極からなる一対の電極と、該電極間に発光層を含む少なくとも一層の有機層とを有する有機電界発光素子であって、前記発光層に燐光発光材料を少なくとも一種含み、かつ、前記少なくとも一層の有機層のいずれか少なくとも一層に本発明の一般式（１）～（３）のいずれかで表される化合物を含む。発光素子の性質上、一対の電極である陽極及び陰極のうち少なくとも一方の電極は、透明若しくは半透明であることが好ましい。
　有機層としては、発光層以外に、正孔注入層、正孔輸送層、ブロック層（正孔ブロック層、励起子ブロック層など）、電子輸送層などが挙げられる。これらの有機層は、それぞれ複数層設けてもよく、複数層設ける場合には同一の材料で形成してもよいし、層毎に異なる材料で形成してもよい。
　図１に、本発明に係る有機電界発光素子の構成の一例を示す。図１の有機電界発光素子１０は、基板２上に、一対の電極（陽極３と陰極９）の間に発光層６を含む有機層を有する。有機層としては、陽極側３から正孔注入層４、正孔輸送層５、発光層６、正孔ブロック層７及び電子輸送層８がこの順に積層されている。 [Organic electroluminescence device]
The organic electroluminescent element of the present invention will be described in detail.
The organic electroluminescent device of the present invention is an organic electroluminescent device having a pair of electrodes comprising an anode and a cathode and at least one organic layer including a light emitting layer between the electrodes on the substrate, wherein the light emitting layer And at least one of the at least one organic layer contains a compound represented by any one of the general formulas (1) to (3) of the present invention. In view of the properties of the light-emitting element, at least one of the pair of electrodes, the anode and the cathode, is preferably transparent or translucent.
Examples of the organic layer include a hole injection layer, a hole transport layer, a block layer (such as a hole block layer and an exciton block layer), and an electron transport layer in addition to the light emitting layer. A plurality of these organic layers may be provided, and when a plurality of layers are provided, they may be formed of the same material, or may be formed of different materials for each layer.
In FIG. 1, an example of a structure of the organic electroluminescent element which concerns on this invention is shown. The organic electroluminescent element 10 of FIG. 1 has an organic layer including a light emitting layer 6 between a pair of electrodes (anode 3 and cathode 9) on a substrate 2. As the organic layer, a hole injection layer 4, a hole transport layer 5, a light emitting layer 6, a hole block layer 7 and an electron transport layer 8 are laminated in this order from the anode side 3.
＜有機層の構成＞
　前記有機層の層構成としては、特に制限はなく、有機電界発光素子の用途、目的に応じて適宜選択することができるが、前記透明電極上に又は前記半透明電極上に形成されるのが好ましい。この場合、有機層は、前記透明電極又は前記半透明電極上の前面又は一面に形成される。
　有機層の形状、大きさ、及び厚み等については、特に制限はなく、目的に応じて適宜選択することができる。 <Structure of organic layer>
There is no restriction | limiting in particular as a layer structure of the said organic layer, Although it can select suitably according to the use and objective of an organic electroluminescent element, It is formed on the said transparent electrode or the said semi-transparent electrode. preferable. In this case, the organic layer is formed on the front surface or one surface of the transparent electrode or the semitransparent electrode.
There is no restriction | limiting in particular about the shape of a organic layer, a magnitude | size, thickness, etc., According to the objective, it can select suitably.
　具体的な層構成として、下記が挙げられるが本発明はこれらの構成に限定されるものではない。
　・陽極／正孔輸送層／発光層／電子輸送層／陰極、
　・陽極／正孔輸送層／発光層／ブロック層／電子輸送層／陰極、
　・陽極／正孔輸送層／発光層／ブロック層／電子輸送層／電子注入層／陰極、
　・陽極／正孔注入層／正孔輸送層／発光層／ブロック層／電子輸送層／陰極、
　・陽極／正孔注入層／正孔輸送層／発光層／電子輸送層／電子注入層／陰極、
　・陽極／正孔注入層／正孔輸送層／発光層／ブロック層／電子輸送層／電子注入層／陰極。
　有機電界発光素子の素子構成、基板、陰極及び陽極については、例えば、特開２００８－２７０７３６号公報に詳述されており、該公報に記載の事項を本発明に適用することができる。 Specific examples of the layer configuration include the following, but the present invention is not limited to these configurations.
Anode / hole transport layer / light emitting layer / electron transport layer / cathode,
Anode / hole transport layer / light emitting layer / block layer / electron transport layer / cathode,
Anode / hole transport layer / light emitting layer / block layer / electron transport layer / electron injection layer / cathode,
Anode / hole injection layer / hole transport layer / light emitting layer / block layer / electron transport layer / cathode,
Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode,
Anode / hole injection layer / hole transport layer / light emitting layer / block layer / electron transport layer / electron injection layer / cathode.
The element configuration, the substrate, the cathode, and the anode of the organic electroluminescence element are described in detail in, for example, Japanese Patent Application Laid-Open No. 2008-270736, and the matters described in the publication can be applied to the present invention.
＜基板＞
　本発明で使用する基板としては、有機層から発せられる光を散乱又は減衰させない基板であることが好ましい。有機材料の場合には、耐熱性、寸法安定性、耐溶剤性、電気絶縁性、及び加工性に優れていることが好ましい。
＜陽極＞
　陽極は、通常、有機層に正孔を供給する電極としての機能を有していればよく、その形状、構造、大きさ等については特に制限はなく、発光素子の用途、目的に応じて、公知の電極材料の中から適宜選択することができる。前述のごとく、陽極は、通常透明陽極として設けられる。
＜陰極＞
　陰極は、通常、有機層に電子を注入する電極としての機能を有していればよく、その形状、構造、大きさ等については特に制限はなく、発光素子の用途、目的に応じて、公知の電極材料の中から適宜選択することができる。 <Board>
The substrate used in the present invention is preferably a substrate that does not scatter or attenuate light emitted from the organic layer. In the case of an organic material, it is preferable that it is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, and workability.
<Anode>
The anode usually only needs to have a function as an electrode for supplying holes to the organic layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials. As described above, the anode is usually provided as a transparent anode.
<Cathode>
The cathode usually has a function as an electrode for injecting electrons into the organic layer, and there is no particular limitation on the shape, structure, size, etc., and it is known depending on the use and purpose of the light emitting device. The electrode material can be selected as appropriate.
＜有機層＞
　本発明における有機層について説明する。 <Organic layer>
The organic layer in the present invention will be described.
（有機層の形成）
　本発明の有機電界発光素子において、各有機層は、蒸着法やスパッタ法等の乾式製膜法、転写法、印刷法、スピンコート法、バーコート法等の溶液塗布法のいずれによっても好適に形成することができる。有機層の少なくとも１層が溶液塗布法により形成されることが好ましい。 (Formation of organic layer)
In the organic electroluminescent device of the present invention, each organic layer is preferably formed by any of dry film forming methods such as vapor deposition and sputtering, and solution coating methods such as transfer, printing, spin coating, and bar coating. Can be formed. It is preferable that at least one of the organic layers is formed by a solution coating method.
（発光層）
　発光層は、電界印加時に、陽極、正孔注入層又は正孔輸送層から正孔を受け取り、陰極、電子注入層又は電子輸送層から電子を受け取り、正孔と電子の再結合の場を提供して発光させる機能を有する層である。本発明の有機電界発光素子における発光層は、少なくとも一種の燐光発光材料を含有する。 (Light emitting layer)
The light emitting layer receives holes from the anode, hole injection layer or hole transport layer and receives electrons from the cathode, electron injection layer or electron transport layer when an electric field is applied, and provides a field for recombination of holes and electrons. And a layer having a function of emitting light. The light emitting layer in the organic electroluminescent element of the present invention contains at least one phosphorescent material.
（発光材料）
　本発明では、発光層に含有される少なくとも一種の燐光発光材料に加えて、発光材料として、蛍光発光材料や、発光層に含有される燐光発光材料とは異なる燐光発光材料を用いることができる。
　これら蛍光発光材料や燐光発光材料については、例えば、特開２００８－２７０７３６号公報の段落番号［０１００］～［０１６４］、特開２００７－２６６４５８号公報の段落番号［００８８］～［００９０］に詳述されており、これら公報の記載の事項を本発明に適用することができる。 (Luminescent material)
In the present invention, in addition to at least one phosphorescent light-emitting material contained in the light-emitting layer, a fluorescent light-emitting material or a phosphorescent light-emitting material different from the phosphorescent light-emitting material contained in the light-emitting layer can be used as the light-emitting material.
Details of these fluorescent materials and phosphorescent materials are described in, for example, paragraph numbers [0100] to [0164] of JP-A-2008-270736 and paragraph numbers [0088] to [0090] of JP-A-2007-266458. The matters described in these publications can be applied to the present invention.
　本発明に使用できる燐光発光材料としては、例えば、ＵＳ６３０３２３８Ｂ１、ＵＳ６０９７１４７、ＷＯ００／５７６７６、ＷＯ００／７０６５５、ＷＯ０１／０８２３０、ＷＯ０１／３９２３４Ａ２、ＷＯ０１／４１５１２Ａ１、ＷＯ０２／０２７１４Ａ２、ＷＯ０２／１５６４５Ａ１、ＷＯ０２／４４１８９Ａ１、ＷＯ０５／１９３７３Ａ２、特開２００１－２４７８５９、特開２００２－３０２６７１、特開２００２－１１７９７８、特開２００３－１３３０７４、特開２００２－２３５０７６、特開２００３－１２３９８２、特開２００２－１７０６８４、ＥＰ１２１１２５７、特開２００２－２２６４９５、特開２００２－２３４８９４、特開２００１－２４７８５９、特開２００１－２９８４７０、特開２００２－１７３６７４、特開２００２－２０３６７８、特開２００２－２０３６７９、特開２００４－３５７７９１、特開２００６－２５６９９９、特開２００７－１９４６２、特開２００７－８４６３５、特開２００７－９６２５９等の特許文献に記載の燐光発光化合物などが挙げられ、中でも、更に好ましい発光材料としては、Ｉｒ錯体、Ｐｔ錯体、Ｃｕ錯体、Ｒｅ錯体、Ｗ錯体、Ｒｈ錯体、Ｒｕ錯体、Ｐｄ錯体、Ｏｓ錯体、Ｅｕ錯体、Ｔｂ錯体、Ｇｄ錯体、Ｄｙ錯体、及びＣｅ錯体等の燐光発光性金属錯体化合物が挙げられる。特に好ましくは、Ｉｒ錯体、Ｐｔ錯体、又はＲｅ錯体であり、中でも金属－炭素結合、金属－窒素結合、金属－酸素結合、金属－硫黄結合の少なくとも一つの配位様式を含むＩｒ錯体、Ｐｔ錯体、又はＲｅ錯体が好ましい。更に、発光効率、駆動耐久性、色度等の観点で、Ｉｒ錯体、Ｐｔ錯体が特に好ましく、Ｉｒ錯体が最も好ましい。
　これら燐光発光性金属錯体化合物は、発光層において、前記一般式（１）～（３）のいずれかで表される化合物と共に含有されるのが好ましい。 Examples of phosphorescent light-emitting materials that can be used in the present invention include US Pat. / 19373A2, JP-A No. 2001-247859, JP-A No. 2002-302671, JP-A No. 2002-117978, JP-A No. 2003-133074, JP-A No. 2002-1235076, JP-A No. 2003-123984, JP-A No. 2002-170684, EP No. 121157, JP-A No. 2002-2000 -226495, JP 2002-234894, JP 2001-247859, JP 2001-298470, JP 2002-17367 , JP-A-2002-203678, JP-A-2002-203679, JP-A-2004-357799, JP-A-2006-256999, JP-A-2007-19462, JP-A-2007-84635, JP-A-2007-96259, etc. Examples of such a light emitting material include Ir complex, Pt complex, Cu complex, Re complex, W complex, Rh complex, Ru complex, Pd complex, Os complex, Eu complex, Tb complex, Gd. Examples include phosphorescent metal complex compounds such as complexes, Dy complexes, and Ce complexes. Particularly preferred is an Ir complex, a Pt complex, or a Re complex, among which an Ir complex or a Pt complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond. Or Re complexes are preferred. Furthermore, from the viewpoints of luminous efficiency, driving durability, chromaticity, etc., an Ir complex and a Pt complex are particularly preferable, and an Ir complex is most preferable.
These phosphorescent metal complex compounds are preferably contained in the light emitting layer together with the compound represented by any one of the general formulas (1) to (3).
　本発明における発光層に含有される燐光発光材料としては、以下に示す一般式（Ｅ－１）で表されるイリジウム錯体、又は以下の一般式（Ｃ－１）で表される白金錯体を用いることが好ましい。 As the phosphorescent material contained in the light emitting layer in the present invention, an iridium complex represented by the following general formula (E-1) or a platinum complex represented by the following general formula (C-1) is used. It is preferable.
　一般式（Ｅ－１）について説明する。 The general formula (E-1) will be described.
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
　一般式（Ｅ－１）中、Ｚ１及びＺ２はそれぞれ独立に、炭素原子又は窒素原子を表す。
　Ａ１はＺ１と窒素原子と共に５又は６員のヘテロ環を形成する原子群を表す。
　Ｂ１はＺ２と炭素原子と共に５又は６員環を形成する原子群を表す。
　（Ｘ－Ｙ）はモノアニオン性の二座配位子を表す。
　ｎＥ１は１～３の整数を表す。 In general formula (E-1), Z 1 and Z 2 each independently represent a carbon atom or a nitrogen atom.
A 1 represents an atomic group that forms a 5- or 6-membered heterocycle with Z 1 and a nitrogen atom.
B 1 represents an atomic group that forms a 5- or 6-membered ring with Z 2 and a carbon atom.
(XY) represents a monoanionic bidentate ligand.
n E1 represents an integer of 1 to 3.
　ｎＥ１は１～３の整数を表し、好ましくは２又は３である。
　Ｚ１及びＺ２はそれぞれ独立に、炭素原子又は窒素原子を表す。Ｚ１及びＺ２として好ましくは炭素原子である。 n E1 represents an integer of 1 to 3, preferably 2 or 3.
Z 1 and Z 2 each independently represent a carbon atom or a nitrogen atom. Z 1 and Z 2 are preferably carbon atoms.
　Ａ１はＺ１と窒素原子と共に５又は６員のヘテロ環を形成する原子群を表す。Ａ１、Ｚ１及び窒素原子を含む５又は６員のヘテロ環としては、ピリジン環、ピリミジン環、ピラジン環、トリアジン環、イミダゾール環、ピラゾール環、オキサゾール環、チアゾール環、トリアゾール環、オキサジアゾール環、チアジアゾール環などが挙げられる。
　錯体の安定性、発光波長制御及び発光量子収率の観点から、Ａ１、Ｚ１及び窒素原子で形成される５又は６員のヘテロ環として好ましくは、ピリジン環、ピラジン環、イミダゾール環、ピラゾール環であり、より好ましくはピリジン環、イミダゾール環、ピラジン環であり、更に好ましくはピリジン環、イミダゾール環であり、最も好ましくはピリジン環である。 A 1 represents an atomic group that forms a 5- or 6-membered heterocycle with Z 1 and a nitrogen atom. Examples of the 5- or 6-membered heterocycle containing A 1 , Z 1 and a nitrogen atom include a pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, triazole ring, oxadiazole Ring, thiadiazole ring and the like.
From the viewpoint of the stability of the complex, emission wavelength control, and emission quantum yield, the 5- or 6-membered heterocycle formed by A 1 , Z 1 and a nitrogen atom is preferably a pyridine ring, a pyrazine ring, an imidazole ring, or a pyrazole. A ring, more preferably a pyridine ring, an imidazole ring and a pyrazine ring, still more preferably a pyridine ring and an imidazole ring, and most preferably a pyridine ring.
　前記Ａ１、Ｚ１及び窒素原子で形成される５又は６員のヘテロ環は置換基を有していてもよく、炭素原子上の置換基としては前記置換基群Ａが、窒素原子上の置換基としては前記置換基群Ｂが適用できる。炭素上の置換基として好ましくはアルキル基、ペルフルオロアルキル基、アリール基、芳香族へテロ環基、ジアルキルアミノ基、ジアリールアミノ基、アルコキシ基、シアノ基、フッ素原子である。 The 5- or 6-membered heterocycle formed by the A 1 , Z 1 and the nitrogen atom may have a substituent, and as the substituent on the carbon atom, the substituent group A is on the nitrogen atom. The substituent group B can be applied as the substituent. Preferred substituents on carbon are alkyl groups, perfluoroalkyl groups, aryl groups, aromatic heterocyclic groups, dialkylamino groups, diarylamino groups, alkoxy groups, cyano groups, and fluorine atoms.
　置換基は発光波長や電位の制御のために適宜選択されるが、短波長化させる場合には電子供与性基、フッ素原子、芳香環基が好ましく、例えばアルキル基、ジアルキルアミノ基、アルコキシ基、フッ素原子、アリール基、芳香族ヘテロ環基などが選択される。また長波長化させる場合には電子求引性基が好ましく、例えばシアノ基、ペルフルオロアルキル基などが選択される。 The substituent is appropriately selected for controlling the emission wavelength and potential, but in the case of shortening the wavelength, an electron donating group, a fluorine atom, and an aromatic ring group are preferable. For example, an alkyl group, a dialkylamino group, an alkoxy group, A fluorine atom, an aryl group, an aromatic heterocyclic group and the like are selected. In the case of increasing the wavelength, an electron withdrawing group is preferable, and for example, a cyano group, a perfluoroalkyl group, or the like is selected.
　窒素上の置換基として好ましくは、アルキル基、アリール基、芳香族ヘテロ環基であり、錯体の安定性の観点からアルキル基、アリール基が好ましい。
　前記置換基同士は連結して縮合環を形成していてもよく、形成される環としては、ベンゼン環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、チオフェン環、フラン環などが挙げられる。これら形成される環は置換基を有していてもよく、置換基としては前述の炭素原子上の置換基、窒素原子上の置換基が挙げられる。 The substituent on nitrogen is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, and an alkyl group or an aryl group is preferable from the viewpoint of the stability of the complex.
The substituents may be linked to form a condensed ring, and the formed ring includes a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyrazole. Ring, thiophene ring, furan ring and the like. These formed rings may have a substituent, and examples of the substituent include the substituent on the carbon atom and the substituent on the nitrogen atom.
　Ｂ１はＺ２と炭素原子を含む５又は６員環を表す。Ｂ１、Ｚ２及び炭素原子で形成される５又は６員環としては、ベンゼン環、ピリジン環、ピリミジン環、ピラジン環、ピリダジン環、トリアジン環、イミダゾール環、ピラゾール環、オキサゾール環、チアゾール環、トリアゾール環、オキサジアゾール環、チアジアゾール環、チオフェン環、フラン環などが挙げられる。
　錯体の安定性、発光波長制御及び発光量子収率の観点からＢ１、Ｚ２及び炭素原子で形成される５又は６員環として好ましくは、ベンゼン環、ピリジン環、ピラジン環、イミダゾール環、ピラゾール環、チオフェン環であり、より好ましくはベンゼン環、ピリジン環、ピラゾール環であり、更に好ましくはベンゼン環、ピリジン環である。 B 1 represents a 5- or 6-membered ring containing Z 2 and a carbon atom. Examples of the 5- or 6-membered ring formed by B 1 , Z 2 and a carbon atom include a benzene ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, Examples include a triazole ring, an oxadiazole ring, a thiadiazole ring, a thiophene ring, and a furan ring.
From the viewpoint of complex stability, emission wavelength control, and emission quantum yield, a 5- or 6-membered ring formed of B 1 , Z 2 and a carbon atom is preferably a benzene ring, a pyridine ring, a pyrazine ring, an imidazole ring, or a pyrazole. A ring and a thiophene ring, more preferably a benzene ring, a pyridine ring and a pyrazole ring, and still more preferably a benzene ring and a pyridine ring.
　前記Ｂ１、Ｚ２及び炭素原子で形成される５又は６員環は置換基を有していてもよく、炭素原子上の置換基としては前記置換基群Ａが、窒素原子上の置換基としては前記置換基群Ｂが適用できる。炭素上の置換基として好ましくはアルキル基、ペルフルオロアルキル基、アリール基、芳香族へテロ環基、ジアルキルアミノ基、ジアリールアミノ基、アルコキシ基、シアノ基、フッ素原子である。 The 5- or 6-membered ring formed of B 1 , Z 2 and a carbon atom may have a substituent, and the substituent group A is a substituent on a nitrogen atom as the substituent on the carbon atom. As the above, the substituent group B can be applied. Preferred substituents on carbon are alkyl groups, perfluoroalkyl groups, aryl groups, aromatic heterocyclic groups, dialkylamino groups, diarylamino groups, alkoxy groups, cyano groups, and fluorine atoms.
　置換基は発光波長や電位の制御のために適宜選択されるが、長波長化させる場合には電子供与性基、芳香環基が好ましく、例えばアルキル基、ジアルキルアミノ基、アルコキシ基、アリール基、芳香族ヘテロ環基などが選択される。また短波長化させる場合には電子求引性基が好ましく、例えばフッ素原子、シアノ基、ペルフルオロアルキル基などが選択される。 The substituent is appropriately selected for controlling the emission wavelength and potential, but in the case of increasing the wavelength, an electron donating group and an aromatic ring group are preferable, for example, an alkyl group, a dialkylamino group, an alkoxy group, an aryl group, An aromatic heterocyclic group or the like is selected. In order to shorten the wavelength, an electron withdrawing group is preferable, and for example, a fluorine atom, a cyano group, a perfluoroalkyl group, and the like are selected.
　窒素上の置換基として好ましくは、アルキル基、アリール基、芳香族ヘテロ環基であり、錯体の安定性の観点からアルキル基、アリール基が好ましい。前記置換基同士は連結して縮合環を形成していてもよく、形成される環としては、ベンゼン環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、チオフェン環、フラン環などが挙げられる。これら形成される環は置換基を有していてもよく、置換基としては前述の炭素原子上の置換基、窒素原子上の置換基が挙げられる。
　また前記Ａ１、Ｚ１及び窒素原子で形成される５又は６員のヘテロ環の置換基と、前記Ｂ１、Ｚ２及び炭素原子で形成される５又は６員環の置換基とが連結して、前述と同様の縮合環を形成していてもよい。 The substituent on nitrogen is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, and an alkyl group or an aryl group is preferable from the viewpoint of the stability of the complex. The substituents may be linked to form a condensed ring, and the formed ring includes a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyrazole. Ring, thiophene ring, furan ring and the like. These formed rings may have a substituent, and examples of the substituent include the substituent on the carbon atom and the substituent on the nitrogen atom.
In addition, a 5- or 6-membered heterocyclic substituent formed by A 1 , Z 1 and a nitrogen atom and a 5- or 6-membered substituent formed by B 1 , Z 2 and a carbon atom are linked. Then, the same condensed ring as described above may be formed.
　（Ｘ－Ｙ）は、二座のモノアニオン性配位子を示す。二座のモノアニオン性配位子の例としては、Ｌａｍａｎｓｋｙらの国際公開第０２／１５６４５号の８９～９０頁に記載されている。
　（Ｘ－Ｙ）で表される二座のモノアニオン性配位子として好ましくは、下記一般式（Ｌ－１）表される二座のモノアニオン配位子である。 (XY) represents a bidentate monoanionic ligand. Examples of bidentate monoanionic ligands are described on pages 89-90 of Lamansky et al., WO 02/15645.
The bidentate monoanionic ligand represented by (XY) is preferably a bidentate monoanionic ligand represented by the following general formula (L-1).
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
　一般式（Ｌ－１）中、ＲＬ１及びＲＬ２はそれぞれ独立に、アルキル基、アリール基、又はヘテロアリール基を表す。
　ＲＬ３は水素原子、アルキル基、アリール基、又はヘテロアリール基を表す。 In General Formula (L-1), R L1 and R L2 each independently represent an alkyl group, an aryl group, or a heteroaryl group.
R L3 represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
　ＲＬ１～ＲＬ３で表されるアルキル基は置換基を有していてもよく、飽和であっても不飽和であってもよい。置換基を有する場合の置換基としては、上記置換基Ｚ’が挙げられ、好ましい置換基Ｚ’としては、フェニル基、芳香族ヘテロ環基、フッ素原子、シリル基、アミノ基、シアノ基又はこれらを組み合わせて成る基であり、フェニル基、フッ素原子、シアノ基がより好ましい。ＲＬ１～ＲＬ３で表されるアルキル基は、好ましくは炭素数１～８のアルキル基であり、より好ましくは炭素数１～５のアルキル基である。 The alkyl group represented by R L1 to R L3 may have a substituent, and may be saturated or unsaturated. Examples of the substituent in the case of having a substituent include the above-described substituent Z ′, and preferred substituent Z ′ includes a phenyl group, an aromatic heterocyclic group, a fluorine atom, a silyl group, an amino group, a cyano group, or these. And a phenyl group, a fluorine atom, and a cyano group are more preferable. The alkyl group represented by R L1 to R L3 is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.
　ＲＬ１～ＲＬ３で表されるアリール基は縮環していてもよく、置換基を有していてもよい。置換基を有する場合の置換基としては、前述の置換基Ｚ’が挙げられ、置換基Ｚ’としては、アルキル基又はアリール基が好ましく、アルキル基がより好ましい。ＲＬ１～ＲＬ３で表されるアリール基は、好ましくは炭素数６～３０のアリール基であり、より好ましくは炭素数６～１８のアリール基である。 The aryl group represented by R L1 to R L3 may be condensed or may have a substituent. In the case of having a substituent, examples of the substituent include the above-described substituent Z ′, and the substituent Z ′ is preferably an alkyl group or an aryl group, and more preferably an alkyl group. The aryl group represented by R L1 to R L3 is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 18 carbon atoms.
　ＲＬ１～ＲＬ３で表されるヘテロアリール基は、縮環していてもよく、置換基を有していてもよい。置換基を有する場合の置換基としては、前述の置換基Ｚ’が挙げられ、置換基Ｚ’としては、アルキル基又はアリール基が好ましく、アルキル基がより好ましい。ＲＬ１～ＲＬ３で表されるヘテロアリール基は、好ましくは炭素数４～１２のヘテロアリール基であり、より好ましくは炭素数４～１０のヘテロアリール基である。 The heteroaryl group represented by R L1 to R L3 may be condensed or may have a substituent. In the case of having a substituent, examples of the substituent include the above-described substituent Z ′, and the substituent Z ′ is preferably an alkyl group or an aryl group, and more preferably an alkyl group. The heteroaryl group represented by R L1 to R L3 is preferably a heteroaryl group having 4 to 12 carbon atoms, more preferably a heteroaryl group having 4 to 10 carbon atoms.
　ＲＬ１及びＲＬ２として好ましくは、アルキル基又はアリール基であり、より好ましくはアルキル基又はフェニル基であり、特に好ましくはアルキル基である。
　ＲＬ１及びＲＬ２で表されるアルキル基として、好ましくは総炭素原子数１～８のアルキル基であり、より好ましくは総炭素原子数１～５のアルキル基であり、例えばメチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｉｓｏ－ブチル基、ｔ－ブチル基、ｎ－ブチル基、シクロヘキシル基等が挙げられ、メチル基、エチル基、ｉｓｏ－ブチル基、又はｔ－ブチル基が好ましく、メチル基が特に好ましい。 R L1 and R L2 are preferably an alkyl group or an aryl group, more preferably an alkyl group or a phenyl group, and particularly preferably an alkyl group.
The alkyl group represented by R L1 and R L2 is preferably an alkyl group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 5 carbon atoms in total, such as a methyl group or an ethyl group N-propyl group, iso-propyl group, iso-butyl group, t-butyl group, n-butyl group, cyclohexyl group and the like, and methyl group, ethyl group, iso-butyl group, or t-butyl group is A methyl group is preferable, and a methyl group is particularly preferable.
　ＲＬ３として好ましくは、水素原子、アルキル基、又はアリール基であり、より好ましくは水素原子又はアルキル基であり、特に好ましくは水素原子である。 R L3 is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
　一般式（Ｅ－１）で表されるＩｒ錯体の好ましい態様は、一般式（Ｅ－２）で表されるＩｒ錯体材料である。
　次に一般式（Ｅ－２）について説明する。 A preferred embodiment of the Ir complex represented by the general formula (E-1) is an Ir complex material represented by the general formula (E-2).
Next, general formula (E-2) will be described.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　一般式（Ｅ－２）中、ＡＥ１～ＡＥ８はそれぞれ独立に、窒素原子又はＣ－ＲＥを表す。
　ＲＥは水素原子又は置換基を表す。
　（Ｘ－Ｙ）はモノアニオン性の二座配位子を表す。
　ｎＥ２は１～３の整数を表す。 In general formula (E-2), A E1 to A E8 each independently represents a nitrogen atom or C—R E.
R E represents a hydrogen atom or a substituent.
(XY) represents a monoanionic bidentate ligand.
n E2 represents an integer of 1 to 3.
　ＡＥ１～ＡＥ８はそれぞれ独立に、窒素原子又はＣ－ＲＥを表す。ＲＥは水素原子又は置換基を表し、ＲＥ同士が互いに連結して環を形成していてもよい。形成される環としては、前述の一般式（Ｅ－１）において述べた縮合環と同様のものが挙げられる。ＲＥで表される置換基としては、前記置換基群Ａとして挙げたものが適用できる。
　ＡＥ１～ＡＥ４として好ましくはＣ－ＲＥであり、ＡＥ１～ＡＥ４がＣ－ＲＥである場合に、ＡＥ３のＲＥとして好ましくは水素原子、アルキル基、アリール基、アミノ基、アルコキシ基、アリールオキシ基、フッ素原子、又はシアノ基であり、より好ましくは水素原子、アルキル基、アミノ基、アルコキシ基、アリールオキシ基、又はフッ素原子であり、特に好ましく水素原子、又はフッ素原子であり、ＡＥ１、ＡＥ２及びＡＥ４のＲＥとして好ましくは水素原子、アルキル基、アリール基、アミノ基、アルコキシ基、アリールオキシ基、フッ素原子、又はシアノ基であり、より好ましくは水素原子、アルキル基、アミノ基、アルコキシ基、アリールオキシ基、又はフッ素原子であり、特に好ましく水素原子である。 A E1 to A E8 each independently represent a nitrogen atom or C—R E. R E represents a hydrogen atom or a substituent, and R E may be connected to each other to form a ring. Examples of the ring formed include the same condensed rings described in the general formula (E-1). Examples of the substituent represented by R E, we are the same as those mentioned above substituent group A.
Preferred as A E1 ~ A E4 is C-R E, if A E1 ~ A E4 is C-R E, preferably a hydrogen atom R E of A E3, alkyl group, aryl group, amino group, An alkoxy group, an aryloxy group, a fluorine atom, or a cyano group, more preferably a hydrogen atom, an alkyl group, an amino group, an alkoxy group, an aryloxy group, or a fluorine atom, and particularly preferably a hydrogen atom or a fluorine atom. And R E of A E1 , A E2 and A E4 is preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine atom or a cyano group, more preferably a hydrogen atom, An alkyl group, an amino group, an alkoxy group, an aryloxy group, or a fluorine atom, particularly preferably a hydrogen atom.
　ＡＥ５～ＡＥ８として好ましくはＣ－ＲＥであり、ＡＥ５～ＡＥ８がＣ－ＲＥである場合に、ＲＥとして好ましくは水素原子、アルキル基、ペルフルオロアルキル基、アリール基、芳香族へテロ環基、ジアルキルアミノ基、ジアリールアミノ基、アルキルオキシ基、シアノ基、又はフッ素原子であり、より好ましくは、水素原子、アルキル基、ペルフルオロアルキル基、アリール基、ジアルキルアミノ基、シアノ基、又はフッ素原子であり、更に好ましくは、水素原子、アルキル基、トリフルオロメチル基、又はフッ素原子である。また可能な場合は置換基同士が連結して縮環構造を形成してもよい。発光波長を短波長側にシフトさせる場合、ＡＥ６が窒素原子であることが好ましい。
　（Ｘ－Ｙ）、及びｎＥ２は一般式（Ｅ－１）における（Ｘ－Ｙ）、及びｎＥ１と同義であり好ましい範囲も同様である。 A E5 to A E8 are preferably C—R E , and when A E5 to A E8 are C—R E , R E is preferably a hydrogen atom, alkyl group, perfluoroalkyl group, aryl group, aromatic A heterocyclic group, a dialkylamino group, a diarylamino group, an alkyloxy group, a cyano group, or a fluorine atom, more preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group, a dialkylamino group, a cyano group, Or a fluorine atom, and more preferably a hydrogen atom, an alkyl group, a trifluoromethyl group, or a fluorine atom. If possible, the substituents may be linked to form a condensed ring structure. In the case where the emission wavelength is shifted to the short wavelength side, A E6 is preferably a nitrogen atom.
(X-Y), and n E2 of the general formula in (E1) (X-Y) , and has the same meaning as n E1 preferable ranges are also the same.
　前記一般式（Ｅ－２）で表される化合物のより好ましい形態は、下記一般式（Ｅ－３）で表される化合物である。 A more preferred form of the compound represented by the general formula (E-2) is a compound represented by the following general formula (E-3).
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
　一般式（Ｅ－３）中、ＲＴ１、ＲＴ２、ＲＴ３、ＲＴ４、ＲＴ５、ＲＴ６及びＲＴ７は、それぞれ独立に水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、－ＣＮ、ペルフルオロアルキル基、トリフルオロビニル基、－ＣＯ２Ｒ、－Ｃ（Ｏ）Ｒ、－ＮＲ２、－ＮＯ２、－ＯＲ、ハロゲン原子、アリール基又はヘテロアリール基を表し、更に置換基Ｚを有していてもよい。Ｒはそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。
　ＡはＣＲ’又は窒素原子を表し、Ｒ’は水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、－ＣＮ、ペルフルオロアルキル基、トリフルオロビニル基、－ＣＯ２Ｒ、－Ｃ（Ｏ）Ｒ、－ＮＲ２、－ＮＯ２、－ＯＲ、ハロゲン原子、アリール基又はヘテロアリール基を表し、更に置換基Ｚを有していてもよい。Ｒはそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。
　ＲＴ１～ＲＴ７、及びＲ’は、任意の２つが互いに結合して縮合４～７員環を形成してもよく、該縮合４～７員環は、シクロアルキル、アリール又はヘテロアリールであり、該縮合４～７員環は更に置換基Ｚを有していてもよい。これらのうち、ＲＴ１とＲＴ７、又はＲＴ５とＲＴ６で縮環してベンゼン環を形成する場合が好ましく、ＲＴ５とＲＴ６で縮環してベンゼン環を形成する場合が特に好ましい。
　Ｚはそれぞれ独立に、ハロゲン原子、－Ｒ”、－ＯＲ”、－Ｎ（Ｒ”）２、－ＳＲ”、－Ｃ（Ｏ）Ｒ”、－Ｃ（Ｏ）ＯＲ”、－Ｃ（Ｏ）Ｎ（Ｒ”）２、－ＣＮ、－ＮＯ２、－ＳＯ２、－ＳＯＲ”、－ＳＯ２Ｒ”、又は－ＳＯ３Ｒ”を表し、Ｒ”はそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。
　（Ｘ－Ｙ）は、モノアニオン性の二座配位子を表す。ｎＥ３は１～３の整数を表す。 In general formula (E-3), R T1 , R T2 , R T3 , R T4 , R T5 , R T6 and R T7 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, —CN, a perfluoroalkyl group, a trifluorovinyl group, —CO 2 R, —C (O) R, —NR 2 , —NO 2 , —OR, a halogen atom, an aryl group or a heteroaryl group, and further a substituent Z may be included. Each R independently represents a hydrogen atom, an alkyl group, a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
A represents CR ′ or a nitrogen atom, and R ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, —CN, a perfluoroalkyl group, a trifluorovinyl group, —CO 2 R, —C (O ) R, —NR 2 , —NO 2 , —OR, a halogen atom, an aryl group or a heteroaryl group, which may further have a substituent Z. Each R independently represents a hydrogen atom, an alkyl group, a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
R T1 to R T7 and R ′ may be bonded to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring is cycloalkyl, aryl or heteroaryl. The condensed 4- to 7-membered ring may further have a substituent Z. Among these, a case where a ring is condensed with R T1 and R T7 , or R T5 and R T6 to form a benzene ring is preferable, and a case where a ring is condensed with R T5 and R T6 to form a benzene ring is particularly preferable.
Z is each independently a halogen atom, —R ″, —OR ″, —N (R ″) 2 , —SR ″, —C (O) R ″, —C (O) OR ″, —C (O) N (R ") 2, -CN , -NO 2, -SO 2, -SOR", - SO 2 R ", or -SO 3 R" represents, R "are each independently a hydrogen atom, an alkyl group, A perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group is represented.
(XY) represents a monoanionic bidentate ligand. n E3 represents an integer of 1 to 3.
　アルキル基としては、置換基を有していてもよく、飽和であっても不飽和であってもよく、置換してもよい基としては、前述の置換基Ｚを挙げることができる。ＲＴ１～ＲＴ７、及びＲ’で表されるアルキル基として、好ましくは総炭素原子数１～８のアルキル基であり、より好ましくは総炭素原子数１～６のアルキル基であり、例えばメチル基、エチル基、ｉ－プロピル基、シクロヘキシル基、ｔ－ブチル基等が挙げられる。
　シクロアルキル基としては、置換基を有していてもよく、飽和であっても不飽和であってもよく、置換してもよい基としては、前述の置換基Ｚを挙げることができる。ＲＴ１～ＲＴ７、及びＲ’で表されるシクロアルキル基として、好ましくは環員数４～７のシクロアルキル基であり、より好ましくは総炭素原子数５～６のシクロアルキル基であり、例えばシクロペンチル基、シクロヘキシル基等が挙げられる。
　ＲＴ１～ＲＴ７、及びＲ’で表されるアルケニル基としては好ましくは炭素数２～３０、より好ましくは炭素数２～２０、特に好ましくは炭素数２～１０であり、例えばビニル、アリル、１－プロペニル、１－イソプロペニル、１－ブテニル、２－ブテニル、３－ペンテニルなどが挙げられる。
　ＲＴ１～ＲＴ７、及びＲ’で表されるアルキニル基としては、好ましくは炭素数２～３０、より好ましくは炭素数２～２０、特に好ましくは炭素数２～１０であり、例えばエチニル、プロパルギル、１－プロピニル、３－ペンチニルなどが挙げられる。 The alkyl group may have a substituent, may be saturated or unsaturated, and examples of the group that may be substituted include the above-described substituent Z. The alkyl group represented by R T1 to R T7 and R ′ is preferably an alkyl group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 6 carbon atoms in total, such as methyl Group, ethyl group, i-propyl group, cyclohexyl group, t-butyl group and the like.
The cycloalkyl group may have a substituent, may be saturated or unsaturated, and examples of the group that may be substituted include the above-described substituent Z. The cycloalkyl group represented by R T1 to R T7 and R ′ is preferably a cycloalkyl group having 4 to 7 ring members, more preferably a cycloalkyl group having 5 to 6 carbon atoms in total, A cyclopentyl group, a cyclohexyl group, etc. are mentioned.
The alkenyl group represented by R T1 to R T7 and R ′ preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. For example, vinyl, allyl, Examples include 1-propenyl, 1-isopropenyl, 1-butenyl, 2-butenyl, 3-pentenyl and the like.
The alkynyl group represented by R T1 to R T7 and R ′ preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. For example, ethynyl, propargyl , 1-propynyl, 3-pentynyl and the like.
　ＲＴ１～ＲＴ７、及びＲ’で表されるペルフルオロアルキル基は、前述のアルキル基の全ての水素原子がフッ素原子に置き換えられたものが挙げられる。 Examples of the perfluoroalkyl group represented by R T1 to R T7 and R ′ include those in which all hydrogen atoms of the aforementioned alkyl group are replaced with fluorine atoms.
　ＲＴ１～ＲＴ７、及びＲ’で表されるアリール基としては、好ましくは、炭素数６から３０の置換若しくは無置換のアリール基、例えば、フェニル基、トリル基、ナフチル基等が挙げられる。 The aryl group represented by R T1 to R T7 and R ′ is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a tolyl group, or a naphthyl group.
　ＲＴ１～ＲＴ７、及びＲ’で表されるヘテロアリール基としては、好ましくは、炭素数５～８のヘテロアリール基であり、より好ましくは、５又は６員の置換若しくは無置換のヘテロアリール基であり、例えば、ピリジル基、ピラジニル基、ピリダジニル基、ピリミジニル基、トリアジニル基、キノリニル基、イソキノリニル基、キナゾリニル基、シンノリニル基、フタラジニル基、キノキサリニル基、ピロリル基、インドリル基、フリル基、ベンゾフリル基、チエニル基、ベンゾチエニル基、ピラゾリル基、イミダゾリル基、ベンズイミダゾリル基、トリアゾリル基、オキサゾリル基、ベンズオキサゾリル基、チアゾリル基、ベンゾチアゾリル基、イソチアゾリル基、ベンズイソチアゾリル基、チアジアゾリル基、イソオキサゾリル基、ベンズイソオキサゾリル基、ピロリジニル基、ピペリジニル基、ピペラジニル基、イミダゾリジニル基、チアゾリニル基、スルホラニル基、カルバゾリル基、ジベンゾフリル基、ジベンゾチエニル基、７ピリドインドリル基などが挙げられる。好ましい例としては、ピリジル基、ピリミジニル基、イミダゾリル基、チエニル基であり、より好ましくは、ピリジル基、ピリミジニル基である。 The heteroaryl group represented by R T1 to R T7 and R ′ is preferably a heteroaryl group having 5 to 8 carbon atoms, more preferably a 5- or 6-membered substituted or unsubstituted heteroaryl group. Groups such as pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, cinnolinyl, phthalazinyl, quinoxalinyl, pyrrolyl, indolyl, furyl, benzofuryl , Thienyl group, benzothienyl group, pyrazolyl group, imidazolyl group, benzimidazolyl group, triazolyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, isothiazolyl group, benzisothiazolyl group, thiadiazolyl group, isoxazolyl group , Lens benzisoxazolyl group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, an imidazolidinyl group, a thiazolinyl group, a sulfolanyl group, a carbazolyl group, a dibenzofuryl group, dibenzothienyl group, such as 7 pyrido-indolyl group. Preferred examples include pyridyl group, pyrimidinyl group, imidazolyl group, and thienyl group, and more preferred are pyridyl group and pyrimidinyl group.
　ＲＴ１～ＲＴ７、及びＲ’として好ましくは、水素原子、アルキル基、シアノ基、トリフルオロメチル基、ペルフルオロアルキル基、ジアルキルアミノ基、フルオロ基、アリール基、ヘテロアリール基であり、より好ましくは水素原子、アルキル基、シアノ基、トリフルオロメチル基、フルオロ基、アリール基であり、更に好ましくは、水素原子、アルキル基、アリール基である。置換基Ｚとしては、アルキル基、アルコキシ基、フルオロ基、シアノ基、ジアルキルアミノ基が好ましく、水素原子がより好ましい。 R T1 to R T7 and R ′ are preferably a hydrogen atom, an alkyl group, a cyano group, a trifluoromethyl group, a perfluoroalkyl group, a dialkylamino group, a fluoro group, an aryl group or a heteroaryl group, more preferably A hydrogen atom, an alkyl group, a cyano group, a trifluoromethyl group, a fluoro group, and an aryl group are preferable, and a hydrogen atom, an alkyl group, and an aryl group are more preferable. As the substituent Z, an alkyl group, an alkoxy group, a fluoro group, a cyano group, and a dialkylamino group are preferable, and a hydrogen atom is more preferable.
　ＲＴ１～ＲＴ７、及びＲ’は任意の２つが互いに結合して縮合４～７員環を形成してもよく、該縮合４～７員環は、シクロアルキル、アリール又はヘテロアリールであり、該縮合４～７員環は更に置換基Ｚを有していてもよい。形成されるシクロアルキル、アリール、ヘテロアリールの定義及び好ましい範囲はＲＴ１～ＲＴ７、及びＲ’で定義したシクロアルキル基、アリール基、ヘテロアリール基と同じである。
　またＡがＣＲ’を表すと共に、ＲＴ１～ＲＴ７、及びＲ’のうち、０～２つがアルキル基又はフェニル基で、残りが全て水素原子である場合が特に好ましく、ＲＴ１～ＲＴ７、及びＲ’のうち、０～２つがアルキル基で、残りが全て水素原子である場合が特に好ましい。 Any one of R T1 to R T7 and R ′ may be bonded to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring is cycloalkyl, aryl, or heteroaryl; The condensed 4- to 7-membered ring may further have a substituent Z. The definition and preferred range of cycloalkyl, aryl and heteroaryl formed are the same as the cycloalkyl group, aryl group and heteroaryl group defined by R T1 to R T7 and R ′.
Further, it is particularly preferable that A represents CR ′, and among R T1 to R T7 , and R ′, 0 to 2 are alkyl groups or phenyl groups, and the rest are all hydrogen atoms, and R T1 to R T7 , And R ′ are particularly preferably a case where 0 to 2 are alkyl groups and the rest are all hydrogen atoms.
　ｎＥ３は２又は３であることが好ましい。錯体中の配位子の種類は１～２種類から構成されることが好ましく、更に好ましくは１種類である。錯体分子内に反応性基を導入する際には合成容易性という観点から配位子が２種類からなることも好ましい。
　（Ｘ－Ｙ）は、一般式（Ｅ－１）における（Ｘ－Ｙ）と同義であり好ましい範囲も同様である。 n E3 is preferably 2 or 3. The type of ligand in the complex is preferably composed of 1 to 2 types, more preferably 1 type. When introducing a reactive group into the complex molecule, it is also preferred that the ligand consists of two types from the viewpoint of ease of synthesis.
(XY) has the same meaning as (XY) in formula (E-1), and the preferred range is also the same.
　前記一般式（Ｅ－３）で表される化合物の好ましい形態の一つは、下記一般式（Ｅ－４）で表される化合物である。 One preferred form of the compound represented by the general formula (E-3) is a compound represented by the following general formula (E-4).
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
　一般式（Ｅ－４）におけるＲＴ１～ＲＴ４、Ａ、（Ｘ－Ｙ）及びｎＥ４は、一般式（Ｅ－３）におけるＲＴ１～ＲＴ４、Ａ、（Ｘ－Ｙ）及びｎＥ３と同義であり、好ましい範囲も同様である。Ｒ１’～Ｒ５’はそれぞれ独立に水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、－ＣＮ、ペルフルオロアルキル基、トリフルオロビニル基、－ＣＯ２Ｒ、－Ｃ（Ｏ）Ｒ、－ＮＲ２、－ＮＯ２、－ＯＲ、ハロゲン原子、アリール基又はヘテロアリール基を表し、更に置換基Ｚを有していてもよい。Ｒはそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。
　Ｒ１’～Ｒ５’は、任意の２つが互いに結合して縮合４～７員環を形成してもよく、該縮合４～７員環は、シクロアルキル、アリール又はヘテロアリールであり、該縮合４～７員環は更に置換基Ｚを有していてもよい。
　Ｚはそれぞれ独立に、ハロゲン原子、－Ｒ”、－ＯＲ”、－Ｎ（Ｒ”）２、－ＳＲ”、－Ｃ（Ｏ）Ｒ”、－Ｃ（Ｏ）ＯＲ”、－Ｃ（Ｏ）Ｎ（Ｒ”）２、－ＣＮ、－ＮＯ２、－ＳＯ２、－ＳＯＲ”、－ＳＯ２Ｒ”、又は－ＳＯ３Ｒ”を表し、Ｒ”はそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。
　また、Ｒ１’～Ｒ５’における好ましい範囲は、一般式（Ｅ－３）におけるＲＴ１～ＲＴ７、Ｒ’と同様である。またＡがＣＲ’を表すと共に、ＲＴ１～ＲＴ４、Ｒ’、及びＲ１’～Ｒ５’のうち、０～２つがアルキル基又はフェニル基で残りが全て水素原子である場合が特に好ましく、ＲＴ１～ＲＴ４、Ｒ’、及びＲ１’～Ｒ５’のうち、０～２つがアルキル基で残りが全て水素原子である場合が更に好ましい。 R T1 to R T4 , A, (XY) and n E4 in the general formula (E-4) are R T1 to R T4 , A, (XY) and n E3 in the general formula (E-3). The preferred range is also the same. R 1 ′ to R 5 ′ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, —CN, perfluoroalkyl group, trifluorovinyl group, —CO 2 R, —C (O) R. , —NR 2 , —NO 2 , —OR, a halogen atom, an aryl group or a heteroaryl group, and optionally having a substituent Z. Each R independently represents a hydrogen atom, an alkyl group, a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
Any one of R 1 ′ to R 5 ′ may be bonded to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring is cycloalkyl, aryl, or heteroaryl; The condensed 4- to 7-membered ring may further have a substituent Z.
Z is each independently a halogen atom, —R ″, —OR ″, —N (R ″) 2 , —SR ″, —C (O) R ″, —C (O) OR ″, —C (O) N (R ") 2, -CN , -NO 2, -SO 2, -SOR", - SO 2 R ", or -SO 3 R" represents, R "are each independently a hydrogen atom, an alkyl group, A perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group is represented.
In addition, preferred ranges for R 1 ′ to R 5 ′ are the same as R T1 to R T7 and R ′ in formula (E-3). Further, it is particularly preferable that A represents CR ′, and 0 to 2 of R T1 to R T4 , R ′, and R 1 ′ to R 5 ′ are alkyl groups or phenyl groups, and the rest are all hydrogen atoms. More preferably, 0 to 2 of R T1 to R T4 , R ′, and R 1 ′ to R 5 ′ are alkyl groups and the rest are all hydrogen atoms.
　前記一般式（Ｅ－３）で表される化合物の好ましい別の形態は、下記一般式（Ｅ－５）で表される化合物である。 Another preferred embodiment of the compound represented by the general formula (E-3) is a compound represented by the following general formula (E-5).
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　一般式（Ｅ－５）におけるＲＴ２～ＲＴ６、Ａ、（Ｘ－Ｙ）及びｎＥ５は、一般式（Ｅ－３）におけるＲＴ２～ＲＴ６、Ａ、（Ｘ－Ｙ）及びｎＥ３と同義であり、好ましい範囲も同様である。Ｒ６’～Ｒ８’はそれぞれ独立に水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、－ＣＮ、ペルフルオロアルキル基、トリフルオロビニル基、－ＣＯ２Ｒ、－Ｃ（Ｏ）Ｒ、－ＮＲ２、－ＮＯ２、－ＯＲ、ハロゲン原子、アリール基又はヘテロアリール基を表し、更に置換基Ｚを有していてもよい。Ｒはそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。
　ＲＴ５、ＲＴ６、Ｒ６’～Ｒ８’は、任意の２つが互いに結合して縮合４～７員環を形成してもよく、該縮合４～７員環は、シクロアルキル、アリール又はヘテロアリールであり、該縮合４～７員環は更に置換基Ｚを有していてもよい。
　Ｚはそれぞれ独立に、ハロゲン原子、－Ｒ”、－ＯＲ”、－Ｎ（Ｒ”）２、－ＳＲ”、－Ｃ（Ｏ）Ｒ”、－Ｃ（Ｏ）ＯＲ”、－Ｃ（Ｏ）Ｎ（Ｒ”）２、－ＣＮ、－ＮＯ２、－ＳＯ２、－ＳＯＲ”、－ＳＯ２Ｒ”、又は－ＳＯ３Ｒ”を表し、Ｒ”はそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。
　また、Ｒ６’～Ｒ８’における好ましい範囲は、一般式（Ｅ－３）におけるＲＴ１～ＲＴ７、Ｒ’と同様である。またＡがＣＲ’を表すと共に、ＲＴ２～ＲＴ６、Ｒ’、及びＲ６’～Ｒ８’のうち、０～２つがアルキル基又はフェニル基で残りが全て水素原子である場合が特に好ましく、ＲＴ２～ＲＴ６、Ｒ’、及びＲ６’～Ｒ８’のうち、０～２つがアルキル基で残りが全て水素原子である場合が更に好ましい。 R T2 to R T6 , A, (XY) and n E5 in the general formula (E-5) are R T2 to R T6 , A, (XY) and n E3 in the general formula (E-3). The preferred range is also the same. R 6 ′ to R 8 ′ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, —CN, perfluoroalkyl group, trifluorovinyl group, —CO 2 R, —C (O) R , —NR 2 , —NO 2 , —OR, a halogen atom, an aryl group or a heteroaryl group, and optionally having a substituent Z. Each R independently represents a hydrogen atom, an alkyl group, a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
R T5 , R T6 , R 6 ′ to R 8 ′ may be combined with each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring is cycloalkyl, aryl or It is a heteroaryl, and the condensed 4- to 7-membered ring may further have a substituent Z.
Z is each independently a halogen atom, —R ″, —OR ″, —N (R ″) 2 , —SR ″, —C (O) R ″, —C (O) OR ″, —C (O) N (R ") 2, -CN , -NO 2, -SO 2, -SOR", - SO 2 R ", or -SO 3 R" represents, R "are each independently a hydrogen atom, an alkyl group, A perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group is represented.
In addition, preferred ranges for R 6 ′ to R 8 ′ are the same as R T1 to R T7 and R ′ in formula (E-3). Particularly preferably, A represents CR ′, and among R T2 to R T6 , R ′, and R 6 ′ to R 8 ′, 0 to 2 are alkyl groups or phenyl groups, and the rest are all hydrogen atoms. , R T2 to R T6 , R ′, and R 6 ′ to R 8 ′ are more preferably a case where 0 to 2 are alkyl groups and the rest are all hydrogen atoms.
　一般式（Ｅ－１）で表される化合物の好ましい別の形態は、下記一般式（Ｅ－６）で表される場合である。 Another preferred embodiment of the compound represented by the general formula (E-1) is a case represented by the following general formula (E-6).
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　一般式（Ｅ－６）中、Ｒ１ａ～Ｒ１ｋは、それぞれ独立に水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、－ＣＮ、ペルフルオロアルキル基、トリフルオロビニル基、－ＣＯ２Ｒ、－Ｃ（Ｏ）Ｒ、－ＮＲ２、－ＮＯ２、－ＯＲ、ハロゲン原子、アリール基又はヘテロアリール基を表し、更に置換基Ｚを有していてもよい。Ｒはそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。
　Ｒ１ａ～Ｒ１ｋは、任意の２つが互いに結合して縮合４～７員環を形成してもよく、該縮合４～７員環は、シクロアルキル、アリール又はヘテロアリールであり、該縮合４～７員環は更に置換基Ｚを有していてもよい。これらのうち、Ｒ１ｊとＲ１ｋとが連結し単結合を形成する場合が特に好ましい。
　Ｚはそれぞれ独立に、ハロゲン原子、－Ｒ”、－ＯＲ”、－Ｎ（Ｒ”）２、－ＳＲ”、－Ｃ（Ｏ）Ｒ”、－Ｃ（Ｏ）ＯＲ”、－Ｃ（Ｏ）Ｎ（Ｒ”）２、－ＣＮ、－ＮＯ２、－ＳＯ２、－ＳＯＲ”、－ＳＯ２Ｒ”、又は－ＳＯ３Ｒ”を表し、Ｒ”はそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。
　（Ｘ－Ｙ）は、モノアニオン性の二座配位子を表す。ｎＥ６は１～３の整数を表す。 In general formula (E-6), R 1a to R 1k each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, —CN, a perfluoroalkyl group, a trifluorovinyl group, —CO 2 R, —C (O) R, —NR 2 , —NO 2 , —OR, a halogen atom, an aryl group, or a heteroaryl group, which may further have a substituent Z. Each R independently represents a hydrogen atom, an alkyl group, a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
Any two of R 1a to R 1k may be bonded to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring is cycloalkyl, aryl, or heteroaryl; The 7-membered ring may further have a substituent Z. Of these, the case where R 1j and R 1k are linked to form a single bond is particularly preferred.
Z is each independently a halogen atom, —R ″, —OR ″, —N (R ″) 2 , —SR ″, —C (O) R ″, —C (O) OR ″, —C (O) N (R ") 2, -CN , -NO 2, -SO 2, -SOR", - SO 2 R ", or -SO 3 R" represents, R "are each independently a hydrogen atom, an alkyl group, A perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group is represented.
(XY) represents a monoanionic bidentate ligand. n E6 represents an integer of 1 to 3.
　一般式（Ｅ－６）において、Ｒ１ａ～Ｒ１ｋの好ましい範囲は、一般式（Ｅ－３）におけるＲＴ１～ＲＴ７、Ｒ’におけるものと同様である。またＲ１ａ～Ｒ１ｋのうち、０～２つがアルキル基又はフェニル基で残りが全て水素原子である場合が特に好ましく、Ｒ１ａ～Ｒ１ｋのうち、０～２つがアルキル基で残りが全て水素原子である場合が更に好ましい。
　（Ｘ－Ｙ）、及びｎＥ６の好ましい範囲は、一般式（Ｅ－３）における（Ｘ－Ｙ）、及びｎＥ３と同様である。 In the general formula (E-6), preferred ranges of R 1a to R 1k are the same as those in R T1 to R T7 and R ′ in the general formula (E-3). Further, it is particularly preferable that 0 to 2 of R 1a to R 1k are alkyl groups or phenyl groups and the rest are all hydrogen atoms, and 0 to 2 of R 1a to R 1k are alkyl groups and the rest are all hydrogen atoms. More preferably, it is an atom.
The preferred range of (XY) and n E6 is the same as (XY) and n E3 in general formula (E-3).
　一般式（Ｅ－６）で表される化合物のより好ましい形態は、下記一般式（Ｅ－７）で表される場合である。 A more preferable form of the compound represented by the general formula (E-6) is a case represented by the following general formula (E-7).
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
　一般式（Ｅ－７）中、Ｒ１ａ～Ｒ１ｉの定義や好ましい範囲は一般式（Ｅ－６）におけるＲ１ａ～Ｒ１ｉと同様である。またＲ１ａ～Ｒ１ｉのうち、０～２つがアルキル基又はアリール基で残りが全て水素原子である場合が特に好ましい。（Ｘ－Ｙ）、及びｎＥ７の定義や好ましい範囲は一般式（Ｅ－３）における（Ｘ－Ｙ）、及びｎＥ３と同様である。 In the formula (E-7), definition and preferable ranges of R 1a ~ R 1i are the same as R 1a ~ R 1i in the formula (E-6). Further, it is particularly preferable that 0 to 2 of R 1a to R 1i are alkyl groups or aryl groups and the rest are all hydrogen atoms. The definitions and preferred ranges of (XY) and n E7 are the same as (XY) and n E3 in general formula (E-3).
　一般式（Ｅ－１）で表される化合物の好ましい具体例を以下に列挙するが、以下に限定されるものではない。 Preferred specific examples of the compound represented by the general formula (E-1) are listed below, but are not limited thereto.
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
　上記一般式（Ｅ－１）で表される化合物として例示した化合物は、特開２００９－９９７８３号公報に記載の方法や、米国特許７２７９２３２号等に記載の種々の方法で合成できる。合成後、カラムクロマトグラフィー、再結晶等による精製を行った後、昇華精製により精製することが好ましい。昇華精製により、有機不純物を分離できるだけでなく、無機塩や残留溶媒等を効果的に取り除くことができる。 The compounds exemplified as the compound represented by the general formula (E-1) can be synthesized by the method described in JP2009-99783A, various methods described in US Pat. No. 7,279,232 and the like. After synthesis, it is preferable to purify by sublimation purification after purification by column chromatography, recrystallization or the like. By sublimation purification, not only can organic impurities be separated, but inorganic salts and residual solvents can be effectively removed.
　一般式（Ｅ－１）で表される化合物は、発光層に含有されるが、その用途が限定されることはなく、更に有機層内のいずれの層に更に含有されてもよい。 The compound represented by the general formula (E-1) is contained in the light emitting layer, but its use is not limited and may be further contained in any layer in the organic layer.
　発光層中の一般式（Ｅ－１）で表される化合物は、は、発光層中に一般的に発光層を形成する全化合物質量に対して、０．１質量％～５０質量％含有されるが、耐久性、外部量子効率の観点から１質量％～５０質量％含有されることが好ましく、２質量％～４０質量％含有されることがより好ましい。 The compound represented by the general formula (E-1) in the light emitting layer is contained in an amount of 0.1% by mass to 50% by mass with respect to the total mass of the compound generally forming the light emitting layer in the light emitting layer. However, from the viewpoint of durability and external quantum efficiency, the content is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 40% by mass.
　発光層の厚さは、特に限定されるものではないが、通常、２ｎｍ～５００ｎｍであるのが好ましく、中でも、外部量子効率の観点で、３ｎｍ～２００ｎｍであるのがより好ましく、５ｎｍ～１００ｎｍであるのが更に好ましい。 The thickness of the light emitting layer is not particularly limited, but is usually preferably 2 nm to 500 nm, and more preferably 3 nm to 200 nm, and more preferably 5 nm to 100 nm from the viewpoint of external quantum efficiency. More preferably.
　本発明の素子における発光層は、発光材料のみで構成されていてもよく、ホスト材料と発光材料の混合層とした構成でもよい。発光材料の種類は一種であっても二種以上であっても良い。ホスト材料は電荷輸送材料であることが好ましい。ホスト材料は一種であっても二種以上であってもよく、例えば、電子輸送性のホスト材料とホール輸送性のホスト材料を混合した構成が挙げられる。更に、発光層中に電荷輸送性を有さず、発光しない材料を含んでいてもよい。
　また、発光層は一層であっても二層以上の多層であってもよく、それぞれの層に同じ発光材料やホスト材料を含んでもよいし、層毎に異なる材料を含んでもよい。発光層が複数の場合、それぞれの発光層が異なる発光色で発光してもよい。 The light emitting layer in the element of the present invention may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material. The kind of the light emitting material may be one kind or two or more kinds. The host material is preferably a charge transport material. The host material may be one kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Furthermore, the light emitting layer may contain a material that does not have charge transporting properties and does not emit light.
Further, the light emitting layer may be a single layer or a multilayer of two or more layers, and each layer may contain the same light emitting material or host material, or each layer may contain a different material. When there are a plurality of light emitting layers, each of the light emitting layers may emit light with different emission colors.
　次に一般式（Ｃ－１）について説明する。 Next, the general formula (C-1) will be described.
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
（一般式（Ｃ－１）中、Ｑ１、Ｑ２、Ｑ３及びＱ４はそれぞれ独立に、Ｐｔに配位する配位子を表す。Ｌ１、Ｌ２及びＬ３はそれぞれ独立に、単結合又は二価の連結基を表す。） (In the general formula (C-1), Q 1 , Q 2 , Q 3 and Q 4 each independently represent a ligand coordinated to Pt. L 1 , L 2 and L 3 are each independently Represents a single bond or a divalent linking group.)
　一般式（Ｃ－１）について説明する。
　Ｑ１、Ｑ２、Ｑ３及びＱ４はそれぞれ独立にＰｔに配位する配位子を表す。この時、Ｑ１、Ｑ２、Ｑ３及びＱ４とＰｔの結合は、共有結合、イオン結合、配位結合などいずれであってもよい。Ｑ１、Ｑ２、Ｑ３及びＱ４中のＰｔに結合する原子としては、炭素原子、窒素原子、酸素原子、硫黄原子、リン原子が好ましく、Ｑ１、Ｑ２、Ｑ３及びＱ４中のＰｔに結合する原子の内、少なくとも１つが炭素原子であることが好ましく、２つが炭素原子であることがより好ましく、２つが炭素原子で、２つが窒素原子であることが特に好ましい。 The general formula (C-1) will be described.
Q 1 , Q 2 , Q 3 and Q 4 each independently represent a ligand coordinated to Pt. At this time, the bond between Q 1 , Q 2 , Q 3 and Q 4 and Pt may be any of a covalent bond, an ionic bond, a coordinate bond, and the like. As an atom couple | bonded with Pt in Q < 1 >, Q < 2 >, Q < 3 > and Q < 4 >, a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom are preferable, and in Q < 1 >, Q < 2 >, Q < 3 > and Q < 4 > Of the atoms bonded to Pt, at least one is preferably a carbon atom, more preferably two are carbon atoms, and particularly preferably two are carbon atoms and two are nitrogen atoms.
　炭素原子でＰｔに結合するＱ１、Ｑ２、Ｑ３及びＱ４としては、アニオン性の配位子でも中性の配位子でもよく、アニオン性の配位子としてはビニル配位子、芳香族炭化水素環配位子（例えばベンゼン配位子、ナフタレン配位子、アントラセン配位子、フェナントレン配位子など）、ヘテロ環配位子（例えばフラン配位子、チオフェン配位子、ピリジン配位子、ピラジン配位子、ピリミジン配位子、ピリダジン配位子、トリアジン配位子、チアゾール配位子、オキサゾール配位子、ピロール配位子、イミダゾール配位子、ピラゾール配位子、トリアゾール配位子及び、それらを含む縮環体（例えばキノリン配位子、ベンゾチアゾール配位子など））が挙げられる。中性の配位子としてはカルベン配位子が挙げられる。 Q 1 , Q 2 , Q 3 and Q 4 bonded to Pt by a carbon atom may be an anionic ligand or a neutral ligand, and the anionic ligand is a vinyl ligand, Aromatic hydrocarbon ring ligand (eg benzene ligand, naphthalene ligand, anthracene ligand, phenanthrene ligand etc.), heterocyclic ligand (eg furan ligand, thiophene ligand, pyridine) Ligand, pyrazine ligand, pyrimidine ligand, pyridazine ligand, triazine ligand, thiazole ligand, oxazole ligand, pyrrole ligand, imidazole ligand, pyrazole ligand, triazole And a condensed ring containing them (for example, quinoline ligand, benzothiazole ligand, etc.). A carbene ligand is mentioned as a neutral ligand.
　窒素原子でＰｔに結合するＱ１、Ｑ２、Ｑ３及びＱ４としては、中性の配位子でもアニオン性の配位子でもよく、中性の配位子としては含窒素芳香族ヘテロ環配位子（ピリジン配位子、ピラジン配位子、ピリミジン配位子、ピリダジン配位子、トリアジン配位子、イミダゾール配位子、ピラゾール配位子、トリアゾール配位子、オキサゾール配位子、チアゾール配位子及びそれらを含む縮環体（例えばキノリン配位子、ベンゾイミダゾール配位子など））、アミン配位子、ニトリル配位子、イミン配位子が挙げられる。アニオン性の配位子としては、アミノ配位子、イミノ配位子、含窒素芳香族ヘテロ環配位子（ピロール配位子、イミダゾール配位子、トリアゾール配位子及びそれらを含む縮環体（例えはインドール配位子、ベンゾイミダゾール配位子など））が挙げられる。 Q 1 , Q 2 , Q 3 and Q 4 bonded to Pt with a nitrogen atom may be neutral ligands or anionic ligands, and as neutral ligands, nitrogen-containing aromatic hetero Ring ligand (pyridine ligand, pyrazine ligand, pyrimidine ligand, pyridazine ligand, triazine ligand, imidazole ligand, pyrazole ligand, triazole ligand, oxazole ligand, Examples include thiazole ligands and condensed rings containing them (for example, quinoline ligands, benzimidazole ligands), amine ligands, nitrile ligands, and imine ligands. Examples of anionic ligands include amino ligands, imino ligands, nitrogen-containing aromatic heterocyclic ligands (pyrrole ligands, imidazole ligands, triazole ligands and condensed rings containing them) (For example, indole ligand, benzimidazole ligand, etc.)).
　酸素原子でＰｔに結合するＱ１、Ｑ２、Ｑ３及びＱ４としては、中性の配位子でもアニオン性の配位子でもよく、中性の配位子としてはエーテル配位子、ケトン配位子、エステル配位子、アミド配位子、含酸素ヘテロ環配位子（フラン配位子、オキサゾール配位子及びそれらを含む縮環体（ベンゾオキサゾール配位子など））が挙げられる。アニオン性の配位子としては、アルコキシ配位子、アリールオキシ配位子、ヘテロアリールオキシ配位子、アシルオキシ配位子、シリルオキシ配位子などが挙げられる。 Q 1 , Q 2 , Q 3 and Q 4 bonded to Pt with an oxygen atom may be neutral ligands or anionic ligands, and neutral ligands are ether ligands, Examples include ketone ligands, ester ligands, amide ligands, oxygen-containing heterocyclic ligands (furan ligands, oxazole ligands and condensed rings containing them (benzoxazole ligands, etc.)). It is done. Examples of the anionic ligand include an alkoxy ligand, an aryloxy ligand, a heteroaryloxy ligand, an acyloxy ligand, a silyloxy ligand, and the like.
　硫黄原子でＰｔに結合するＱ１、Ｑ２、Ｑ３及びＱ４としては、中性の配位子でもアニオン性の配位子でもよく、中性の配位子としてはチオエーテル配位子、チオケトン配位子、チオエステル配位子、チオアミド配位子、含硫黄ヘテロ環配位子（チオフェン配位子、チアゾール配位子及びそれらを含む縮環体（ベンゾチアゾール配位子など））が挙げられる。アニオン性の配位子としては、アルキルメルカプト配位子、アリールメルカプト配位子、ヘテロアリールメルカプト配位子などが挙げられる。 Q 1 , Q 2 , Q 3 and Q 4 bonded to Pt with a sulfur atom may be neutral ligands or anionic ligands, and neutral ligands include thioether ligands, Examples include thioketone ligands, thioester ligands, thioamide ligands, sulfur-containing heterocyclic ligands (thiophene ligands, thiazole ligands and condensed rings containing them (such as benzothiazole ligands)). It is done. Examples of the anionic ligand include an alkyl mercapto ligand, an aryl mercapto ligand, and a heteroaryl mercapto ligand.
　リン原子でＰｔに結合するＱ１、Ｑ２、Ｑ３及びＱ４としては、中性の配位子でもアニオン性の配位子でもよく、中性の配位子としてはホスフィン配位子、リン酸エステル配位子、亜リン酸エステル配位子、含リンヘテロ環配位子（ホスフィニン配位子など）が挙げられ、アニオン性の配位子としては、ホスフィノ配位子、ホスフィニル配位子、ホスホリル配位子などが挙げられる。 Q 1 , Q 2 , Q 3 and Q 4 bonded to Pt with a phosphorus atom may be neutral ligands or anionic ligands, and neutral ligands include phosphine ligands, Examples include phosphate ester ligands, phosphite ester ligands, and phosphorus-containing heterocyclic ligands (phosphinin ligands, etc.). Anionic ligands include phosphino ligands and phosphinyl ligands. And phosphoryl ligands.
　Ｑ１、Ｑ２、Ｑ３及びＱ４で表される基は、置換基を有していてもよく、置換基としては前記置換基群Ａとして挙げたものが適宜適用できる。また置換基同士が連結していても良い（Ｑ３とＱ４が連結した場合、環状四座配位子のＰｔ錯体になる）。 The groups represented by Q 1 , Q 2 , Q 3, and Q 4 may have a substituent, and those listed as the substituent group A can be appropriately applied as the substituent. Moreover, substituents may be connected to each other (when Q 3 and Q 4 are connected, a Pt complex of a cyclic tetradentate ligand is formed).
　Ｑ１、Ｑ２、Ｑ３及びＱ４で表される基として好ましくは、炭素原子でＰｔに結合する芳香族炭化水素環配位子、炭素原子でＰｔに結合する芳香族ヘテロ環配位子、窒素原子でＰｔに結合する含窒素芳香族ヘテロ環配位子、アシルオキシ配位子、アルキルオキシ配位子、アリールオキシ配位子、ヘテロアリールオキシ配位子、シリルオキシ配位子であり、より好ましくは、炭素原子でＰｔに結合する芳香族炭化水素環配位子、炭素原子でＰｔに結合する芳香族ヘテロ環配位子、窒素原子でＰｔに結合する含窒素芳香族ヘテロ環配位子、アシルオキシ配位子、アリールオキシ配位子であり、更に好ましくは炭素原子でＰｔに結合する芳香族炭化水素環配位子、炭素原子でＰｔに結合する芳香族ヘテロ環配位子、窒素原子でＰｔに結合する含窒素芳香族ヘテロ環配位子、アシルオキシ配位子である。 The group represented by Q 1 , Q 2 , Q 3 and Q 4 is preferably an aromatic hydrocarbon ring ligand bonded to Pt with a carbon atom, and an aromatic heterocyclic ligand bonded to Pt with a carbon atom. A nitrogen-containing aromatic heterocyclic ligand that binds to Pt with a nitrogen atom, an acyloxy ligand, an alkyloxy ligand, an aryloxy ligand, a heteroaryloxy ligand, a silyloxy ligand, and more Preferably, an aromatic hydrocarbon ring ligand bonded to Pt by a carbon atom, an aromatic heterocyclic ligand bonded to Pt by a carbon atom, a nitrogen-containing aromatic heterocyclic ligand bonded to Pt by a nitrogen atom , An acyloxy ligand, an aryloxy ligand, more preferably an aromatic hydrocarbon ring ligand bonded to Pt with a carbon atom, an aromatic heterocyclic ligand bonded to Pt with a carbon atom, a nitrogen atom Containing Pt Containing aromatic heterocyclic ligand, an acyloxy ligand.
　Ｌ１、Ｌ２及びＬ３は、単結合又は二価の連結基を表す。Ｌ１、Ｌ２及びＬ３で表される二価の連結基としては、アルキレン基（メチレン、エチレン、プロピレンなど）、アリーレン基（フェニレン、ナフタレンジイル）、ヘテロアリーレン基（ピリジンジイル、チオフェンジイルなど）、イミノ基（－ＮＲＬ－）（フェニルイミノ基など）、オキシ基（－Ｏ－）、チオ基（－Ｓ－）、ホスフィニデン基（－ＰＲＬ－）（フェニルホスフィニデン基など）、シリレン基（－ＳｉＲＬＲＬ’－）（ジメチルシリレン基、ジフェニルシリレン基など）、又はこれらを組み合わせたものが挙げられる。ここで、ＲＬ及びＲＬ’としてはアルキル基、アリール基等が挙げられる。これらの連結基は、更に置換基を有していてもよい。置換基としては前記置換基群Ａとして挙げたものが適宜適用できる。
　錯体の安定性及び発光量子収率の観点から、Ｌ１、Ｌ２及びＬ３として好ましくは単結合、アルキレン基、アリーレン基、ヘテロアリーレン基、イミノ基、オキシ基、チオ基、シリレン基であり、より好ましくは単結合、アルキレン基、アリーレン基、イミノ基であり、更に好ましくは単結合、アルキレン基、アリーレン基であり、更に好ましくは、単結合、メチレン基、フェニレン基であり、更に好ましくは単結合、ジ置換のメチレン基であり、更に好ましくは単結合、ジメチルメチレン基、ジエチルメチレン基、ジイソブチルメチレン基、ジベンジルメチレン基、エチルメチルメチレン基、メチルプロピルメチレン基、イソブチルメチルメチレン基、ジフェニルメチレン基、メチルフェニルメチレン基、シクロヘキサンジイル基、シクロペンタンジイル基、フルオレンジイル基、フルオロメチルメチレン基であり、特に好ましくは単結合、ジメチルメチレン基、ジフェニルメチレン基、シクロヘキサンジイル基である。 L 1 , L 2 and L 3 represent a single bond or a divalent linking group. Divalent linking groups represented by L 1 , L 2 and L 3 include alkylene groups (methylene, ethylene, propylene, etc.), arylene groups (phenylene, naphthalenediyl), heteroarylene groups (pyridinediyl, thiophenediyl, etc.) ), Imino group (—NR L —) (such as phenylimino group), oxy group (—O—), thio group (—S—), phosphinidene group (—PR L —) (such as phenylphosphinidene group), silylene (-SiR L R L '-) ( dimethylsilylene group, a diphenylsilylene group), or the like combinations thereof. Here, examples of R L and R L ′ include an alkyl group and an aryl group. These linking groups may further have a substituent. As the substituent, those exemplified as the substituent group A can be appropriately applied.
From the viewpoint of the stability of the complex and the emission quantum yield, L 1 , L 2 and L 3 are preferably a single bond, an alkylene group, an arylene group, a heteroarylene group, an imino group, an oxy group, a thio group or a silylene group. More preferably a single bond, an alkylene group, an arylene group or an imino group, still more preferably a single bond, an alkylene group or an arylene group, still more preferably a single bond, a methylene group or a phenylene group, still more preferably. Single bond, disubstituted methylene group, more preferably single bond, dimethylmethylene group, diethylmethylene group, diisobutylmethylene group, dibenzylmethylene group, ethylmethylmethylene group, methylpropylmethylene group, isobutylmethylmethylene group, diphenyl Methylene, methylphenylmethylene, cyclohexanediyl, cycl A lopentanediyl group, a fluorenediyl group, and a fluoromethylmethylene group, particularly preferably a single bond, a dimethylmethylene group, a diphenylmethylene group, and a cyclohexanediyl group.
　一般式（Ｃ－１）で表される白金錯体のうち、より好ましくは下記一般式（Ｃ－２）で表される白金錯体である。 Of the platinum complexes represented by the general formula (C-1), a platinum complex represented by the following general formula (C-2) is more preferable.
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
　一般式（Ｃ－２）中、Ｌ２１は単結合又は二価の連結基を表す。Ａ２１、Ａ２２はそれぞれ独立に炭素原子又は窒素原子を表す。Ｚ２１、Ｚ２２はそれぞれ独立に含窒素芳香族ヘテロ環を表す。Ｚ２３、Ｚ２４はそれぞれ独立にベンゼン環又は芳香族ヘテロ環を表す。 In general formula (C-2), L 21 represents a single bond or a divalent linking group. A 21 and A 22 each independently represent a carbon atom or a nitrogen atom. Z 21 and Z 22 each independently represent a nitrogen-containing aromatic heterocycle. Z 23 and Z 24 each independently represent a benzene ring or an aromatic heterocycle.
　一般式（Ｃ－２）について説明する。
　Ｌ２１は、前記一般式（Ｃ－１）中のＬ１と同義であり、また好ましい範囲も同様である。 The general formula (C-2) will be described.
L 21 has the same meaning as L 1 in formula (C-1), and the preferred range is also the same.
　Ａ２１、Ａ２２はそれぞれ独立に炭素原子又は窒素原子を表す。Ａ２１、Ａ２２の内、少なくとも一方は炭素原子であることが好ましく、Ａ２１、Ａ２２が共に炭素原子であることが、錯体の安定性の観点及び錯体の発光量子収率の観点から好ましい。 A 21 and A 22 each independently represent a carbon atom or a nitrogen atom. Of A 21, A 22, Preferably, at least one is a carbon atom, it A 21, A 22 are both carbon atoms are preferred from the standpoint of emission quantum yield stability aspects and complexes of the complex .
　Ｚ２１、Ｚ２２は、それぞれ独立に含窒素芳香族ヘテロ環を表す。Ｚ２１、Ｚ２２で表される含窒素芳香族ヘテロ環としては、ピリジン環、ピリミジン環、ピラジン環、トリアジン環、イミダゾール環、ピラゾール環、オキサゾール環、チアゾール環、トリアゾール環、オキサジアゾール環、チアジアゾール環などが挙げられる。錯体の安定性、発光波長制御及び発光量子収率の観点から、Ｚ２１、Ｚ２２で表される環として好ましくは、ピリジン環、ピラジン環、イミダゾール環、ピラゾール環であり、より好ましくはピリジン環、イミダゾール環、ピラゾール環であり、更に好ましくはピリジン環、ピラゾール環であり、特に好ましくはピリジン環である。 Z 21 and Z 22 each independently represent a nitrogen-containing aromatic heterocycle. Examples of the nitrogen-containing aromatic heterocycle represented by Z 21 and Z 22 include a pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, triazole ring, oxadiazole ring, Examples include thiadiazole rings. From the viewpoint of the stability of the complex, emission wavelength control and emission quantum yield, the ring represented by Z 21 and Z 22 is preferably a pyridine ring, a pyrazine ring, an imidazole ring or a pyrazole ring, more preferably a pyridine ring. , An imidazole ring and a pyrazole ring, more preferably a pyridine ring and a pyrazole ring, and particularly preferably a pyridine ring.
　前記Ｚ２１、Ｚ２２で表される含窒素芳香族ヘテロ環は置換基を有していてもよく、炭素原子上の置換基としては前記置換基群Ａが、窒素原子上の置換基としては前記置換基群Ｂが適用できる。炭素上の置換基として好ましくはアルキル基、ペルフルオロアルキル基、アリール基、芳香族へテロ環基、ジアルキルアミノ基、ジアリールアミノ基、アルコキシ基、シアノ基、ハロゲン原子である。置換基は発光波長や電位の制御のために適宜選択されるが、短波長化させる場合には電子供与性基、フッ素原子、芳香環基が好ましく、例えばアルキル基、ジアルキルアミノ基、アルコキシ基、フッ素原子、アリール基、芳香族ヘテロ環基などが選択される。また長波長化させる場合には電子求引性基が好ましく、例えばシアノ基、ペルフルオロアルキル基などが選択される。窒素原子上の置換基として好ましくは、アルキル基、アリール基、芳香族ヘテロ環基であり、錯体の安定性の観点からアルキル基、アリール基が好ましい。前記置換基同士は連結して縮合環を形成していてもよく、形成される環としては、ベンゼン環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、チオフェン環、フラン環などが挙げられる。 The nitrogen-containing aromatic heterocycle represented by Z 21 and Z 22 may have a substituent, and the substituent group A is a substituent on a carbon atom, and the substituent on a nitrogen atom is The substituent group B can be applied. The substituent on carbon is preferably an alkyl group, a perfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diarylamino group, an alkoxy group, a cyano group, or a halogen atom. The substituent is appropriately selected for controlling the emission wavelength and potential, but in the case of shortening the wavelength, an electron donating group, a fluorine atom, and an aromatic ring group are preferable. For example, an alkyl group, a dialkylamino group, an alkoxy group, A fluorine atom, an aryl group, an aromatic heterocyclic group and the like are selected. In the case of increasing the wavelength, an electron withdrawing group is preferable, and for example, a cyano group, a perfluoroalkyl group, or the like is selected. The substituent on the nitrogen atom is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, and an alkyl group or an aryl group is preferable from the viewpoint of the stability of the complex. The substituents may be linked to form a condensed ring, and the formed ring includes a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyrazole. Ring, thiophene ring, furan ring and the like.
　Ｚ２３、Ｚ２４は、それぞれ独立にベンゼン環又は芳香族ヘテロ環を表す。Ｚ２３、Ｚ２４で表される含窒素芳香族ヘテロ環としては、ピリジン環、ピリミジン環、ピラジン環、ピリダジン環、トリアジン環、イミダゾール環、ピラゾール環、オキサゾール環、チアゾール環、トリアゾール環、オキサジアゾール環、チアジアゾール環、チオフェン環、フラン環などが挙げられる。錯体の安定性、発光波長制御及び発光量子収率の観点からＺ２３、Ｚ２４で表される環として好ましくは、ベンゼン環、ピリジン環、ピラジン環、イミダゾール環、ピラゾール環、チオフェン環であり、より好ましくはベンゼン環、ピリジン環、ピラゾール環であり、更に好ましくはベンゼン環、ピリジン環である。 Z 23 and Z 24 each independently represent a benzene ring or an aromatic heterocycle. Examples of the nitrogen-containing aromatic heterocycle represented by Z 23 and Z 24 include a pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, triazole ring, oxadi Examples include an azole ring, a thiadiazole ring, a thiophene ring, and a furan ring. From the viewpoint of stability of the complex, emission wavelength control and emission quantum yield, the ring represented by Z 23 and Z 24 is preferably a benzene ring, a pyridine ring, a pyrazine ring, an imidazole ring, a pyrazole ring, or a thiophene ring, More preferred are a benzene ring, a pyridine ring and a pyrazole ring, and still more preferred are a benzene ring and a pyridine ring.
　前記Ｚ２３、Ｚ２４で表されるベンゼン環、含窒素芳香族ヘテロ環は置換基を有していてもよく、炭素原子上の置換基としては前記置換基群Ａが、窒素原子上の置換基としては前記置換基群Ｂが適用できる。炭素上の置換基として好ましくはアルキル基、ペルフルオロアルキル基、アリール基、芳香族へテロ環基、ジアルキルアミノ基、ジアリールアミノ基、アルコキシ基、シアノ基、ハロゲン原子である。置換基は発光波長や電位の制御のために適宜選択されるが、長波長化させる場合には電子供与性基、芳香環基が好ましく、例えばアルキル基、ジアルキルアミノ基、アルコキシ基、アリール基、芳香族ヘテロ環基などが選択される。また短波長化させる場合には電子求引性基が好ましく、例えばフッ素原子、シアノ基、ペルフルオロアルキル基などが選択される。窒素原子上の置換基として好ましくは、アルキル基、アリール基、芳香族ヘテロ環基であり、錯体の安定性の観点からアルキル基、アリール基が好ましい。前記置換基同士は連結して縮合環を形成していてもよく、形成される環としては、ベンゼン環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、チオフェン環、フラン環などが挙げられる。 The benzene ring and nitrogen-containing aromatic heterocycle represented by Z 23 and Z 24 may have a substituent. As the substituent on the carbon atom, the substituent group A is substituted on the nitrogen atom. The substituent group B can be applied as the group. The substituent on carbon is preferably an alkyl group, a perfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diarylamino group, an alkoxy group, a cyano group, or a halogen atom. The substituent is appropriately selected for controlling the emission wavelength and potential, but in the case of increasing the wavelength, an electron donating group and an aromatic ring group are preferable, for example, an alkyl group, a dialkylamino group, an alkoxy group, an aryl group, An aromatic heterocyclic group or the like is selected. In order to shorten the wavelength, an electron withdrawing group is preferable, and for example, a fluorine atom, a cyano group, a perfluoroalkyl group, and the like are selected. The substituent on the nitrogen atom is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, and an alkyl group or an aryl group is preferable from the viewpoint of the stability of the complex. The substituents may be linked to form a condensed ring, and the formed ring includes a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyrazole. Ring, thiophene ring, furan ring and the like.
　一般式（Ｃ－２）で表される白金錯体のうち、より好ましい態様の一つは下記一般式（Ｃ－３）で表される白金錯体である。 Of the platinum complexes represented by the general formula (C-2), one of more preferred embodiments is a platinum complex represented by the following general formula (C-3).
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
　一般式（Ｃ－３）中、Ａ３０１～Ａ３１３は、それぞれ独立に、Ｃ－Ｒ又は窒素原子を表す。Ｒは水素原子又は置換基を表す。Ｌ３１は単結合又は二価の連結基を表す。 In general formula (C-3), A 301 to A 313 each independently represent C—R or a nitrogen atom. R represents a hydrogen atom or a substituent. L 31 represents a single bond or a divalent linking group.
　一般式（Ｃ－３）について説明する。
　Ｌ３１は一般式（Ｃ－２）におけるＬ２１と同義であり、また好ましい範囲も同様である。
　Ａ３０１～Ａ３０６はそれぞれ独立にＣ－Ｒ又は窒素原子を表す。Ｒは水素原子又は置換基を表す。Ｒで表される置換基としては、前記置換基群Ａとして挙げたものが適用できる。Ａ３０１～Ａ３０６として好ましくはＣ－Ｒであり、Ｒ同士が互いに連結して環を形成していてもよい。Ａ３０１～Ａ３０６がＣ－Ｒである場合に、Ａ３０２、Ａ３０５のＲとして好ましくは水素原子、アルキル基、アリール基、アミノ基、アルコキシ基、アリールオキシ基、フッ素原子、シアノ基であり、より好ましくは水素原子、アミノ基、アルコキシ基、アリールオキシ基、フッ素原子であり、特に好ましく水素原子、フッ素原子であり、Ａ３０１、Ａ３０３、Ａ３０４、Ａ３０６のＲとして好ましくは水素原子、アルキル基、アリール基、アミノ基、アルコキシ基、アリールオキシ基、フッ素原子、シアノ基であり、より好ましくは水素原子、アミノ基、アルコキシ基、アリールオキシ基、フッ素原子であり、特に好ましく水素原子である。
　Ａ３０７、Ａ３０８、Ａ３０９及びＡ３１０は、それぞれ独立に、Ｃ－Ｒ又は窒素原子を表す。Ｒは水素原子又は置換基を表す。Ｒで表される置換基としては、前記置換基群Ａとして挙げたものが適用できる。Ａ３０７、Ａ３０８、Ａ３０９及びＡ３１０がＣ－Ｒである場合に、Ｒとして好ましくは水素原子、アルキル基、ペルフルオロアルキル基、アリール基、芳香族へテロ環基、ジアルキルアミノ基、ジアリールアミノ基、アルキルオキシ基、シアノ基、ハロゲン原子であり、より好ましくは、水素原子、アルキル基、ペルフルオロアルキル基、アリール基、ジアルキルアミノ基、シアノ基、フッ素原子、更に好ましくは、水素原子、アルキル基、トリフルオロメチル基、フッ素原子である。また可能な場合は置換基同士が連結して縮環構造を形成してもよい。発光波長を短波長側にシフトさせる場合、Ａ３０８が窒素原子であることが好ましい。 The general formula (C-3) will be described.
L 31 has the same meaning as L 21 in formula (C-2), and the preferred range is also the same.
A 301 to A 306 each independently represents C—R or a nitrogen atom. R represents a hydrogen atom or a substituent. As the substituent represented by R, those exemplified as the substituent group A can be applied. A 301 to A 306 are preferably C—R, and Rs may be connected to each other to form a ring. When A 301 to A 306 are CR , R in A 302 and A 305 is preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine atom, or a cyano group. More preferably a hydrogen atom, an amino group, an alkoxy group, an aryloxy group, or a fluorine atom, particularly preferably a hydrogen atom or a fluorine atom, and R as A 301 , A 303 , A 304 , or A 306 is preferably a hydrogen atom. , Alkyl group, aryl group, amino group, alkoxy group, aryloxy group, fluorine atom, cyano group, more preferably hydrogen atom, amino group, alkoxy group, aryloxy group, fluorine atom, particularly preferably hydrogen atom. It is.
A 307 , A 308 , A 309 and A 310 each independently represent C—R or a nitrogen atom. R represents a hydrogen atom or a substituent. As the substituent represented by R, those exemplified as the substituent group A can be applied. When A 307 , A 308 , A 309 and A 310 are C—R, R is preferably a hydrogen atom, alkyl group, perfluoroalkyl group, aryl group, aromatic heterocyclic group, dialkylamino group, diarylamino Group, alkyloxy group, cyano group, halogen atom, more preferably hydrogen atom, alkyl group, perfluoroalkyl group, aryl group, dialkylamino group, cyano group, fluorine atom, more preferably hydrogen atom, alkyl group. , A trifluoromethyl group and a fluorine atom. If possible, the substituents may be linked to form a condensed ring structure. When shifting the emission wavelength to the short wavelength side, A 308 is preferably a nitrogen atom.
　上記の如くＡ３０７～Ａ３１０を選択した場合、２つの炭素原子とＡ３０７、Ａ３０８、Ａ３０９及びＡ３１０から形成される６員環としては、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、トリアジン環が挙げられ、より好ましくは、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環であり、特に好ましくはピリジン環である。前記６員環が、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環（特に好ましくはピリジン環）であることにより、ベンゼン環と比較して、金属－炭素結合を形成する位置に存在する水素原子の酸性度が向上する為、より金属錯体を形成しやすくなり有利である。 When A 307 to A 310 are selected as described above, the 6-membered ring formed from two carbon atoms and A 307 , A 308 , A 309 and A 310 includes a pyridine ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring. And a triazine ring, more preferably a pyridine ring, a pyrazine ring, a pyrimidine ring and a pyridazine ring, and particularly preferably a pyridine ring. Since the 6-membered ring is a pyridine ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring (particularly preferably a pyridine ring), a hydrogen atom present at a position where a metal-carbon bond is formed as compared with a benzene ring. Since the acidity is improved, a metal complex is more easily formed, which is advantageous.
　Ａ３１１、Ａ３１２及びＡ３１３は、それぞれ独立に、Ｃ－Ｒ又は窒素原子を表す。Ｒは水素原子又は置換基を表す。Ｒで表される置換基としては、前記置換基群Ａとして挙げたものが適用できる。Ａ３１１、Ａ３１２及びＡ３１３がＣ－Ｒである場合に、Ｒとして好ましくは水素原子、アルキル基、ペルフルオロアルキル基、アリール基、芳香族へテロ環基、ジアルキルアミノ基、ジアリールアミノ基、アルキルオキシ基、シアノ基、ハロゲン原子であり、より好ましくは、水素原子、アルキル基、ペルフルオロアルキル基、アリール基、ジアルキルアミノ基、シアノ基、フッ素原子、更に好ましくは、水素原子、アルキル基、トリフルオロメチル基、フッ素原子である。また可能な場合は置換基同士が連結して、縮環構造を形成してもよい。
　Ａ３１１、Ａ３１２及びＡ３１３と１つの窒素原子及び１つの炭素原子とで形成される５員環としては、ピロール環、ピラゾール環、イミダゾール環、フラン環、チオフェン環等が挙げられ、より好ましくは、ピロール環、ピラゾール環、イミダゾール環であり、更に好ましくはピロール環、ピラゾール環である。前記５員環が、ピロール環、ピラゾール環、イミダゾール環（更に好ましくはピロール環、ピラゾール環）であることにより、金属錯体の安定性が向上するため、有利である。 A 311 , A 312 and A 313 each independently represent C—R or a nitrogen atom. R represents a hydrogen atom or a substituent. As the substituent represented by R, those exemplified as the substituent group A can be applied. When A 311 , A 312 and A 313 are C—R, R is preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diarylamino group, an alkyl An oxy group, a cyano group, and a halogen atom, more preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group, a dialkylamino group, a cyano group, and a fluorine atom, and more preferably a hydrogen atom, an alkyl group, and trifluoro A methyl group and a fluorine atom. If possible, the substituents may be linked to form a condensed ring structure.
Examples of the 5-membered ring formed by A 311 , A 312 and A 313 and one nitrogen atom and one carbon atom include a pyrrole ring, a pyrazole ring, an imidazole ring, a furan ring, and a thiophene ring, and more preferable. Is a pyrrole ring, a pyrazole ring or an imidazole ring, more preferably a pyrrole ring or a pyrazole ring. Since the 5-membered ring is a pyrrole ring, a pyrazole ring, or an imidazole ring (more preferably, a pyrrole ring or a pyrazole ring), it is advantageous because the stability of the metal complex is improved.
　一般式（Ｃ－２）で表される白金錯体のうち、より好ましい態様の一つは下記一般式（Ｃ－４）で表される白金錯体である。 Of the platinum complexes represented by the general formula (C-2), one of the more preferred embodiments is a platinum complex represented by the following general formula (C-4).
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
　一般式（Ｃ－４）中、Ａ４０１～Ａ４１４はそれぞれ独立にＣ－Ｒ又は窒素原子を表す。Ｒは水素原子又は置換基を表す。Ｌ４１は単結合又は二価の連結基を表す。 In general formula (C-4), A 401 to A 414 each independently represents C—R or a nitrogen atom. R represents a hydrogen atom or a substituent. L 41 represents a single bond or a divalent linking group.
　一般式（Ｃ－４）について説明する。
　Ａ４０１～Ａ４１４はそれぞれ独立にＣ－Ｒ又は窒素原子を表す。Ｒは水素原子又は置換基を表す。Ａ４０１～Ａ４０６及びＬ４１は、前記一般式（Ｃ－３）におけるＡ３０１～Ａ３０６及びＬ３１と同義であり、好ましい範囲も同様である。 The general formula (C-4) will be described.
A 401 to A 414 each independently represents C—R or a nitrogen atom. R represents a hydrogen atom or a substituent. A 401 to A 406 and L 41 have the same meanings as A 301 to A 306 and L 31 in formula (C-3), and preferred ranges thereof are also the same.
　Ａ４０７～Ａ４１４としては、Ａ４０７～Ａ４１０とＡ４１１～Ａ４１４のそれぞれにおいて、窒素原子の数は、０～２が好ましく、０～１がより好ましい。発光波長を短波長側にシフトさせる場合、Ａ４０８、Ａ４１２が窒素原子であることが好ましく、Ａ４０８とＡ４１２が共に窒素原子であることが更に好ましい。
　Ａ４０７～Ａ４１４がＣ－Ｒを表す場合に、Ａ４０８、Ａ４１２のＲとして好ましくは水素原子、アルキル基、ペルフルオロアルキル基、アリール基、アミノ基、アルコキシ基、アリールオキシ基、フッ素原子、シアノ基であり、より好ましくは水素原子、ペルフルオロアルキル基、アルキル基、アリール基、フッ素原子、シアノ基であり、特に好ましくは、水素原子、ペルフルオロアルキル基、シアノ基である。Ａ４０７、Ａ４０９、Ａ４１１、Ａ４１３の表すＲとして好ましくは水素原子、アルキル基、ペルフルオロアルキル基、アリール基、アミノ基、アルコキシ基、アリールオキシ基、フッ素原子、シアノ基であり、より好ましくは水素原子、ペルフルオロアルキル基、フッ素原子、シアノ基であり、特に好ましく水素原子、フッ素原子である。Ａ４１０、Ａ４１４の表すＲとして好ましくは水素原子、フッ素原子であり、より好ましくは水素原子である。Ａ４０７～Ａ４０９、Ａ４１１～Ａ４１３のいずれかがＣ－Ｒを表す場合に、Ｒ同士が互いに連結して環を形成していてもよい。 As A 407 to A 414 , in each of A 407 to A 410 and A 411 to A 414 , the number of nitrogen atoms is preferably 0 to 2, and more preferably 0 to 1. In the case of shifting the emission wavelength to the short wavelength side, A 408 and A 412 are preferably nitrogen atoms, and both A 408 and A 412 are more preferably nitrogen atoms.
In the case where A 407 to A 414 represent C—R, R in A 408 and A 412 is preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine atom, A cyano group, more preferably a hydrogen atom, a perfluoroalkyl group, an alkyl group, an aryl group, a fluorine atom and a cyano group, and particularly preferably a hydrogen atom, a perfluoroalkyl group and a cyano group. R represented by A 407 , A 409 , A 411 and A 413 is preferably a hydrogen atom, alkyl group, perfluoroalkyl group, aryl group, amino group, alkoxy group, aryloxy group, fluorine atom or cyano group, more preferably Is a hydrogen atom, a perfluoroalkyl group, a fluorine atom or a cyano group, particularly preferably a hydrogen atom or a fluorine atom. R represented by A 410 and A 414 is preferably a hydrogen atom or a fluorine atom, and more preferably a hydrogen atom. When any of A 407 to A 409 and A 411 to A 413 represents CR, Rs may be connected to each other to form a ring.
　一般式（Ｃ－１）で表される白金錯体のうち、より好ましい別の態様は下記一般式（Ｃ－５）で表される白金錯体である。 Among the platinum complexes represented by the general formula (C-1), another more preferable embodiment is a platinum complex represented by the following general formula (C-5).
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
　一般式（Ｃ－５）中、Ｌ５１は単結合又は二価の連結基を表す。Ａ５１はそれぞれ独立に炭素原子又は窒素原子を表す。Ｚ５１、Ｚ５２はそれぞれ独立に含窒素芳香族ヘテロ環を表す。Ｚ５３はそれぞれ独立にベンゼン環又は芳香族ヘテロ環を表す。ＹはＰｔに結合するアニオン性の非環状配位子である。 In the general formula (C-5), L 51 represents a single bond or a divalent linking group. A 51 each independently represents a carbon atom or a nitrogen atom. Z 51 and Z 52 each independently represent a nitrogen-containing aromatic heterocycle. Z 53 each independently represents a benzene ring or an aromatic heterocycle. Y is an anionic acyclic ligand that binds to Pt.
　一般式（Ｃ－５）について説明する。
　Ｌ５１は、前記一般式（Ｃ－１）中のＬ１と同義であり、また好ましい範囲も同様である。 The general formula (C-5) will be described.
L 51 has the same meaning as L 1 in formula (C-1), and the preferred range is also the same.
　Ａ５１は炭素原子又は窒素原子を表す。錯体の安定性の観点及び錯体の発光量子収率の観点からＡ５１は炭素原子であることが好ましい。 A 51 represents a carbon atom or a nitrogen atom. In view of the stability of the complex and the light emission quantum yield of the complex, A 51 is preferably a carbon atom.
　Ｚ５１、Ｚ５２は、それぞれ前記一般式（Ｃ－２）におけるＺ２１、Ｚ２２と同義であり、また好ましい範囲も同様である。Ｚ５３は、前記一般式（Ｃ－２）におけるＺ２３と同義であり、また好ましい範囲も同様である。 Z 51 and Z 52 are synonymous with Z 21 and Z 22 in the general formula (C-2), respectively, and preferred ranges thereof are also the same. Z 53 has the same meaning as Z 23 in formula (C-2), and the preferred range is also the same.
　ＹはＰｔに結合するアニオン性の非環状配位子である。非環状配位子とはＰｔに結合する原子が配位子の状態で環を形成していないものである。Ｙ中のＰｔに結合する原子としては、炭素原子、窒素原子、酸素原子、硫黄原子が好ましく、窒素原子、酸素原子がより好ましく、酸素原子が最も好ましい。炭素原子でＰｔに結合するＹとしてはビニル配位子が挙げられる。窒素原子でＰｔに結合するＹとしてはアミノ配位子、イミノ配位子が挙げられる。酸素原子でＰｔに結合するＹとしては、アルコキシ配位子、アリールオキシ配位子、ヘテロアリールオキシ配位子、アシルオキシ配位子、シリルオキシ配位子、カルボキシル配位子、リン酸配位子、スルホン酸配位子などが挙げられる。硫黄原子でＰｔに結合するＹとしては、アルキルメルカプト配位子、アリールメルカプト配位子、ヘテロアリールメルカプト配位子、チオカルボン酸配位子などが挙げられる。
　Ｙで表される配位子は、置換基を有していてもよく、置換基としては前記置換基群Ａとして挙げたものが適宜適用できる。また置換基同士が連結していてもよい。 Y is an anionic acyclic ligand that binds to Pt. An acyclic ligand is one in which atoms bonded to Pt do not form a ring in the form of a ligand. As an atom couple | bonded with Pt in Y, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom are preferable, a nitrogen atom and an oxygen atom are more preferable, and an oxygen atom is the most preferable. A vinyl ligand is mentioned as Y couple | bonded with Pt by a carbon atom. Examples of Y bonded to Pt with a nitrogen atom include an amino ligand and an imino ligand. Examples of Y bonded to Pt with an oxygen atom include an alkoxy ligand, an aryloxy ligand, a heteroaryloxy ligand, an acyloxy ligand, a silyloxy ligand, a carboxyl ligand, a phosphate ligand, Examples thereof include sulfonic acid ligands. Examples of Y bonded to Pt with a sulfur atom include alkyl mercapto ligands, aryl mercapto ligands, heteroaryl mercapto ligands, and thiocarboxylic acid ligands.
The ligand represented by Y may have a substituent, and those exemplified as the substituent group A can be appropriately applied as the substituent. Moreover, substituents may be connected to each other.
　Ｙで表される配位子として好ましくは酸素原子でＰｔに結合する配位子であり、より好ましくはアシルオキシ配位子、アルキルオキシ配位子、アリールオキシ配位子、ヘテロアリールオキシ配位子、シリルオキシ配位子であり、更に好ましくはアシルオキシ配位子である。 The ligand represented by Y is preferably a ligand bonded to Pt with an oxygen atom, more preferably an acyloxy ligand, an alkyloxy ligand, an aryloxy ligand, a heteroaryloxy ligand. , A silyloxy ligand, and more preferably an acyloxy ligand.
　一般式（Ｃ－５）で表される白金錯体のうち、より好ましい態様の一つは下記一般式（Ｃ－６）で表される白金錯体である。 Of the platinum complexes represented by the general formula (C-5), one of more preferred embodiments is a platinum complex represented by the following general formula (C-6).
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
　一般式（Ｃ－６）中、Ａ６０１～Ａ６１０は、それぞれ独立に、Ｃ－Ｒ又は窒素原子を表す。Ｒは水素原子又は置換基を表す。Ｌ６１は単結合又は二価の連結基を表す。ＹはＰｔに結合するアニオン性の非環状配位子である。 In general formula (C-6), A 601 to A 610 each independently represents C—R or a nitrogen atom. R represents a hydrogen atom or a substituent. L 61 represents a single bond or a divalent linking group. Y is an anionic acyclic ligand that binds to Pt.
　一般式（Ｃ－６）について説明する。
　Ｌ６１は、前記一般式（Ｃ－５）中のＬ５１と同義であり、また好ましい範囲も同様である。Ａ６０１～Ａ６１０は一般式（Ｃ－３）におけるＡ３０１～Ａ３１０と同義であり、また好ましい範囲も同様である。Ｙは一般式（Ｃ－５）におけるそれと同義であり、また好ましい範囲も同様である。 The general formula (C-6) will be described.
L 61 has the same meaning as L 51 in formula (C-5), and the preferred range is also the same. A 601 to A 610 have the same meanings as A 301 to A 310 in formula (C-3), and preferred ranges are also the same. Y has the same meaning as that in formula (C-5), and the preferred range is also the same.
　一般式（Ｃ－１）で表される白金錯体として具体的には、特開２００５－３１０７３３号公報の段落番号［０１４３］～［０１５２］、［０１５７］～［０１５８］、［０１６２］～［０１６８］に記載の化合物、特開２００６－２５６９９９号公報の段落番号［００６５］～［００８３］に記載の化合物、特開２００６－９３５４２号公報の段落番号［００６５］～［００９０］に記載の化合物、特開２００７－７３８９１号公報の段落番号［００６３］～［００７１］に記載の化合物、特開２００７－３２４３０９号公報の段落番号［００７９］～［００８３］に記載の化合物、特開２００６－９３５４２号公報の段落番号［００６５］～［００９０］に記載の化合物、特開２００７－９６２５５号公報の段落番号［００５５］～［００７１］に記載の化合物、特開２００６－３１３７９６号公報の［００４３］～［００４６］が挙げられる。より具体的には、以下に例示する白金錯体が挙げられるが、本発明はこれらに限定されるものではない。 Specific examples of the platinum complex represented by the general formula (C-1) include paragraph numbers [0143] to [0152], [0157] to [0158], [0162] to [0162] to [0162] of [2005-310733]. 0168], compounds described in JP-A-2006-256999, paragraphs [0065] to [0083], compounds described in JP-A-2006-93542, paragraphs [0065]-[0090] , Compounds described in paragraph numbers [0063] to [0071] of JP-A No. 2007-73891, compounds described in paragraph numbers [0079] to [0083] of JP-A No. 2007-324309, and JP-A 2006-93542 Compounds described in paragraph Nos. [0065] to [0090] of JP, No. 2007-96255, paragraph Nos. [0055] to [0] of JP 2007-96255 A A compound according to 71] include [0043] to [0046] of JP 2006-313796. More specifically, although the platinum complex illustrated below is mentioned, this invention is not limited to these.
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
　一般式（Ｃ－１）で表される白金錯体化合物は、例えば、Ｊｏｕｒｎａｌ　ｏｆ　Ｏｒｇａｎｉｃ　Ｃｈｅｍｉｓｔｒｙ　５３，７８６，（１９８８）、Ｇ．Ｒ．　Ｎｅｗｋｏｍｅ　ｅｔ　ａｌ．）の、７８９頁、左段５３行～右段７行に記載の方法、７９０頁、左段１８行～３８行に記載の方法、７９０頁、右段１９行～３０行に記載の方法及びその組み合わせ、Ｃｈｅｍｉｓｃｈｅ　Ｂｅｒｉｃｈｔｅ　１１３，　２７４９（１９８０）、Ｈ．Ｌｅｘｙほか）の、２７５２頁、２６行～３５行に記載の方法等、種々の手法で合成できる。
　例えば、配位子、又はその解離体と金属化合物を溶媒（例えば、ハロゲン系溶媒、アルコール系溶媒、エーテル系溶媒、エステル系溶媒、ケトン系溶媒、ニトリル系溶媒、アミド系溶媒、スルホン系溶媒、スルホキサイド系溶媒、水などが挙げられる）の存在下、若しくは、溶媒非存在下、塩基の存在下（無機、有機の種々の塩基、例えば、ナトリウムメトキシド、ｔ－ブトキシカリウム、トリエチルアミン、炭酸カリウムなどが挙げられる）、若しくは、塩基非存在下、室温以下、若しくは加熱し（通常の加熱以外にもマイクロウェーブで加熱する手法も有効である）得ることができる。　 Examples of the platinum complex compound represented by the general formula (C-1) include Journal of Organic Chemistry 53,786, (1988), G.S. R. Newkome et al. ), Page 789, method described in left column 53 to right column 7, line 790, method described in left column 18 to 38, method 790, method described in right column 19 to 30 and The combination, Chemische Berichte 113, 2749 (1980), H.C. Lexy et al.), Page 2752, lines 26 to 35, and the like.
For example, a ligand or a dissociated product thereof and a metal compound are mixed with a solvent (for example, a halogen solvent, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, a nitrile solvent, an amide solvent, a sulfone solvent, In the presence of a sulfoxide solvent, water, etc., or in the absence of a solvent, in the presence of a base (inorganic or organic various bases such as sodium methoxide, t-butoxypotassium, triethylamine, potassium carbonate, etc.) Or in the absence of a base, at room temperature or below, or by heating (in addition to normal heating, a method of heating with a microwave is also effective).
　本発明の発光層における一般式（Ｃ－１）で表される化合物の含有量は発光層中１～３０質量％であることが好ましく、３～２５質量％であることがより好ましく、５～２０質量％であることが更に好ましい。 The content of the compound represented by formula (C-1) in the light emitting layer of the present invention is preferably 1 to 30% by mass, more preferably 3 to 25% by mass in the light emitting layer. More preferably, it is 20 mass%.
（ホスト材料）
　ホスト材料とは、発光層において主に電荷の注入、輸送を担う化合物であり、また、それ自体は実質的に発光しない化合物のことである。ここで「実質的に発光しない」とは、該実質的に発光しない化合物からの発光量が好ましくは素子全体での全発光量の５％以下であり、より好ましくは３％以下であり、更に好ましくは１％以下であることを言う。
　ホスト材料としては、本発明の一般式（１）～（３）のいずれかで表される化合物を用いることができる。 (Host material)
The host material is a compound mainly responsible for charge injection and transport in the light emitting layer, and itself is a compound that does not substantially emit light. Here, “substantially does not emit light” means that the amount of light emitted from the compound that does not substantially emit light is preferably 5% or less, more preferably 3% or less of the total amount of light emitted from the entire device. Preferably it says 1% or less.
As the host material, a compound represented by any one of the general formulas (1) to (3) of the present invention can be used.
　その他の本発明に用いることのできるホスト材料としては、例えば、以下の化合物を挙げることができる。
　ピロール、インドール、カルバゾール、アザインドール、アザカルバゾール、トリアゾール、オキサゾール、オキサジアゾール、ピラゾール、イミダゾール、チオフェン、ポリアリールアルカン、ピラゾリン、ピラゾロン、フェニレンジアミン、アリールアミン、アミノ置換カルコン、スチリルアントラセン、フルオレノン、ヒドラゾン、スチルベン、シラザン、芳香族第三級アミン化合物、スチリルアミン化合物、ポルフィリン系化合物、ポリシラン系化合物、ポリ（Ｎ－ビニルカルバゾール）、アニリン系共重合体、チオフェンオリゴマー、ポリチオフェン等の導電性高分子オリゴマー、有機シラン、カーボン膜、ピリジン、ピリミジン、トリアジン、イミダゾール、ピラゾール、トリアゾ－ル、オキサゾ－ル、オキサジアゾ－ル、フルオレノン、アントラキノジメタン、アントロン、ジフェニルキノン、チオピランジオキシド、カルボジイミド、フルオレニリデンメタン、ジスチリルピラジン、フッ素置換芳香族化合物、ナフタレン、ペリレン等の複素環テトラカルボン酸無水物、フタロシアニン、８－キノリノ－ル誘導体の金属錯体やメタルフタロシアニン、ベンゾオキサゾ－ルやベンゾチアゾ－ルを配位子とする金属錯体に代表される各種金属錯体及びそれらの誘導体（置換基や縮環を有していてもよい）等を挙げることができる。 Examples of other host materials that can be used in the present invention include the following compounds.
Pyrrole, indole, carbazole, azaindole, azacarbazole, triazole, oxazole, oxadiazole, pyrazole, imidazole, thiophene, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone, hydrazone , Stilbene, silazane, aromatic tertiary amine compounds, styrylamine compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole), aniline copolymers, thiophene oligomers, polythiophene and other conductive polymer oligomers , Organic silane, carbon film, pyridine, pyrimidine, triazine, imidazole, pyrazole, triazole, oxazole, oxadiazol, full Lenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyrandioxide, carbodiimide, fluorenylidenemethane, distyrylpyrazine, fluorine-substituted aromatic compounds, heterocyclic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine, 8 -Various metal complexes represented by metal complexes of quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles, and their derivatives (even if they have substituents or condensed rings) Good).
　本発明において、併用することができるホスト材料としては、正孔輸送性ホスト材料であっても、電子輸送性ホスト材料であってもよいが、正孔輸送性ホスト材料を用いることができる。
　本発明において、前記発光層が、ホスト材料を含むことが好ましい。前記ホスト材料は下記一般式（４－１）又は（４－２）で表される化合物であることが好ましい。
　本発明においては、発光層に一般式（４－１）又は（４－２）で表される化合物の少なくとも１つ以上を含むことがより好ましい。 In the present invention, the host material that can be used in combination may be a hole transporting host material or an electron transporting host material, but a hole transporting host material can be used.
In the present invention, the light emitting layer preferably contains a host material. The host material is preferably a compound represented by the following general formula (4-1) or (4-2).
In the present invention, it is more preferable that the light emitting layer contains at least one compound represented by the general formula (4-1) or (4-2).
　本発明において、一般式（４－１）又は（４－２）で表される化合物が発光層に含有される場合、一般式（４－１）又は（４－２）で表される化合物は発光層中に３０～１００質量％含まれることが好ましく、４０～１００質量％含まれることがより好ましく、５０～１００質量％含まれることが特に好ましい。また、一般式（４－１）又は（４－２）で表される化合物を、複数の有機層に用いる場合はそれぞれの層において、上記の範囲で含有することが好ましい。 In the present invention, when the compound represented by the general formula (4-1) or (4-2) is contained in the light emitting layer, the compound represented by the general formula (4-1) or (4-2) is The light emitting layer preferably contains 30 to 100% by mass, more preferably 40 to 100% by mass, and particularly preferably 50 to 100% by mass. In addition, when the compound represented by the general formula (4-1) or (4-2) is used in a plurality of organic layers, it is preferable that each layer contains the above-mentioned range.
　一般式（４－１）又は（４－２）で表される化合物は、いずれかの有機層に、一種類のみを含有していてもよく、複数の一般式（４－１）又は（４－２）で表される化合物を任意の割合で組み合わせて含有していてもよい。 The compound represented by the general formula (4-1) or (4-2) may contain only one kind in any organic layer, and a plurality of general formulas (4-1) or (4) The compound represented by -2) may be contained in combination at any ratio.
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
　（一般式（４－１）及び（４－２）中、ｄ、ｅは０～３の整数を表し、少なくとも一方は１以上である。ｆは１～４の整数を表す。Ｒ’８はそれぞれ独立に置換基を表し、ｄ、ｅ、ｆが２以上である場合Ｒ’８は互いに異なっていても同じでも良い。また、Ｒ’８の少なくとも１つは下記一般式（５）で表されるカルバゾール基を表す。） (In the general formulas (4-1) and (4-2), d and e each represent an integer of 0 to 3, at least one of which is 1 or more, f represents an integer of 1 to 4. R ′ 8 is Each independently represents a substituent, and when d, e and f are 2 or more, R ′ 8 may be different or the same, and at least one of R ′ 8 is represented by the following general formula (5). Represents a carbazole group.)
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
（一般式（５）中、Ｒ’９はそれぞれ独立に置換基を表す。ｇは０～８の整数を表す。） (In general formula (5), R ′ 9 each independently represents a substituent. G represents an integer of 0 to 8.)
　Ｒ’８はそれぞれ独立に置換基を表し、具体的にはハロゲン原子、アルコキシ基、シアノ基、ニトロ基、アルキル基、アリール基、ヘテロ環基、又は一般式（５）で表される置換基である。Ｒ’８が一般式（５）を表さない場合、好ましくは炭素数１０以下のアルキル基、炭素数１０以下の置換又は無置換のアリール基であり、更に好ましくは炭素数６以下のアルキル基である。 R ′ 8 independently represents a substituent, specifically, a halogen atom, an alkoxy group, a cyano group, a nitro group, an alkyl group, an aryl group, a heterocyclic group, or a substituent represented by the general formula (5) It is. When R ′ 8 does not represent the general formula (5), it is preferably an alkyl group having 10 or less carbon atoms, a substituted or unsubstituted aryl group having 10 or less carbon atoms, and more preferably an alkyl group having 6 or less carbon atoms. It is.
　Ｒ’９はそれぞれ独立に置換基を表し、具体的にはハロゲン原子、アルコキシ基、シアノ基、ニトロ基、アルキル基、アリール基、ヘテロ環基であり、好ましくは炭素数１０以下のアルキル基、炭素数１０以下の置換又は無置換のアリール基であり、更に好ましくは炭素数６以下のアルキル基である。
　ｇは０～８の整数を表し、電荷輸送を担うカルバゾール骨格を遮蔽しすぎない観点から０～４が好ましい。また、合成容易さの観点から、カルバゾールが置換基を有する場合、窒素原子に対し、対称になるように置換基を持つものが好ましい。 R ′ 9 each independently represents a substituent, specifically a halogen atom, an alkoxy group, a cyano group, a nitro group, an alkyl group, an aryl group, or a heterocyclic group, preferably an alkyl group having 10 or less carbon atoms, A substituted or unsubstituted aryl group having 10 or less carbon atoms, more preferably an alkyl group having 6 or less carbon atoms.
g represents an integer of 0 to 8 and is preferably 0 to 4 from the viewpoint of not shielding too much the carbazole skeleton responsible for charge transport. From the viewpoint of ease of synthesis, when carbazole has a substituent, those having a substituent so as to be symmetric with respect to the nitrogen atom are preferable.
　一般式（４－１）において、電荷輸送能を保持する観点で、ｄとｅの和は２以上であることが好ましい。また、他方のベンゼン環に対しＲ’８がメタで置換することが好ましい。その理由として、オルト置換では隣り合う置換基の立体障害が大きいため結合が開裂しやすく、耐久性が低くなる。また、パラ置換では分子形状が剛直な棒状へと近づき、結晶化しやすくなるため高温条件での素子劣化が起こりやすくなる。具体的には以下の構造で表される化合物であることが好ましい。 In general formula (4-1), the sum of d and e is preferably 2 or more from the viewpoint of maintaining the charge transport ability. Further, R ′ 8 is preferably substituted with meta for the other benzene ring. The reason for this is that in ortho substitution, the steric hindrance between adjacent substituents is large, so that the bond is easily cleaved, and the durability is lowered. In addition, in para substitution, the molecular shape approaches a rigid rod shape and is easily crystallized, so that element degradation is likely to occur under high temperature conditions. Specifically, a compound represented by the following structure is preferable.
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
　一般式（４－２）において、電荷輸送能を保持する観点で、ｆは２以上であることが好ましい。ｆが２又は３の場合、同様の観点からＲ’８が互いにメタで置換することが好ましい。具体的には以下の構造で表される化合物であることが好ましい。 In the general formula (4-2), f is preferably 2 or more from the viewpoint of maintaining the charge transport ability. When f is 2 or 3, it is preferable that R ′ 8 is substituted with meta from the same viewpoint. Specifically, a compound represented by the following structure is preferable.
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
　一般式（４－１）及び（４－２）が水素原子を有する場合、水素の同位体（重水素原子等）も含む。この場合化合物中の全ての水素原子が水素同位体に置き換わっていてもよく、また一部が水素同位体を含む化合物である混合物でもよい。好ましくは一般式（５）におけるＲ’９が重水素によって置換されたものであり、特に好ましくは以下の構造が挙げられる。 When the general formulas (4-1) and (4-2) have a hydrogen atom, an isotope of hydrogen (such as a deuterium atom) is also included. In this case, all hydrogen atoms in the compound may be replaced with hydrogen isotopes, or a mixture in which a part is a compound containing hydrogen isotopes may be used. Preferably, R ′ 9 in the general formula (5) is substituted with deuterium, and the following structures are particularly preferable.
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
　更に置換基を構成する原子は、その同位体も含んでいることを表す。 Furthermore, the atoms constituting the substituents also include their isotopes.
　一般式（４－１）及び（４－２）で表される化合物は、種々の公知の合成法を組み合わせて合成することが可能である。最も一般的には、カルバゾール化合物に関してはアリールヒドラジンとシクロヘキサン誘導体との縮合体のアザーコープ転位反応の後、脱水素芳香族化による合成（Ｌ．Ｆ．Ｔｉｅｚｅ，Ｔｈ．Ｅｉｃｈｅｒ著、高野、小笠原訳、精密有機合成、３３９頁（南江堂刊））が挙げられる。また、得られたカルバゾール化合物とハロゲン化アリール化合物のパラジウム触媒を用いるカップリング反応に関してはテトラヘドロン・レターズ３９巻６１７頁（１９９８年）、同３９巻２３６７頁（１９９８年）及び同４０巻６３９３頁（１９９９年）等に記載の方法が挙げられる。反応温度、反応時間については特に限定されることはなく、前記文献に記載の条件が適用できる。また、ｍＣＰなどのいくつかの化合物は市販されているものを好適に用いることができる。 The compounds represented by the general formulas (4-1) and (4-2) can be synthesized by combining various known synthesis methods. Most commonly, carbazole compounds are synthesized by dehydroaromatization after the Athercorp rearrangement reaction of a condensate of an aryl hydrazine and a cyclohexane derivative (LF Tieze, by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo). Regarding the coupling reaction of the obtained carbazole compound and halogenated aryl compound using a palladium catalyst, Tetrahedron Letters 39: 617 (1998), 39: 2367 (1998) and 40: 6393 (1999) and the like. The reaction temperature and reaction time are not particularly limited, and the conditions described in the above literature can be applied. Some compounds such as mCP that are commercially available can be suitably used.
　本発明において、一般式（４－１）及び（４－２）で表される化合物は、真空蒸着プロセスで薄層を形成することが好ましいが、溶液塗布などのウェットプロセスも好適に用いることが出来る。化合物の分子量は、蒸着適性や溶解性の観点から２０００以下であることが好ましく、１２００以下であることがより好ましく、８００以下であることが特に好ましい。また蒸着適性の観点では、分子量が小さすぎると蒸気圧が小さくなり、気相から固相への変化がおきず、有機層を形成することが困難となるので、２５０以上が好ましく、３００以上が特に好ましい。 In the present invention, the compounds represented by the general formulas (4-1) and (4-2) preferably form a thin layer by a vacuum deposition process, but a wet process such as solution coating is also preferably used. I can do it. The molecular weight of the compound is preferably 2000 or less, more preferably 1200 or less, and particularly preferably 800 or less from the viewpoints of deposition suitability and solubility. Also, from the viewpoint of vapor deposition suitability, if the molecular weight is too small, the vapor pressure becomes small, the change from the gas phase to the solid phase does not occur, and it is difficult to form an organic layer. Particularly preferred.
　一般式（４－１）及び（４－２）は、以下に示す構造若しくはその水素原子が１つ以上重水素原子で置換された化合物であることが好ましい。以下に示す構造中のＲ’９は、前記一般式（５）におけるＲ’９と同義である。 The general formulas (4-1) and (4-2) are preferably compounds represented by the following structures or compounds in which one or more hydrogen atoms are substituted with deuterium atoms. R in the structure shown below '9, R in the formula (5)' is synonymous with 9.
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
　以下に、本発明における一般式（４－１）及び（４－２）で表される化合物の具体例を例示するが、本発明はこれらに限定されるものではない。 Specific examples of the compounds represented by the general formulas (4-1) and (4-2) in the present invention are illustrated below, but the present invention is not limited to these.
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
　発光層において、前記ホスト材料の三重項最低励起エネルギー（Ｔ１エネルギー）が、前記燐光発光材料のＴ１エネルギーより高いことが色純度、発光効率、駆動耐久性の点で好ましい。ホスト材料のＴ１が燐光発光材料のＴ１より０．１ｅＶ以上大きいことが好ましく、０．２ｅＶ以上大きいことがより好ましく、０．３ｅＶ以上大きいことが更に好ましい。
　ホスト材料のＴ１が燐光発光材料のＴ１より小さいと発光を消光してしまうためホスト材料には燐光発光材料より大きなＴ１が求められる。また、ホスト材料のＴ１が燐光発光材料より大きい場合でも、両者のＴ１差が小さい場合には一部、燐光発光材料からホスト材料への逆エネルギー移動が起こるため、効率低下や耐久性低下の原因となる。従って、Ｔ１が十分に大きく、化学的安定性及びキャリア注入・輸送性の高いホスト材料が求められている。 In the light emitting layer, the triplet lowest excitation energy (T 1 energy) of the host material is preferably higher than the T 1 energy of the phosphorescent light emitting material in terms of color purity, light emission efficiency, and driving durability. It is preferable T 1 is greater 0.1eV higher than the T 1 of the phosphorescent material of the host material, more preferably at least 0.2eV higher, and further preferably more than 0.3eV large.
T 1 of the host material is a large T 1 is obtained from the phosphorescent material to the host material for thereby quench T 1 is less than the light emission of the phosphorescent material. Even if the T 1 of the host material is larger than the phosphorescent light emitting material, if the difference in T 1 between the two is small, the reverse energy transfer from the phosphorescent light emitting material to the host material occurs in part, resulting in a decrease in efficiency and durability. Cause. Therefore, there is a demand for a host material having a sufficiently large T 1 and high chemical stability and carrier injection / transport properties.
　また、本発明におけるホスト化合物の含有量は、特に限定されるものではないが、発光効率、駆動電圧の観点から、発光層を形成する全化合物質量に対して１５質量％以上９５質量％以下であることが好ましい。発光層に、一般式（１）～（３）のいずれかで表される化合物を含む複数種類のホスト化合物を含む場合、一般式（１）～（３）のいずれかで表される化合物は全ホスト化合物中５０質量％以上９９質量％以下であることが好ましい。 Further, the content of the host compound in the present invention is not particularly limited, but from the viewpoint of light emission efficiency and driving voltage, it is 15% by mass to 95% by mass with respect to the total compound mass forming the light emitting layer. Preferably there is. When the light emitting layer contains a plurality of types of host compounds including the compound represented by any one of the general formulas (1) to (3), the compound represented by any one of the general formulas (1) to (3) is It is preferable that it is 50 to 99 mass% in all the host compounds.
〔一般式（Ｍ－１）で表される化合物〕
　本発明の有機電界発光素子は、前記一対の電極が陽極を含み、前記発光層と該陽極との間に少なくとも一層の有機層を含むことが好ましく、該有機層に少なくとも一種の下記一般式（Ｍ－１）で表される化合物を含有することが好ましい。 [Compound represented by formula (M-1)]
In the organic electroluminescent element of the present invention, it is preferable that the pair of electrodes include an anode, and at least one organic layer is included between the light emitting layer and the anode, and at least one of the following general formulas ( It is preferable to contain a compound represented by M-1).
　一般式（Ｍ－１）で表される化合物は発光層と陽極の間の発光層に隣接する有機層に含有されることがより好ましいが、その用途が限定されることはなく、有機層内のいずれの層に更に含有されてもよい。本発明にかかる一般式（Ｍ－１）で表される化合物の導入層としては、発光層、正孔注入層、正孔輸送層、電子輸送層、電子注入層、励起子ブロック層、電荷ブロック層のいずれか、若しくは複数に含有することができる。
　一般式（Ｍ－１）で表される化合物が含有される、発光層と陽極の間の発光層に隣接する有機層は正孔輸送層であることがより好ましい。 The compound represented by the general formula (M-1) is more preferably contained in an organic layer adjacent to the light emitting layer between the light emitting layer and the anode, but its use is not limited, and It may be further contained in any of these layers. As the introduction layer of the compound represented by the general formula (M-1) according to the present invention, a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an exciton block layer, a charge block It can be contained in any or a plurality of layers.
The organic layer adjacent to the light emitting layer between the light emitting layer and the anode and containing the compound represented by formula (M-1) is more preferably a hole transport layer.
Figure JPOXMLDOC01-appb-C000067
Figure JPOXMLDOC01-appb-C000067
　一般式（Ｍ－１）中、Ａｒ１及びＡｒ２はそれぞれ独立してアルキル、アリール、ヘテロアリール、アリールアミノ、アルキルアミノ、モルホリノ、チオモルホリノ、Ｎ、Ｏ、及びＳから選択される１以上のヘテロ原子を含有する５若しくは６員へテロシクロアルキル又はシクロアルキルを表し、更に置換基Ｚを有していてもよい。またＡｒ１及びＡｒ２は、単結合、アルキレン、若しくはアルケニレン（縮合環の有無を問わない）により互いに結合して、縮合５～９員環を形成してもよい。
　Ａｒ３はアルキル、アリール、ヘテロアリール、アリールアミノを表し、更に置換基Ｚを有していてもよい。
　Ｚはそれぞれ独立に、ハロゲン原子、－Ｒ”、－ＯＲ”、－Ｎ（Ｒ”）２、－ＳＲ”、－Ｃ（Ｏ）Ｒ”、－Ｃ（Ｏ）ＯＲ”、－Ｃ（Ｏ）Ｎ（Ｒ”）２、－ＣＮ、－ＮＯ２、－ＳＯ２、－ＳＯＲ”、－ＳＯ２Ｒ”、又は－ＳＯ３Ｒ”を表し、Ｒ”はそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。
　ｐは１～４の整数であり、ｐが２以上のときＡｒ１及びＡｒ２はそれぞれ同一でも異なっていてもよい。 In General Formula (M-1), Ar 1 and Ar 2 are each independently one or more selected from alkyl, aryl, heteroaryl, arylamino, alkylamino, morpholino, thiomorpholino, N, O, and S It represents a 5- or 6-membered heterocycloalkyl or cycloalkyl containing a hetero atom, and may further have a substituent Z. Ar 1 and Ar 2 may be bonded to each other by a single bond, alkylene, or alkenylene (with or without a condensed ring) to form a condensed 5- to 9-membered ring.
Ar 3 represents alkyl, aryl, heteroaryl, or arylamino, and may further have a substituent Z.
Z is each independently a halogen atom, —R ″, —OR ″, —N (R ″) 2 , —SR ″, —C (O) R ″, —C (O) OR ″, —C (O) N (R ") 2, -CN , -NO 2, -SO 2, -SOR", - SO 2 R ", or -SO 3 R" represents, R "are each independently a hydrogen atom, an alkyl group, A perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group is represented.
p is an integer of 1 to 4, and when p is 2 or more, Ar 1 and Ar 2 may be the same or different.
　一般式（Ｍ－１）で表される化合物の好ましい別の形態は、下記一般式（Ｍ－２）で表される場合である。 Another preferred embodiment of the compound represented by the general formula (M-1) is a case represented by the following general formula (M-2).
Figure JPOXMLDOC01-appb-C000068
Figure JPOXMLDOC01-appb-C000068
　一般式（Ｍ－２）中、ＲＭ１はアルキル基、アリール基、又はヘテロアリール基を表す。
　ＲＭ２～ＲＭ２３はそれぞれ独立に、水素原子、アルキル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、アミノ基、シリル基、シアノ基、ニトロ基、又はフッ素原子を表す。 In general formula (M-2), R M1 represents an alkyl group, an aryl group, or a heteroaryl group.
R M2 to R M23 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, an amino group, a silyl group, a cyano group, a nitro group, or a fluorine atom.
　一般式（Ｍ－２）中、ＲＭ１はアルキル基（好ましくは炭素数１～８）、アリール基（好ましくは炭素数６～３０）、又はヘテロアリール基（好ましくは炭素数４～１２）を表し、これらは前述の置換基Ｚを有していても良い。ＲＭ１として好ましくは、アリール基、又はヘテロアリール基であり、より好ましくはアリール基である。ＲＭ１のアリール基が置換基を有する場合の好ましい置換基としては、アルキル基、ハロゲン原子、シアノ基、アリール基、アルコキシ基が挙げられ、アルキル基、ハロゲン原子、シアノ基、又はアリール基がより好ましく、アルキル基、シアノ基、又はアリール基が更に好ましい。ＲＭ１のアリール基は、好ましくは置換基Ｚを有していてもよいフェニル基であり、より好ましくはアルキル基又はシアノ基を有していてもよいフェニル基である。 In general formula (M-2), R M1 represents an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms), or a heteroaryl group (preferably having 4 to 12 carbon atoms). Which may have the aforementioned substituent Z. R M1 is preferably an aryl group or a heteroaryl group, and more preferably an aryl group. Preferred substituents when the aryl group of R M1 has a substituent include an alkyl group, a halogen atom, a cyano group, an aryl group, and an alkoxy group, and an alkyl group, a halogen atom, a cyano group, and an aryl group are more preferable. An alkyl group, a cyano group, or an aryl group is more preferable. The aryl group of R M1 is preferably a phenyl group that may have a substituent Z, and more preferably a phenyl group that may have an alkyl group or a cyano group.
　ＲＭ２～ＲＭ２３はそれぞれ独立に、水素原子、アルキル基（好ましくは炭素数１～８）、アリール基（好ましくは炭素数６～３０）、ヘテロアリール基（好ましくは炭素数４～１２）、アルコキシ基（好ましくは炭素数１～８）、アリールオキシ基（好ましくは炭素数６～３０）、アミノ基（好ましくは炭素数０～２４）、シリル基（好ましくは炭素数０～１８）、シアノ基、ニトロ基、又はフッ素原子を表し、これらは前述の置換基Ｚを有していても良い。 R M2 to R M23 are each independently a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms), a heteroaryl group (preferably having 4 to 12 carbon atoms), Alkoxy group (preferably having 1 to 8 carbon atoms), aryloxy group (preferably having 6 to 30 carbon atoms), amino group (preferably having 0 to 24 carbon atoms), silyl group (preferably having 0 to 18 carbon atoms), cyano Represents a group, a nitro group, or a fluorine atom, and these may have the aforementioned substituent Z.
　ＲＭ２、ＲＭ７、ＲＭ８、ＲＭ１５、ＲＭ１６及びＲＭ２３として好ましくは、水素原子、又は置換基Ｚを有していても良いアルキル基若しくはアリール基であり、更に好ましくは水素原子である。
　ＲＭ４、ＲＭ５、ＲＭ１１、ＲＭ１２、ＲＭ１９及びＲＭ２０として好ましくは、水素原子、置換基Ｚを有していても良いアルキル基若しくはアリール基、又はフッ素原子であり、更に好ましくは水素原子である。
　ＲＭ３、ＲＭ６、ＲＭ９、ＲＭ１４、ＲＭ１７及びＲＭ２２として好ましくは、水素原子、置換基Ｚを有していても良いアルキル基若しくはアリール基、フッ素原子、又はシアノ基であり、より好ましくは水素原子、又は置換基Ｚを有していても良いアルキル基であり、更に好ましくは水素原子である。
　ＲＭ１０、ＲＭ１３、ＲＭ１８及びＲＭ２１として好ましくは、水素原子、置換基Ｚを有していても良いアルキル基、アリール基、ヘテロアリール基若しくはアミノ基、ニトロ基、フッ素原子、又はシアノ基であり、より好ましくは水素原子、置換基Ｚを有していても良いアルキル基若しくはアリール基、ニトロ基、フッ素原子、又はシアノ基であり、更に好ましくは水素原子、又は置換基Ｚを有していても良いアルキル基である。アルキル基が置換基を有する場合の置換基としては、フッ素原子が好ましく、置換基Ｚを有していても良いアルキル基の炭素数は好ましくは１～６であり、より好ましくは１～４である。 R M2 , R M7 , R M8 , R M15 , R M16 and R M23 are preferably a hydrogen atom or an alkyl group or an aryl group which may have a substituent Z, more preferably a hydrogen atom. .
R M4 , R M5 , R M11 , R M12 , R M19, and R M20 are preferably a hydrogen atom, an alkyl or aryl group optionally having substituent Z, or a fluorine atom, more preferably a hydrogen atom. Is an atom.
R M3 , R M6 , R M9 , R M14 , R M17 and R M22 are preferably a hydrogen atom, an alkyl or aryl group optionally having substituent Z, a fluorine atom, or a cyano group, and more A hydrogen atom or an alkyl group which may have a substituent Z is preferable, and a hydrogen atom is more preferable.
R M10 , R M13 , R M18 and R M21 are preferably a hydrogen atom, an alkyl group optionally having a substituent Z, an aryl group, a heteroaryl group or an amino group, a nitro group, a fluorine atom, or a cyano group More preferably a hydrogen atom, an alkyl or aryl group optionally having a substituent Z, a nitro group, a fluorine atom, or a cyano group, still more preferably a hydrogen atom or a substituent Z. It is an alkyl group that may be present. When the alkyl group has a substituent, the substituent is preferably a fluorine atom, and the alkyl group which may have the substituent Z preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. is there.
　一般式（Ｍ－１）で表される化合物の好ましい別の形態は、下記一般式（Ｍ－３）で表される場合である。 Another preferred embodiment of the compound represented by the general formula (M-1) is a case represented by the following general formula (M-3).
Figure JPOXMLDOC01-appb-C000069
Figure JPOXMLDOC01-appb-C000069
　一般式（Ｍ－３）中、ＲＳ１～ＲＳ５はそれぞれ独立にアルキル基、シクロアルキル基、アルケニル基、アルキニル基、－ＣＮ、ペルフルオロアルキル基、トリフルオロビニル基、－ＣＯ２Ｒ、－Ｃ（Ｏ）Ｒ、－ＮＲ２、－ＮＯ２、－ＯＲ、ハロゲン原子、アリール基又はヘテロアリール基を表し、更に置換基Ｚを有していてもよい。Ｒはそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。複数のＲＳ１～ＲＳ５が存在するとき、それらは互いに結合して環を形成してもよく、更に置換基Ｚを有していてもよい。
　ａは０～４の整数を表し、複数のＲＳ１が存在するとき、それらは同一でも異なっていてもよく、互いに結合して環を形成してもよい。ｂ～ｅはそれぞれ独立に０～５の整数を表し、それぞれ複数のＲＳ２～ＲＳ５が存在するとき、それらは同一でも異なっていてもよく、任意の２つが結合し環を形成してもよい。
　ｑは１～５の整数であり、ｑが２以上のとき複数のＲＳ１は同一でも異なっていてもよく、互いに結合して環を形成していてもよい。 In the general formula (M-3), R S1 to R S5 are each independently an alkyl group, cycloalkyl group, alkenyl group, alkynyl group, —CN, perfluoroalkyl group, trifluorovinyl group, —CO 2 R, —C (O) represents R, —NR 2 , —NO 2 , —OR, a halogen atom, an aryl group or a heteroaryl group, and may further have a substituent Z. Each R independently represents a hydrogen atom, an alkyl group, a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group. When a plurality of R S1 to R S5 are present, they may be bonded to each other to form a ring, and may further have a substituent Z.
a represents an integer of 0 to 4, and when a plurality of R S1 are present, they may be the same or different and may be bonded to each other to form a ring. b to e each independently represent an integer of 0 to 5, and when there are a plurality of R S2 to R S5 , they may be the same or different, and any two may combine to form a ring. Good.
q is an integer of 1 to 5, and when q is 2 or more, a plurality of R S1 may be the same or different, and may be bonded to each other to form a ring.
　アルキル基としては、置換基を有していてもよく、飽和であっても不飽和であってもよく、置換してもよい基としては、前述の置換基Ｚを挙げることができる。ＲＳ１～ＲＳ５で表されるアルキル基として、好ましくは総炭素原子数１～８のアルキル基であり、より好ましくは総炭素原子数１～６のアルキル基であり、例えばメチル基、エチル基、ｉ－プロピル基、シクロヘキシル基、ｔ－ブチル基等が挙げられる。
　シクロアルキル基としては、置換基を有していてもよく、飽和であっても不飽和であってもよく、置換してもよい基としては、前述の置換基Ｚを挙げることができる。ＲＳ１～ＲＳ５で表されるシクロアルキル基として、好ましくは環員数４～７のシクロアルキル基であり、より好ましくは総炭素原子数５～６のシクロアルキル基であり、例えばシクロペンチル基、シクロヘキシル基等が挙げられる。
　ＲＳ１～ＲＳ５で表されるアルケニル基としては好ましくは炭素数２～３０、より好ましくは炭素数２～２０、特に好ましくは炭素数２～１０であり、例えばビニル、アリル、１－プロペニル、１－イソプロペニル、１－ブテニル、２－ブテニル、３－ペンテニルなどが挙げられる。
　ＲＳ１～ＲＳ５で表されるアルキニル基としては、好ましくは炭素数２～３０、より好ましくは炭素数２～２０、特に好ましくは炭素数２～１０であり、例えばエチニル、プロパルギル、１－プロピニル、３－ペンチニルなどが挙げられる。 The alkyl group may have a substituent, may be saturated or unsaturated, and examples of the group that may be substituted include the above-described substituent Z. The alkyl group represented by R S1 to R S5 is preferably an alkyl group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 6 carbon atoms in total, such as a methyl group or an ethyl group. , I-propyl group, cyclohexyl group, t-butyl group and the like.
The cycloalkyl group may have a substituent, may be saturated or unsaturated, and examples of the group that may be substituted include the above-described substituent Z. The cycloalkyl group represented by R S1 to R S5 is preferably a cycloalkyl group having 4 to 7 ring members, more preferably a cycloalkyl group having 5 to 6 carbon atoms in total, such as a cyclopentyl group and cyclohexyl group. Groups and the like.
The alkenyl group represented by R S1 to R S5 preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. For example, vinyl, allyl, 1-propenyl, Examples include 1-isopropenyl, 1-butenyl, 2-butenyl, 3-pentenyl and the like.
The alkynyl group represented by R S1 to R S5 preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. For example, ethynyl, propargyl, 1-propynyl , 3-pentynyl and the like.
　ＲＳ１～ＲＳ５で表されるペルフルオロアルキル基は、前述のアルキル基の全ての水素原子がフッ素原子に置き換えられたものが挙げられる。 Examples of the perfluoroalkyl group represented by R S1 to R S5 include those in which all hydrogen atoms of the aforementioned alkyl group are replaced with fluorine atoms.
　ＲＳ１～ＲＳ５で表されるアリール基としては、好ましくは、炭素数６から３０の置換若しくは無置換のアリール基、例えば、フェニル基、トリル基、ビフェニル基、ターフェニル基等が挙げられる。 The aryl group represented by R S1 to R S5 is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a tolyl group, a biphenyl group, and a terphenyl group.
　ＲＳ１～ＲＳ５で表されるヘテロアリール基としては、好ましくは、炭素数５～８のヘテロアリール基であり、より好ましくは、５又は６員の置換若しくは無置換のヘテロアリール基であり、例えば、ピリジル基、ピラジニル基、ピリダジニル基、ピリミジニル基、トリアジニル基、キノリニル基、イソキノリニル基、キナゾリニル基、シンノリニル基、フタラジニル基、キノキサリニル基、ピロリル基、インドリル基、フリル基、ベンゾフリル基、チエニル基、ベンゾチエニル基、ピラゾリル基、イミダゾリル基、ベンズイミダゾリル基、トリアゾリル基、オキサゾリル基、ベンズオキサゾリル基、チアゾリル基、ベンゾチアゾリル基、イソチアゾリル基、ベンズイソチアゾリル基、チアジアゾリル基、イソオキサゾリル基、ベンズイソオキサゾリル基、ピロリジニル基、ピペリジニル基、ピペラジニル基、イミダゾリジニル基、チアゾリニル基、スルホラニル基、カルバゾリル基、ジベンゾフリル基、ジベンゾチエニル基、ピリドインドリル基などが挙げられる。好ましい例としては、ピリジル基、ピリミジニル基、イミダゾリル基、チエニル基であり、より好ましくは、ピリジル基、ピリミジニル基である。 The heteroaryl group represented by R S1 to R S5 is preferably a heteroaryl group having 5 to 8 carbon atoms, more preferably a 5- or 6-membered substituted or unsubstituted heteroaryl group, For example, pyridyl group, pyrazinyl group, pyridazinyl group, pyrimidinyl group, triazinyl group, quinolinyl group, isoquinolinyl group, quinazolinyl group, cinnolinyl group, phthalazinyl group, quinoxalinyl group, pyrrolyl group, indolyl group, furyl group, benzofuryl group, thienyl group, Benzothienyl, pyrazolyl, imidazolyl, benzimidazolyl, triazolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, thiadiazolyl, isoxazolyl, benziso Kisazoriru group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, an imidazolidinyl group, a thiazolinyl group, a sulfolanyl group, a carbazolyl group, a dibenzofuryl group, dibenzothienyl group, a pyrido-indolyl group. Preferred examples include pyridyl group, pyrimidinyl group, imidazolyl group, and thienyl group, and more preferred are pyridyl group and pyrimidinyl group.
　ＲＳ１～ＲＳ５として好ましくは、水素原子、アルキル基、シアノ基、トリフルオロメチル基、ペルフルオロアルキル基、ジアルキルアミノ基、フルオロ基、アリール基、ヘテロアリール基であり、より好ましくは水素原子、アルキル基、シアノ基、トリフルオロメチル基、フルオロ基、アリール基であり、更に好ましくは、水素原子、アルキル基、アリール基である。置換基Ｚとしては、アルキル基、アルコキシ基、フルオロ基、シアノ基、ジアルキルアミノ基が好ましく、水素原子、アルキル基がより好ましい。 R S1 to R S5 are preferably a hydrogen atom, an alkyl group, a cyano group, a trifluoromethyl group, a perfluoroalkyl group, a dialkylamino group, a fluoro group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. Group, cyano group, trifluoromethyl group, fluoro group and aryl group, more preferably a hydrogen atom, an alkyl group and an aryl group. As the substituent Z, an alkyl group, an alkoxy group, a fluoro group, a cyano group, and a dialkylamino group are preferable, and a hydrogen atom and an alkyl group are more preferable.
　ＲＳ１～ＲＳ５は任意の２つが互いに結合して縮合４～７員環を形成してもよく、該縮合４～７員環は、シクロアルキル、アリール又はヘテロアリールであり、該縮合４～７員環は更に置換基Ｚを有していてもよい。形成されるシクロアルキル、アリール、ヘテロアリールの定義及び好ましい範囲はＲＳ１～ＲＳ５で定義したシクロアルキル基、アリール基、ヘテロアリール基と同じである。 Any one of R S1 to R S5 may be bonded to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring is cycloalkyl, aryl, or heteroaryl; The 7-membered ring may further have a substituent Z. The definition and preferred range of cycloalkyl, aryl, and heteroaryl formed are the same as the cycloalkyl group, aryl group, and heteroaryl group defined by R S1 to R S5 .
　一般式（Ｍ－１）で表される化合物を、正孔輸送層中で用いる場合は、一般式（Ｍ－１）で表される化合物は５０～１００質量％含まれることが好ましく、８０～１００質量％含まれることが好ましく、９５～１００質量％含まれることが特に好ましい。
　また、一般式（Ｍ－１）で表される化合物を、複数の有機層に用いる場合はそれぞれの層において、上記の範囲で含有することが好ましい。 When the compound represented by the general formula (M-1) is used in the hole transport layer, the compound represented by the general formula (M-1) is preferably contained in an amount of 50 to 100% by mass, The content is preferably 100% by mass, and particularly preferably 95 to 100% by mass.
In addition, when the compound represented by the general formula (M-1) is used in a plurality of organic layers, it is preferable that each layer contains the above-mentioned range.
　一般式（Ｍ－１）で表される化合物は、いずれかの有機層に、一種類のみを含有していてもよく、複数の一般式（Ｍ－１）で表される化合物を任意の割合で組み合わせて含有していてもよい。 The compound represented by the general formula (M-1) may contain only one kind in any organic layer, and the compound represented by the plurality of general formulas (M-1) You may contain in combination.
　一般式（Ｍ－１）で表される化合物を含む正孔輸送層の厚さとしては、１ｎｍ～５００ｎｍであるのが好ましく、３ｎｍ～２００ｎｍであるのがより好ましく、５ｎｍ～１００ｎｍであるのが更に好ましい。また、該正孔輸送層は発光層に接して設けられている事が好ましい。
　該正孔輸送層は、上述した材料の一種又は二種以上からなる単層構造であってもよいし、同一組成又は異種組成の複数層からなる多層構造であってもよい。 The thickness of the hole transport layer containing the compound represented by the general formula (M-1) is preferably 1 nm to 500 nm, more preferably 3 nm to 200 nm, and more preferably 5 nm to 100 nm. Further preferred. The hole transport layer is preferably provided in contact with the light emitting layer.
The hole transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
　一般式（Ｍ－１）で表される化合物の膜状態での最低励起三重項（Ｔ１）エネルギーは２．５２ｅＶ（５８ｋｃａｌ／ｍｏｌ）以上３．４７ｅＶ（８０ｋｃａｌ／ｍｏｌ）以下であることが好ましく、２．６０ｅＶ（６０ｋｃａｌ／ｍｏｌ）以上３．２５ｅＶ（７５ｋｃａｌ／ｍｏｌ）以下であることがより好ましく、２．６９ｅＶ（６２ｋｃａｌ／ｍｏｌ）以上３．０４ｅＶ（７０ｋｃａｌ／ｍｏｌ）以下であることが更に好ましい The lowest excited triplet (T 1 ) energy in the film state of the compound represented by the general formula (M-1) is preferably 2.52 eV (58 kcal / mol) or more and 3.47 eV (80 kcal / mol) or less. It is more preferably 2.60 eV (60 kcal / mol) or more and 3.25 eV (75 kcal / mol) or less, and further preferably 2.69 eV (62 kcal / mol) or more and 3.04 eV (70 kcal / mol) or less.
　一般式（Ｍ－１）を構成する水素原子は、水素の同位体（重水素原子等）も含む。この場合化合物中の全ての水素原子が水素同位体に置き換わっていてもよく、また一部が水素同位体を含む化合物である混合物でもよい。 The hydrogen atom constituting the general formula (M-1) includes hydrogen isotopes (such as deuterium atoms). In this case, all hydrogen atoms in the compound may be replaced with hydrogen isotopes, or a mixture in which a part is a compound containing hydrogen isotopes may be used.
　一般式（Ｍ－１）で表される化合物は、種々の公知の合成法を組み合わせて合成することが可能である。最も一般的には、カルバゾール化合物に関してはアリールヒドラジンとシクロヘキサン誘導体との縮合体のアザーコープ転位反応の後、脱水素芳香族化による合成（Ｌ．Ｆ．Ｔｉｅｚｅ，Ｔｈ．Ｅｉｃｈｅｒ著、高野、小笠原訳、精密有機合成、３３９頁（南江堂刊））が挙げられる。また、得られたカルバゾール化合物とハロゲン化アリール化合物のパラジウム触媒を用いるカップリング反応に関してはテトラヘドロン・レターズ３９巻６１７頁（１９９８年）、同３９巻２３６７頁（１９９８年）及び同４０巻６３９３頁（１９９９年）等に記載の方法が挙げられる。反応温度、反応時間については特に限定されることはなく、前記文献に記載の条件が適用できる。 The compound represented by the general formula (M-1) can be synthesized by combining various known synthesis methods. Most commonly, carbazole compounds are synthesized by dehydroaromatization after the Athercorp rearrangement reaction of a condensate of an aryl hydrazine and a cyclohexane derivative (LF Tieze, by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo). Regarding the coupling reaction of the obtained carbazole compound and halogenated aryl compound using a palladium catalyst, Tetrahedron Letters 39: 617 (1998), 39: 2367 (1998) and 40: 6393 (1999) and the like. The reaction temperature and reaction time are not particularly limited, and the conditions described in the above literature can be applied.
　本発明の一般式（Ｍ－１）で表される化合物は、真空蒸着プロセスで薄層を形成することが好ましいが、溶液塗布などのウェットプロセスも好適に用いることが出来る。化合物の分子量は、蒸着適性や溶解性の観点から２０００以下であることが好ましく、１２００以下であることがより好ましく、８００以下であることが特に好ましい。また蒸着適性の観点では、分子量が小さすぎると蒸気圧が小さくなり、気相から固相への変化がおきず、有機層を形成することが困難となるので、２５０以上が好ましく、３００以上が特に好ましい。　 The compound represented by the general formula (M-1) of the present invention is preferably formed into a thin layer by a vacuum deposition process, but a wet process such as solution coating can also be suitably used. The molecular weight of the compound is preferably 2000 or less, more preferably 1200 or less, and particularly preferably 800 or less from the viewpoints of deposition suitability and solubility. Also, from the viewpoint of vapor deposition suitability, if the molecular weight is too small, the vapor pressure becomes small, the change from the gas phase to the solid phase does not occur, and it is difficult to form an organic layer. Particularly preferred. *
　以下に、一般式（Ｍ－１）で表される化合物の具体例を示すが、本発明がこれらに限定されることはない。 Specific examples of the compound represented by the general formula (M-1) are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000070
Figure JPOXMLDOC01-appb-C000070
Figure JPOXMLDOC01-appb-C000071
Figure JPOXMLDOC01-appb-C000071
Figure JPOXMLDOC01-appb-C000072
Figure JPOXMLDOC01-appb-C000072
Figure JPOXMLDOC01-appb-C000073
Figure JPOXMLDOC01-appb-C000073
Figure JPOXMLDOC01-appb-C000074
Figure JPOXMLDOC01-appb-C000074
〔芳香族炭化水素化合物〕
　本発明の有機電界発光素子は、前記一対の電極が陰極を含み、前記発光層と該陰極との間に少なくとも一層の有機層を含むことが好ましく、該有機層に芳香族炭化水素化合物を含有することが好ましい。
　芳香族炭化水素化合物は、発光層と陰極の間の発光層に隣接する有機層に含有されることがより好ましいが、その用途が限定されることはなく、有機層内のいずれの層に更に含有されてもよい。本発明にかかる芳香族炭化水素化合物の導入層としては、発光層、正孔注入層、正孔輸送層、電子輸送層、電子注入層、励起子ブロック層、電荷ブロック層のいずれか、若しくは複数に含有することができる。
　芳香族炭化水素化合物が含有される、発光層と陰極の間の発光層に隣接する有機層は電荷ブロック層又は電子輸送層であることが好ましく、電子輸送層であることがより好ましい。 [Aromatic hydrocarbon compounds]
In the organic electroluminescent element of the present invention, the pair of electrodes preferably includes a cathode, and preferably includes at least one organic layer between the light emitting layer and the cathode, and the organic layer includes an aromatic hydrocarbon compound. It is preferable to do.
The aromatic hydrocarbon compound is more preferably contained in an organic layer adjacent to the light emitting layer between the light emitting layer and the cathode, but its use is not limited, and any of the organic layers may be further added. It may be contained. As the introduction layer of the aromatic hydrocarbon compound according to the present invention, any one or more of a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an exciton block layer, and a charge block layer are used. It can contain.
The organic layer adjacent to the light emitting layer between the light emitting layer and the cathode and containing the aromatic hydrocarbon compound is preferably a charge blocking layer or an electron transporting layer, and more preferably an electron transporting layer.
　芳香族炭化水素化合物は合成容易さの観点から炭素原子と水素原子のみからなることが好ましい。
　芳香族炭化水素化合物を発光層以外の層に含有させる場合は、７０～１００質量％含まれることが好ましく、８５～１００質量％含まれることがより好ましい。芳香族炭化水素化合物を発光層に含有させる場合は、発光層の全質量に対して０．１～９９質量％含ませることが好ましく、１～９５質量％含ませることがより好ましく、１０～９５質量％含ませることがより好ましい。
　炭素原子と水素原子のみからなり、分子量が４００～１２００の範囲にあり、総炭素数１３～２２の縮合多環骨格を有する炭化水素化合物を用いることが好ましい。総炭素数１３～２２の縮合多環骨格としては、フルオレン、アントラセン、フェナントレン、テトラセン、クリセン、ペンタセン、ピレン、ペリレン、トリフェニレンのいずれかであることが好ましく、Ｔ１の観点からフルオレン、トリフェニレン、フェナントレンがより好ましく、化合物の安定性、電荷注入・輸送性の観点からトリフェニレンが更に好ましく、一般式（Ｔｐ－１）で表される化合物であることが特に好ましい。 The aromatic hydrocarbon compound preferably comprises only carbon atoms and hydrogen atoms from the viewpoint of ease of synthesis.
When the aromatic hydrocarbon compound is contained in a layer other than the light emitting layer, it is preferably contained in an amount of 70 to 100% by mass, more preferably 85 to 100% by mass. When the aromatic hydrocarbon compound is contained in the light emitting layer, it is preferably contained in an amount of 0.1 to 99% by weight, more preferably 1 to 95% by weight, based on the total weight of the light emitting layer. It is more preferable to include the mass%.
It is preferable to use a hydrocarbon compound having only a carbon atom and a hydrogen atom, a molecular weight in the range of 400 to 1200, and a condensed polycyclic skeleton having a total carbon number of 13 to 22. The condensed polycyclic skeleton having 13 to 22 carbon atoms is preferably any one of fluorene, anthracene, phenanthrene, tetracene, chrysene, pentacene, pyrene, perylene, and triphenylene. From the viewpoint of T 1 , fluorene, triphenylene, phenanthrene. Is more preferable, and triphenylene is more preferable from the viewpoint of stability of the compound and charge injection / transport properties, and a compound represented by the general formula (Tp-1) is particularly preferable.
　一般式（Ｔｐ－１）で表される炭化水素化合物は、分子量が４００～１２００の範囲であることが好ましく、より好ましくは４００～１０００であり、更に好ましくは４００～８００である。分子量が４００以上であれば良質なアモルファス薄膜が形成でき、分子量が１２００以下であると溶媒への溶解性や昇華及び蒸着適正の面で好ましい。 The hydrocarbon compound represented by the general formula (Tp-1) preferably has a molecular weight in the range of 400 to 1200, more preferably 400 to 1000, and still more preferably 400 to 800. If the molecular weight is 400 or more, a high-quality amorphous thin film can be formed, and if the molecular weight is 1200 or less, it is preferable in terms of solubility in a solvent, sublimation, and appropriate deposition.
　一般式（Ｔｐ－１）で表される炭化水素化合物はその用途が限定されることはなく、発光層に隣接する有機層だけでなく有機層内のいずれの層に更に含有されてもよい。 The use of the hydrocarbon compound represented by the general formula (Tp-1) is not limited, and it may be further contained not only in the organic layer adjacent to the light emitting layer but also in any layer within the organic layer.
Figure JPOXMLDOC01-appb-C000075
Figure JPOXMLDOC01-appb-C000075
（一般式（Ｔｐ－１）において、Ｒ１２～Ｒ２３はそれぞれ独立に水素原子、アルキル基又はアルキル基、フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基で置換されていてもよいフェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基を表す。ただし、Ｒ１２～Ｒ２３が全て水素原子になることはない。） (In the general formula (Tp-1), R 12 to R 23 are each independently a hydrogen atom, an alkyl group or an alkyl group, a phenyl group optionally substituted with a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group, Represents a fluorenyl group, a naphthyl group, or a triphenylenyl group, provided that R 12 to R 23 are not all hydrogen atoms.)
　Ｒ１２～Ｒ２３が表すアルキル基としては、置換基若しくは無置換の、例えば、メチル基、エチル基、イソプロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－オクチル基、ｎ－デシル基、ｎ－ヘキサデシル基、シクロプロピル基、シクロペンチル基、シクロヘキシル基などが挙げられ、好ましくはメチル基、エチル基、イソプロピル基、ｔｅｒｔ－ブチル基、シクロヘキシル基であり、より好ましくはメチル基、エチル基、又はｔｅｒｔ－ブチル基である。 Examples of the alkyl group represented by R 12 to R 23 are substituted or unsubstituted, for example, methyl group, ethyl group, isopropyl group, n-butyl group, tert-butyl group, n-octyl group, n-decyl group, and an n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like, preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a cyclohexyl group, more preferably a methyl group, an ethyl group, or A tert-butyl group.
　Ｒ１２～Ｒ２３として好ましくは、炭素数１～４のアルキル基又は炭素数１～４のアルキル基、フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基（これらは更にアルキル基、フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基で置換されていてもよい）で置換されていてもよい、フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基であることが更に好ましい。
　フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基（これらは更にアルキル基、フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基で置換されていてもよい）で置換されていてもよい、ベンゼン環であることが特に好ましい。 R 12 to R 23 are preferably an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (these are further an alkyl group, a phenyl group, a fluorenyl group). More preferably a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group, which may be substituted with a group, a naphthyl group, or a triphenylenyl group.
A benzene ring that may be substituted with a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (which may be further substituted with an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group); It is particularly preferred.
　一般式（Ｔｐ－１）におけるアリール環の総数は２～８個であることが好ましく、３～５個であることが好ましい。この範囲とすることで、良質なアモルファス薄膜が形成でき、溶媒への溶解性や昇華及び蒸着適正が良好になる。 In the general formula (Tp-1), the total number of aryl rings is preferably 2 to 8, and preferably 3 to 5. By setting it as this range, a high-quality amorphous thin film can be formed, and solubility in a solvent, sublimation, and deposition suitability are improved.
　Ｒ１２～Ｒ２３は、それぞれ独立に、総炭素数が２０～５０であることが好ましく、総炭素数が２０～３６であることがより好ましい。この範囲とすることで、良質なアモルファス薄膜が形成でき、溶媒への溶解性や昇華及び蒸着適正が良好になる。 R 12 to R 23 each independently preferably has a total carbon number of 20 to 50, more preferably a total carbon number of 20 to 36. By setting it as this range, a high-quality amorphous thin film can be formed, and solubility in a solvent, sublimation, and deposition suitability are improved.
　本発明の一の態様において、前記一般式（Ｔｐ－１）で表される炭化水素化合物は下記一般式（Ｔｐ－２）で表される炭化水素化合物であることが好ましい。 In one embodiment of the present invention, the hydrocarbon compound represented by the general formula (Tp-1) is preferably a hydrocarbon compound represented by the following general formula (Tp-2).
Figure JPOXMLDOC01-appb-C000076
Figure JPOXMLDOC01-appb-C000076
（一般式（Ｔｐ－２）中、複数のＡｒ１は同一であり、アルキル基、フェニル基、フルオレニル基、ナフチル基、又はトリフェニレニル基で置換されていてもよいフェニル基、フルオレニル基、ナフチル基、又はトリフェニレニル基を表す。） (In the general formula (Tp-2), a plurality of Ar 1 are the same, and a phenyl group, a fluorenyl group, a naphthyl group, which may be substituted with an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group, Or represents a triphenylenyl group.)
　Ａｒ１が表すアルキル基及びアルキル基、フェニル基、フルオレニル基、ナフチル基、又はトリフェニレニル基で置換されていてもよいフェニル基、フルオレニル基、ナフチル基、又はトリフェニレニル基としては、Ｒ１２～Ｒ２３で挙げたものと同義であり、好ましいものも同様である。 An alkyl group and an alkyl group represented by Ar 1 , a phenyl group, a fluorenyl group, a naphthyl group, or a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group that may be substituted with a triphenylenyl group include R 12 to R 23 . It is synonymous with what was mentioned, and a preferable thing is also the same.
　本発明の他の態様において、前記一般式（Ｔｐ－１）で表される炭化水素化合物は、下記一般式（Ｔｐ－３）で表される炭化水素化合物であることが好ましい。 In another embodiment of the present invention, the hydrocarbon compound represented by the general formula (Tp-1) is preferably a hydrocarbon compound represented by the following general formula (Tp-3).
Figure JPOXMLDOC01-appb-C000077
Figure JPOXMLDOC01-appb-C000077
（一般式（Ｔｐ－３）中、Ｌはアルキル基、フェニル基、フルオレニル基、ナフチル基、又はトリフェニレニル基で置換されていてもよいフェニル基、フルオレニル基、ナフチル基、トリフェニレニル基又はこれらを組み合わせて成るｎ価の連結基を表す。ｎは１～６の整数を表す。） (In the general formula (Tp-3), L represents an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a phenyl group, a fluorenyl group, a naphthyl group, a triphenylenyl group which may be substituted with a triphenylenyl group, or a combination thereof. And n represents an integer of 1 to 6.)
　Ｌが表すｎ価の連結基を形成するアルキル基、フェニル基、フルオレニル基、ナフチル基、又はトリフェニレニル基としては、Ｒ１２～Ｒ２３で挙げたものと同義である。
　Ｌとして好ましくは、アルキル基又はベンゼン環で置換されていてもよいベンゼン環、フルオレン環、又はこれらを組み合わせて成るｎ価の連結基である。
　以下にＬの好ましい具体例を挙げるがこれらに限定されるものではない。なお具体例中＊でトリフェニレン環と結合する。 The alkyl group, phenyl group, fluorenyl group, naphthyl group, or triphenylenyl group that forms the n-valent linking group represented by L has the same meaning as that described for R 12 to R 23 .
L is preferably an alkyl group or an n-valent linking group formed by combining a benzene ring, a fluorene ring, or a combination thereof, which may be substituted with a benzene ring.
Although the preferable specific example of L is given to the following, it is not limited to these. In the specific examples, it is bonded to the triphenylene ring by *.
Figure JPOXMLDOC01-appb-C000078
Figure JPOXMLDOC01-appb-C000078
　ｎは１～５であることが好ましく、１～４であることがより好ましい。 N is preferably 1 to 5, and more preferably 1 to 4.
　本発明の他の態様において、前記一般式（Ｔｐ－１）で表される炭化水素化合物は、下記一般式（Ｔｐ－４）で表される炭化水素化合物であることが好ましい。 In another embodiment of the present invention, the hydrocarbon compound represented by the general formula (Tp-1) is preferably a hydrocarbon compound represented by the following general formula (Tp-4).
Figure JPOXMLDOC01-appb-C000079
Figure JPOXMLDOC01-appb-C000079
（一般式（Ｔｐ－４）において、複数存在する場合のＡｒ２は同一であり、Ａｒ２はアルキル基、フェニル基、ナフチル基、トリフェニレニル基で置換、又はこれらを組み合わせてなる基を表す。ｐ、及びｑはそれぞれ独立に０又は１を表すが、ｐとｑが同時に０になることはない。ｐ、及びｑが０を表す場合、Ａｒ２は水素原子を表す。） (In General Formula (Tp-4), Ar 2 in the case where a plurality of Ar 2 are present is the same, and Ar 2 represents a group formed by substitution with an alkyl group, phenyl group, naphthyl group, or triphenylenyl group, or a combination thereof. , And q each independently represent 0 or 1, but p and q are not simultaneously 0. When p and q represent 0, Ar 2 represents a hydrogen atom.)
　Ａｒ２として好ましくは、炭素数１～４のアルキル基、フェニル基、ナフチル基、トリフェニレニル基を組み合わせてなる基であり、より好ましくは、メチル基、ｔ－ブチル基、フェニル基、トリフェニレニル基を組み合わせてなる基である。
　Ａｒ２は、メタ位が炭素数１～４のアルキル基、フェニル基、ナフチル基、トリフェニレニル基、又はこれらを組み合わせてなる基で置換されたベンゼン環であることが特に好ましい。 Ar 2 is preferably a group formed by combining an alkyl group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, or a triphenylenyl group, and more preferably a combination of a methyl group, a t-butyl group, a phenyl group, or a triphenylenyl group. It is a group consisting of
Ar 2 is particularly preferably a benzene ring substituted with an alkyl group having 1 to 4 carbon atoms at the meta position, a phenyl group, a naphthyl group, a triphenylenyl group, or a combination thereof.
　本発明にかかる炭化水素化合物を有機電界発光素子の発光層のホスト材料や発光層に隣接する層の電荷輸送材料として使用する場合、発光材料より薄膜状態でのエネルギーギャップ（発光材料が燐光発光材料の場合には、薄膜状態での最低励起三重項（Ｔ１）エネルギー）が大きいと、発光がクエンチしてしまうことを防ぎ、効率向上に有利である。一方、化合物の化学的安定性の観点からは、エネルギーギャップ及びＴ１エネルギーは大き過ぎない方が好ましい。一般式（Ｔｐ－１）で表される炭化水素化合物の膜状態でのＴ１エネルギーは、５２ｋｃａｌ／ｍｏｌ以上８０ｋｃａｌ／ｍｏｌ以下であることが好ましく、５５ｋｃａｌ／ｍｏｌ以上６８ｋｃａｌ／ｍｏｌ）以下であることがより好ましく、５８ｋｃａｌ／ｍｏｌ以上６３ｋｃａｌ／ｍｏｌ以下であることが更に好ましい。特に、発光材料として燐光発光材料を用いる場合には、Ｔ１エネルギーが上記範囲となることが好ましい。 When the hydrocarbon compound according to the present invention is used as a host material of a light emitting layer of an organic electroluminescent device or a charge transport material of a layer adjacent to the light emitting layer, an energy gap in a thin film state than the light emitting material (the light emitting material is a phosphorescent light emitting material) In the case of ( 2 ), when the lowest excited triplet (T 1 ) energy in the thin film state is large, the emission is prevented from quenching, which is advantageous for improving the efficiency. On the other hand, from the viewpoint of chemical stability of the compound, it is preferable that the energy gap and T 1 energy are not too large. The T 1 energy in the film state of the hydrocarbon compound represented by the general formula (Tp-1) is preferably 52 kcal / mol or more and 80 kcal / mol or less, and 55 kcal / mol or more and 68 kcal / mol or less. Is more preferable, and it is still more preferable that they are 58 kcal / mol or more and 63 kcal / mol or less. In particular, when a phosphorescent light emitting material is used as the light emitting material, the T 1 energy is preferably in the above range.
　Ｔ１エネルギーは、前述の一般式（１）の説明における方法と同様の方法により求めることができる。 The T 1 energy can be obtained by a method similar to the method in the description of the general formula (1) described above.
　有機電界発光素子を高温駆動時や素子駆動中の発熱に対して安定して動作させる観点から、本発明にかかる炭化水素化合物のガラス転移温度（Ｔｇ）は８０℃以上４００℃以下であることが好ましく、１００℃以上４００℃以下であることがより好ましく、１２０℃以上４００℃以下であることが更に好ましい。 The glass transition temperature (Tg) of the hydrocarbon compound according to the present invention is 80 ° C. or more and 400 ° C. or less from the viewpoint of stably operating the organic electroluminescence device against heat generation during high temperature driving or during device driving. The temperature is preferably 100 ° C. or higher and 400 ° C. or lower, more preferably 120 ° C. or higher and 400 ° C. or lower.
　以下に、本発明にかかる炭化水素化合物の具体例を例示するが、本発明はこれらに限定されるものではない。 Hereinafter, specific examples of the hydrocarbon compound according to the present invention will be exemplified, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000080
Figure JPOXMLDOC01-appb-C000080
Figure JPOXMLDOC01-appb-C000081
Figure JPOXMLDOC01-appb-C000081
　上記本発明にかかる炭化水素化合物として例示した化合物は、国際公開第０５／０１３３８８号パンフレット、国際公開第０６／１３０５９８号パンフレット、国際公開第０９／０２１１０７号パンフレット、ＵＳ２００９／０００９０６５、国際公開第０９／００８３１１号パンフレット及び国際公開第０４／０１８５８７号パンフレットに記載の方法で合成できる。
　合成後、カラムクロマトグラフィー、再結晶等による精製を行った後、昇華精製により精製することが好ましい。昇華精製により、有機不純物を分離できるだけでなく、無機塩や残留溶媒等を効果的に取り除くことができる。 The compounds exemplified as the hydrocarbon compounds according to the present invention include those described in International Publication No. 05/013388, International Publication No. 06/130598, International Publication No. 09/021107, US2009 / 0009065, International Publication No. 09 / It can be synthesized by the methods described in the 008311 pamphlet and the international publication 04/018587 pamphlet.
After synthesis, it is preferable to purify by sublimation purification after purification by column chromatography, recrystallization or the like. By sublimation purification, not only can organic impurities be separated, but inorganic salts and residual solvents can be effectively removed.
〔一般式（Ｏ－１）で表される化合物〕
　本発明の発光素子は、発光層と陰極との間に少なくとも一層の有機層を含むことが好ましく、該有機層に少なくとも一種の下記一般式（Ｏ－１）で表される化合物を含有することが素子の効率や駆動電圧の観点から好ましい。以下に、一般式（Ｏ－１）について説明する。 [Compound represented by formula (O-1)]
The light emitting device of the present invention preferably contains at least one organic layer between the light emitting layer and the cathode, and the organic layer contains at least one compound represented by the following general formula (O-1). Is preferable from the viewpoints of element efficiency and driving voltage. The general formula (O-1) will be described below.
Figure JPOXMLDOC01-appb-C000082
Figure JPOXMLDOC01-appb-C000082
　（一般式（Ｏ－１）中、ＲＯ１は、アルキル基、アリール基、又はヘテロアリール基を表す。ＡＯ１～ＡＯ４はそれぞれ独立に、Ｃ－ＲＡ又は窒素原子を表す。ＲＡは水素原子、アルキル基、アリール基、又はヘテロアリール基を表し、複数のＲＡは同じでも異なっていても良い。ＬＯ１は、アリール環又はヘテロアリール環からなる二価～六価の連結基を表す。ｎＯ１は２～６の整数を表す。） (In the general formula (O1), R O1 represents an alkyl group, an aryl group, or each independently .A O1 ~ A O4 representing the heteroaryl group, the C-R A or .R A representing the nitrogen atom Represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R A may be the same or different, and L O1 represents a divalent to hexavalent linking group comprising an aryl ring or a heteroaryl ring. N O1 represents an integer of 2 to 6.)
　ＲＯ１は、アルキル基（好ましくは炭素数１～８）、アリール基（好ましくは炭素数６～３０）、又はヘテロアリール基（好ましくは炭素数４～１２）を表し、これらは前述の置換基Ｚ’を有していても良い。ＲＯ１として好ましくはアリール基、又はヘテロアリール基であり、より好ましくはアリール基である。ＲＯ１のアリール基が置換基を有する場合の好ましい置換基としては、アルキル基、アリール基又はシアノ基が挙げられ、アルキル基又はアリール基がより好ましく、アリール基が更に好ましい。ＲＯ１のアリール基が複数の置換基を有する場合、該複数の置換基は互いに結合して５又は６員環を形成していても良い。ＲＯ１のアリール基は、好ましくは置換基Ｚ’を有していても良いフェニル基であり、より好ましくはアルキル基又はアリール基が置換していてもよいフェニル基であり、更に好ましくは無置換のフェニル基又は２－フェニルフェニル基である。 R O1 represents an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms), or a heteroaryl group (preferably having 4 to 12 carbon atoms). Z ′ may be included. R O1 is preferably an aryl group or a heteroaryl group, more preferably an aryl group. As a preferable substituent when the aryl group of R O1 has a substituent, an alkyl group, an aryl group or a cyano group can be mentioned, an alkyl group or an aryl group is more preferable, and an aryl group is still more preferable. When the aryl group of R O1 has a plurality of substituents, the plurality of substituents may be bonded to each other to form a 5- or 6-membered ring. The aryl group of R O1 is preferably a phenyl group which may have a substituent Z ′, more preferably a phenyl group which may be substituted with an alkyl group or an aryl group, still more preferably unsubstituted. A phenyl group or a 2-phenylphenyl group.
　ＡＯ１～ＡＯ４はそれぞれ独立に、Ｃ－ＲＡ又は窒素原子を表す。ＡＯ１～ＡＯ４のうち、０～２つが窒素原子であるのが好ましく、０又は１つが窒素原子であるのがより好ましい。ＡＯ１～ＡＯ４の全てがＣ－ＲＡであるか、又はＡＯ１が窒素原子で、ＡＯ２～ＡＯ４がＣ－ＲＡであるのが好ましく、ＡＯ１が窒素原子で、ＡＯ２～ＡＯ４がＣ－ＲＡであるのがより好ましく、ＡＯ１が窒素原子で、ＡＯ２～ＡＯ４がＣ－ＲＡであり、ＲＡが全て水素原子であるのが更に好ましい。 A O1 to A O4 each independently represent C—R A or a nitrogen atom. Of A O1 to A O4 , 0 to 2 are preferably nitrogen atoms, and 0 or 1 is more preferably a nitrogen atom. Or all of A O1 ~ A O4 is C-R A, or A O1 be a nitrogen atom, is preferably A O2 ~ A O4 is C-R A, A O1 be a nitrogen atom, A O2 ~ More preferably, A O4 is C—R A , more preferably A O1 is a nitrogen atom, A O2 to A O4 are C—R A , and R A is all a hydrogen atom.
　ＲＡは水素原子、アルキル基（好ましくは炭素数１～８）、アリール基（好ましくは炭素数６～３０）、又はヘテロアリール基（好ましくは炭素数４～１２）を表し、これらは前述の置換基Ｚ’を有していても良い。また複数のＲＡは同じでも異なっていても良い。ＲＡとして好ましくは水素原子又はアルキル基であり、より好ましくは水素原子である。 R A represents a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms), or a heteroaryl group (preferably having 4 to 12 carbon atoms). It may have a substituent Z ′. The plurality of RA may be the same or different. R A is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
　ＬＯ１は、アリール環（好ましくは炭素数６～３０）又はヘテロアリール環（好ましくは炭素数４～１２）からなる二価～六価の連結基を表す。ＬＯ１として好ましくは、アリーレン基、ヘテロアリーレン基、アリールトリイル基、又はヘテロアリールトリイル基であり、より好ましくはフェニレン基、ビフェニレン基、又はベンゼントリイル基であり、更に好ましくはビフェニレン基、又はベンゼントリイル基である。ＬＯ１は前述の置換基Ｚ’を有していても良く、置換基を有する場合の置換基としてはアルキル基、アリール基、又はシアノ基が好ましい。ＬＯ１の具体例としては、以下のものが挙げられる。 L O1 represents a divalent to hexavalent linking group composed of an aryl ring (preferably having 6 to 30 carbon atoms) or a heteroaryl ring (preferably having 4 to 12 carbon atoms). L O1 is preferably an arylene group, heteroarylene group, aryltriyl group, or heteroaryltriyl group, more preferably a phenylene group, a biphenylene group, or a benzenetriyl group, still more preferably a biphenylene group, Or it is a benzenetriyl group. L O1 may have the above-described substituent Z ′, and when it has a substituent, the substituent is preferably an alkyl group, an aryl group, or a cyano group. Specific examples of L O1 include the following.
Figure JPOXMLDOC01-appb-C000083
Figure JPOXMLDOC01-appb-C000083
　ｎＯ１は２～６の整数を表し、好ましくは２～４の整数であり、より好ましくは２又は３である。ｎＯ１は、素子効率の観点では最も好ましくは３であり、素子の耐久性の観点では最も好ましくは２である。
　一般式（Ｏ－１）で表される化合物は、より好ましくは下記一般式（Ｏ－２）で表される化合物である。 n O1 represents an integer of 2 to 6, preferably an integer of 2 to 4, more preferably 2 or 3. n O1 is most preferably 3 from the viewpoint of device efficiency, and most preferably 2 from the viewpoint of device durability.
The compound represented by the general formula (O-1) is more preferably a compound represented by the following general formula (O-2).
Figure JPOXMLDOC01-appb-C000084
Figure JPOXMLDOC01-appb-C000084
　（一般式（Ｏ－２）中、ＲＯ１はアルキル基、アリール基、又はヘテロアリール基を表す。ＲＯ２～ＲＯ４はそれぞれ独立に、水素原子、アルキル基、アリール基、又はヘテロアリール基を表す。ＡＯ１～ＡＯ４はそれぞれ独立に、Ｃ－ＲＡ又は窒素原子を表す。ＲＡは水素原子、アルキル基、アリール基、又はヘテロアリール基を表し、複数のＲＡは同じでも異なっていても良い。） (In the general formula (O-2), R O1 represents an alkyl group, an aryl group, or a heteroaryl group. R O2 to R O4 each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. A O1 to A O4 each independently represent C—R A or a nitrogen atom, R A represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R A may be the same or different. May be.)
　ＲＯ１及びＡＯ１～ＡＯ４は、前記一般式（Ｏ－１）中のＲＯ１及びＡＯ１～ＡＯ４と同義であり、またそれらの好ましい範囲も同様である。
　Ｒ０２～Ｒ０４はそれぞれ独立に、水素原子、アルキル基（好ましくは炭素数１～８）、アリール基（好ましくは炭素数６～３０）、又はヘテロアリール基（好ましくは炭素数４～１２）を表し、これらは前述の置換基Ｚ’を有していても良い。Ｒ０２～Ｒ０４として好ましくは水素原子、アルキル基、又はアリール基であり、より好ましくは水素原子、又はアリール基であり、最も好ましくは水素原子である。 R O1 and A O1 ~ A O4, the general formula (O1) in the same meaning as R O1 and A O1 ~ A O4 of, also the same preferable ranges thereof.
R 02 to R 04 are each independently a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms), or a heteroaryl group (preferably having 4 to 12 carbon atoms). Which may have the aforementioned substituent Z ′. R 02 to R 04 are preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an aryl group, and most preferably a hydrogen atom.
　前記一般式（Ｏ－１）で表される化合物は、高温保存時の安定性、高温駆動時、駆動時の発熱に対して安定して動作させる観点から、ガラス転移温度（Ｔｇ）は１００℃～３００℃であることが好ましく、１２０℃～３００℃であることがより好ましく、１３０℃～３００℃であることが更に好ましく、１４０℃～３００℃であることが更により好ましい。 The compound represented by the general formula (O-1) has a glass transition temperature (Tg) of 100 ° C. from the viewpoint of stable operation at high temperature storage, stable operation against high temperature driving, and heat generation during driving. It is preferably from ˜300 ° C., more preferably from 120 ° C. to 300 ° C., further preferably from 130 ° C. to 300 ° C., and still more preferably from 140 ° C. to 300 ° C.
　一般式（Ｏ－１）で表される化合物の具体例を以下に示すが、本発明はこれらに限定されない。 Specific examples of the compound represented by the general formula (O-1) are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000085
Figure JPOXMLDOC01-appb-C000085
Figure JPOXMLDOC01-appb-C000086
Figure JPOXMLDOC01-appb-C000086
　前記一般式（Ｏ－１）で表される化合物は、特開２００１－３３５７７６号に記載の方法で合成可能である。合成後、カラムクロマトグラフィー、再結晶、再沈殿などによる精製を行った後、昇華精製により精製することが好ましい。昇華精製により有機不純物を分離できるだけではなく、無機塩や残留溶媒、水分等を効果的に取り除くことが可能である。 The compound represented by the general formula (O-1) can be synthesized by the method described in JP-A No. 2001-335776. After synthesis, purification by column chromatography, recrystallization, reprecipitation, etc., followed by purification by sublimation is preferred. Not only can organic impurities be separated by sublimation purification, but inorganic salts, residual solvents, moisture, and the like can be effectively removed.
　本発明の発光素子において、一般式（Ｏ－１）で表される化合物は発光層と陰極との間の有機層に含有されるが、発光層に隣接する陰極側の層に含有されることが好ましい。 In the light emitting device of the present invention, the compound represented by the general formula (O-1) is contained in an organic layer between the light emitting layer and the cathode, but is contained in a layer on the cathode side adjacent to the light emitting layer. Is preferred.
（電荷輸送層）
　電荷輸送層とは、有機電界発光素子に電圧を印加した際に電荷移動が起こる層をいう。具体的には正孔注入層、正孔輸送層、電子ブロック層、発光層、正孔ブロック層、電子輸送層又は電子注入層が挙げられる。好ましくは、正孔注入層、正孔輸送層、電子ブロック層又は発光層である。塗布法により形成される電荷輸送層が正孔注入層、正孔輸送層、電子ブロック層又は発光層であれば、低コストかつ高効率な有機電界発光素子の製造が可能となる。また、電荷輸送層として、より好ましくは、正孔注入層、正孔輸送層又は電子ブロック層である。 (Charge transport layer)
The charge transport layer refers to a layer in which charge transfer occurs when a voltage is applied to the organic electroluminescent element. Specific examples include a hole injection layer, a hole transport layer, an electron block layer, a light emitting layer, a hole block layer, an electron transport layer, and an electron injection layer. A hole injection layer, a hole transport layer, an electron blocking layer, or a light emitting layer is preferable. If the charge transport layer formed by the coating method is a hole injection layer, a hole transport layer, an electron block layer, or a light emitting layer, it is possible to produce an organic electroluminescent element with low cost and high efficiency. The charge transport layer is more preferably a hole injection layer, a hole transport layer, or an electron block layer.
（正孔注入層、正孔輸送層）
　正孔注入層、正孔輸送層は、陽極又は陽極側から正孔を受け取り陰極側に輸送する機能を有する層である。
　正孔注入層、正孔輸送層については、特開２００８－２７０７３６号公報の段落番号〔０１６５〕～〔０１６７〕に記載の事項を本発明に適用することができる。　 (Hole injection layer, hole transport layer)
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side.
For the hole injection layer and the hole transport layer, the matters described in paragraph numbers [0165] to [0167] of JP-A-2008-270736 can be applied to the present invention.
　正孔注入層には電子受容性ドーパントを含有することが好ましい。正孔注入層に電子受容性ドーパントを含有することにより、正孔注入性が向上し、駆動電圧が低下する、効率が向上するなどの効果がある。電子受容性ドーパントとは、ドープされる材料から電子を引き抜くき、ラジカルカチオンを発生させることが可能な材料であれば有機材料、無機材料のうちいかなるものでもよいが、例えば、テトラシアノキノジメタン（ＴＣＮＱ）、テトラフルオロテトラシアノキノジメタン（Ｆ４－ＴＣＮＱ）、酸化モリブデンなどが挙げられる。 The hole injection layer preferably contains an electron accepting dopant. By containing an electron-accepting dopant in the hole injection layer, hole injection properties are improved, driving voltage is reduced, and efficiency is improved. The electron-accepting dopant may be any organic material or inorganic material as long as it can extract electrons from the doped material and generate radical cations, for example, tetracyanoquinodimethane. (TCNQ), tetrafluorotetracyanoquinodimethane (F 4 -TCNQ), molybdenum oxide, and the like.
　正孔注入層中の電子受容性ドーパントは、正孔注入層を形成する全化合物質量に対して、０．０１質量％～５０質量％含有されることが好ましく、０．１質量％～４０質量％含有されることがより好ましく、０．２質量％～３０質量％含有されることがより好ましい。 The electron-accepting dopant in the hole injection layer is preferably contained in an amount of 0.01% by mass to 50% by mass, and preferably 0.1% by mass to 40% by mass with respect to the total mass of the compound forming the hole injection layer. %, More preferably 0.2% by mass to 30% by mass.
（電子注入層、電子輸送層）
　電子注入層、電子輸送層は、陰極又は陰極側から電子を受け取り陽極側に輸送する機能を有する層である。これらの層に用いる電子注入材料、電子輸送材料は低分子化合物であっても高分子化合物であってもよい。
　電子輸送材料としては、本発明の一般式（１）～（３）のいずれかで表される化合物を用いることができる。その他の材料としては、ピリジン誘導体、キノリン誘導体、ピリミジン誘導体、ピラジン誘導体、フタラジン誘導体、フェナントロリン誘導体、トリアジン誘導体、トリアゾール誘導体、オキサゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、フルオレノン誘導体、アントラキノジメタン誘導体、アントロン誘導体、ジフェニルキノン誘導体、チオピランジオキシド誘導体、カルボジイミド誘導体、フルオレニリデンメタン誘導体、ジスチリルピラジン誘導体、ナフタレン、ペリレン等の芳香環テトラカルボン酸無水物、フタロシアニン誘導体、８－キノリノール誘導体の金属錯体やメタルフタロシアニン、ベンゾオキサゾールやベンゾチアゾールを配位子とする金属錯体に代表される各種金属錯体、シロールに代表される有機シラン誘導体、等を含有する層であることが好ましい。 (Electron injection layer, electron transport layer)
The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. The electron injection material and the electron transport material used for these layers may be a low molecular compound or a high molecular compound.
As the electron transport material, a compound represented by any one of the general formulas (1) to (3) of the present invention can be used. Other materials include pyridine derivatives, quinoline derivatives, pyrimidine derivatives, pyrazine derivatives, phthalazine derivatives, phenanthroline derivatives, triazine derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, Metal complexes of anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthalene, perylene, and other aromatic ring tetracarboxylic anhydrides, phthalocyanine derivatives, 8-quinolinol derivatives And metal phthalocyanines, various metal complexes represented by metal complexes with benzoxazole and benzothiazole ligands, It is preferable that a layer containing a silane derivative, and the like.
　電子注入層、電子輸送層の厚さは、駆動電圧を下げるという観点から、各々５００ｎｍ以下であることが好ましい。
　電子輸送層の厚さとしては、１ｎｍ～５００ｎｍであるのが好ましく、５ｎｍ～２００ｎｍであるのがより好ましく、１０ｎｍ～１００ｎｍであるのが更に好ましい。また、電子注入層の厚さとしては、０．１ｎｍ～２００ｎｍであるのが好ましく、０．２ｎｍ～１００ｎｍであるのがより好ましく、０．５ｎｍ～５０ｎｍであるのが更に好ましい。
　電子注入層、電子輸送層は、上述した材料の１種又は２種以上からなる単層構造であってもよいし、同一組成又は異種組成の複数層からなる多層構造であってもよい。　 The thicknesses of the electron injection layer and the electron transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the electron transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm. The thickness of the electron injection layer is preferably from 0.1 nm to 200 nm, more preferably from 0.2 nm to 100 nm, and even more preferably from 0.5 nm to 50 nm.
The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
　電子注入層には電子供与性ドーパントを含有することが好ましい。電子注入層に電子供与性ドーパントを含有させることにより、電子注入性が向上し、駆動電圧が低下する、効率が向上するなどの効果がある。電子供与性ドーパントとは、ドープされる材料に電子を与え、ラジカルアニオンを発生させることが可能な材料であれば有機材料、無機材料のうちいかなるものでもよいが、例えば、テトラチアフルバレン（ＴＴＦ）、テトラチアナフタセン（ＴＴＴ）、ビス－［１，３　ジエチル－２－メチル－１，２－ジヒドロベンズイミダゾリル］などのジヒドロイミダゾール化合物、リチウム、セシウムなどが挙げられる。 The electron injection layer preferably contains an electron donating dopant. By including an electron donating dopant in the electron injection layer, the electron injection property is improved, the driving voltage is lowered, and the efficiency is improved. The electron donating dopant may be any organic material or inorganic material as long as it can give electrons to the doped material and generate radical anions. For example, tetrathiafulvalene (TTF) And dithiaimidazole compounds such as tetrathianaphthacene (TTT) and bis- [1,3 diethyl-2-methyl-1,2-dihydrobenzimidazolyl], lithium and cesium.
　電子注入層中の電子供与性ドーパントは、電子注入層を形成する全化合物質量に対して、０．０１質量％～５０質量％含有されることが好ましく、０．１質量％～４０質量％含有されることがより好ましく、０．５質量％～３０質量％含有されることがより好ましい。 The electron donating dopant in the electron injection layer is preferably contained in an amount of 0.01% by mass to 50% by mass, and 0.1% by mass to 40% by mass with respect to the total mass of the compound forming the electron injection layer. More preferably, the content is 0.5 to 30% by mass.
（正孔ブロック層）
　正孔ブロック層は、陽極側から発光層に輸送された正孔が、陰極側に通りぬけることを防止する機能を有する層である。本発明において、発光層と陰極側で隣接する有機層として、正孔ブロック層を設けることができる。
　正孔ブロック層を構成する有機化合物の例としては、アルミニウム（ＩＩＩ）ビス（２－メチル－８－キノリノラート）４－フェニルフェノレート（Ａｌｕｍｉｎｕｍ　（ＩＩＩ）ｂｉｓ（２－ｍｅｔｈｙｌ－８－ｑｕｉｎｏｌｉｎａｔｏ）４－ｐｈｅｎｙｌｐｈｅｎｏｌａｔｅ（Ｂａｌｑと略記する））等のアルミニウム錯体、トリアゾール誘導体、２，９－ジメチル－４，７－ジフェニル－１，１０－フェナントロリン（２，９－Ｄｉｍｅｔｈｙｌ－４，７－ｄｉｐｈｅｎｙｌ－１，１０－ｐｈｅｎａｎｔｈｒｏｌｉｎｅ（ＢＣＰと略記する））等のフェナントロリン誘導体、等が挙げられる。
　正孔ブロック層の厚さとしては、１ｎｍ～５００ｎｍであるのが好ましく、５ｎｍ～２００ｎｍであるのがより好ましく、１０ｎｍ～１００ｎｍであるのが更に好ましい。
　正孔ブロック層は、上述した材料の一種又は二種以上からなる単層構造であってもよいし、同一組成又は異種組成の複数層からなる多層構造であってもよい。 (Hole blocking layer)
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic layer adjacent to the light emitting layer on the cathode side.
Examples of organic compounds constituting the hole blocking layer include aluminum (III) bis (2-methyl-8-quinolinolato) 4-phenylphenolate (Aluminum (III) bis (2-methyl-8-quinolinato) 4- aluminum complexes such as phenylphenolate (abbreviated as Balq)), triazole derivatives, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (2,9-dimethyl-4,7-diphenyl-1,10-) phenanthroline derivatives such as phenanthroline (abbreviated as BCP)) and the like.
The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
The hole blocking layer may have a single layer structure made of one or more of the materials described above, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions.
（電子ブロック層）
　電子ブロック層は、陰極側から発光層に輸送された電子が、陽極側に通りぬけることを防止する機能を有する層である。本発明において、発光層と陽極側で隣接する有機層として、電子ブロック層を設けることができる。
　電子ブロック層を構成する有機化合物の例としては、例えば前述の正孔輸送材料として挙げたものが適用できる。
　電子ブロック層の厚さとしては、１ｎｍ～５００ｎｍであるのが好ましく、５ｎｍ～２００ｎｍであるのがより好ましく、１０ｎｍ～１００ｎｍであるのが更に好ましい。
　電子ブロック層は、上述した材料の一種又は二種以上からなる単層構造であってもよいし、同一組成又は異種組成の複数層からなる多層構造であってもよい。 (Electronic block layer)
The electron blocking layer is a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side. In the present invention, an electron blocking layer can be provided as an organic layer adjacent to the light emitting layer on the anode side.
As an example of the organic compound constituting the electron blocking layer, for example, those mentioned as the hole transport material described above can be applied.
The thickness of the electron blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
The electron blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
（保護層）
　本発明において、有機ＥＬ素子全体は、保護層によって保護されていてもよい。
　保護層については、特開２００８－２７０７３６号公報の段落番号〔０１６９〕～〔０１７０〕に記載の事項を本発明に適用することができる。 (Protective layer)
In the present invention, the entire organic EL element may be protected by a protective layer.
As for the protective layer, the matters described in JP-A-2008-270736, paragraphs [0169] to [0170] can be applied to the present invention.
（封止容器）
　本発明の素子は、封止容器を用いて素子全体を封止してもよい。
　封止容器については、特開２００８－２７０７３６号公報の段落番号〔０１７１〕に記載の事項を本発明に適用することができる。 (Sealing container)
The element of this invention may seal the whole element using a sealing container.
Regarding the sealing container, the matters described in paragraph [0171] of JP-A-2008-270736 can be applied to the present invention.
（駆動）
　本発明の有機電界発光素子は、陽極と陰極との間に直流（必要に応じて交流成分を含んでもよい）電圧（通常２ボルト～１５ボルト）、又は直流電流を印加することにより、発光を得ることができる。
　本発明の有機電界発光素子の駆動方法については、特開平２－１４８６８７号、同６－３０１３５５号、同５－２９０８０号、同７－１３４５５８号、同８－２３４６８５号、同８－２４１０４７号の各公報、特許第２７８４６１５号、米国特許５８２８４２９号、同６０２３３０８号の各明細書等に記載の駆動方法を適用することができる。 (Drive)
The organic electroluminescence device of the present invention emits light by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. Obtainable.
The driving method of the organic electroluminescence device of the present invention is described in JP-A-2-148687, JP-A-6-301355, JP-A-5-290080, JP-A-7-134558, JP-A-8-234585, and JP-A-8-2441047. The driving methods described in each publication, Japanese Patent No. 2784615, US Pat. Nos. 5,828,429 and 6,023,308 can be applied.
　本発明の有機電界発光素子の外部量子効率としては、７％以上が好ましく、１０％以上がより好ましく、１２％以上が更に好ましい。外部量子効率の数値は２０℃で素子を駆動したときの外部量子効率の最大値、若しくは、２０℃で素子を駆動したときの３００～４００ｃｄ／ｍ２付近での外部量子効率の値を用いることができる。 The external quantum efficiency of the organic electroluminescent element of the present invention is preferably 7% or more, more preferably 10% or more, and further preferably 12% or more. The value of the external quantum efficiency should be the maximum value of the external quantum efficiency when the device is driven at 20 ° C., or the value of the external quantum efficiency around 300 to 400 cd / m 2 when the device is driven at 20 ° C. Can do.
　本発明の有機電界発光素子の内部量子効率は、３０％以上であることが好ましく、５０％以上が更に好ましく、７０％以上が更に好ましい。素子の内部量子効率は、外部量子効率を光取り出し効率で除して算出される。通常の有機ＥＬ素子では光取り出し効率は約２０％であるが、基板の形状、電極の形状、有機層の膜厚、無機層の膜厚、有機層の屈折率、無機層の屈折率等を工夫することにより、光取り出し効率を２０％以上にすることが可能である。 The internal quantum efficiency of the organic electroluminescence device of the present invention is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more. The internal quantum efficiency of the device is calculated by dividing the external quantum efficiency by the light extraction efficiency. In a normal organic EL element, the light extraction efficiency is about 20%. However, the shape of the substrate, the shape of the electrode, the thickness of the organic layer, the thickness of the inorganic layer, the refractive index of the organic layer, the refractive index of the inorganic layer, etc. By devising it, it is possible to increase the light extraction efficiency to 20% or more.
（本発明の素子の用途）
　本発明の素子は、表示素子、ディスプレイ、バックライト、電子写真、照明光源、記録光源、露光光源、読み取り光源、標識、看板、インテリア、又は光通信等に好適に利用できる。特に、照明装置、表示装置等の発光輝度が高い領域で駆動されるデバイスに好ましく用いられる。 (Use of the element of the present invention)
The element of the present invention can be suitably used for a display element, a display, a backlight, electrophotography, an illumination light source, a recording light source, an exposure light source, a reading light source, a sign, a signboard, an interior, or optical communication. In particular, it is preferably used for a device driven in a region having a high light emission luminance such as a lighting device and a display device.
（発光装置）
　次に、図２を参照して本発明の発光装置について説明する。
　本発明の発光装置は、前記有機電界発光素子を用いてなる。
　図２は、本発明の発光装置の一例を概略的に示した断面図である。図２の発光装置２０は、基板（支持基板）２、有機電界発光素子１０、封止容器１６等により構成されている。 (Light emitting device)
Next, the light emitting device of the present invention will be described with reference to FIG.
The light emitting device of the present invention uses the organic electroluminescent element.
FIG. 2 is a cross-sectional view schematically showing an example of the light emitting device of the present invention. The light-emitting device 20 of FIG. 2 is comprised by the board | substrate (support substrate) 2, the organic electroluminescent element 10, the sealing container 16, etc. FIG.
　有機電界発光素子１０は、基板２上に、陽極（第一電極）３、有機層１１、陰極（第二電極）９が順次積層されて構成されている。また、陰極９上には、保護層１２が積層されており、更に、保護層１２上には接着層１４を介して封止容器１６が設けられている。なお、各電極３、９の一部、隔壁、絶縁層等は省略されている。
　ここで、接着層１４としては、エポキシ樹脂等の光硬化型接着剤や熱硬化型接着剤を用いることができ、例えば熱硬化性の接着シートを用いることもできる。 The organic electroluminescent device 10 is configured by sequentially laminating an anode (first electrode) 3, an organic layer 11, and a cathode (second electrode) 9 on a substrate 2. A protective layer 12 is laminated on the cathode 9, and a sealing container 16 is provided on the protective layer 12 with an adhesive layer 14 interposed therebetween. In addition, a part of each electrode 3 and 9, a partition, an insulating layer, etc. are abbreviate | omitted.
Here, as the adhesive layer 14, a photocurable adhesive such as an epoxy resin or a thermosetting adhesive can be used, and for example, a thermosetting adhesive sheet can also be used.
　本発明の発光装置の用途は特に制限されるものではなく、例えば、照明装置のほか、テレビ、パーソナルコンピュータ、携帯電話、電子ペーパ等の表示装置とすることができる。 The use of the light-emitting device of the present invention is not particularly limited, and for example, it can be a display device such as a television, a personal computer, a mobile phone, and electronic paper in addition to a lighting device.
（照明装置）
　次に、図３を参照して本発明の照明装置について説明する。
　図３は、本発明の照明装置の一例を概略的に示した断面図である。本発明の照明装置４０は、図３に示すように、前述した有機ＥＬ素子１０と、光散乱部材３０とを備えている。より具体的には、照明装置４０は、有機ＥＬ素子１０の基板２と光散乱部材３０とが接触するように構成されている。
　光散乱部材３０は、光を散乱できるものであれば特に制限されないが、図３においては、透明基板３１に微粒子３２が分散した部材とされている。透明基板３１としては、例えば、ガラス基板を好適に挙げることができる。微粒子３２としては、透明樹脂微粒子を好適に挙げることができる。ガラス基板及び透明樹脂微粒子としては、いずれも、公知のものを使用できる。このような照明装置４０は、有機電界発光素子１０からの発光が散乱部材３０の光入射面３０Ａに入射されると、入射光を光散乱部材３０により散乱させ、散乱光を光出射面３０Ｂから照明光として出射するものである。 (Lighting device)
Next, the illumination device of the present invention will be described with reference to FIG.
FIG. 3 is a cross-sectional view schematically showing an example of the illumination device of the present invention. As shown in FIG. 3, the illumination device 40 of the present invention includes the organic EL element 10 and the light scattering member 30 described above. More specifically, the lighting device 40 is configured such that the substrate 2 of the organic EL element 10 and the light scattering member 30 are in contact with each other.
The light scattering member 30 is not particularly limited as long as it can scatter light. In FIG. 3, the light scattering member 30 is a member in which fine particles 32 are dispersed on a transparent substrate 31. As the transparent substrate 31, for example, a glass substrate can be preferably cited. As the fine particles 32, transparent resin fine particles can be preferably exemplified. As the glass substrate and the transparent resin fine particles, known ones can be used. In such an illuminating device 40, when light emitted from the organic electroluminescent element 10 is incident on the light incident surface 30A of the scattering member 30, the incident light is scattered by the light scattering member 30, and the scattered light is emitted from the light emitting surface 30B. It is emitted as illumination light.
　以下、実施例により本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
１．合成例
（合成例１）化合物３の合成 1. Synthesis Example (Synthesis Example 1) Synthesis of Compound 3
Figure JPOXMLDOC01-appb-C000087
Figure JPOXMLDOC01-appb-C000087
　３，５－ジブロモベンゾニトリル１０．０ｇ（３８．３ｍｍｏｌ）、フェニルボロン酸４．６ｇ（３８．３ｍｍｏｌ）、酢酸パラジウム０．２２ｇ（１．０ｍｍｏｌ）、トリフェニルホスフィン０．９１ｇ（４．０ｍｍｏｌ）、炭酸ナトリウム１０．６ｇ（１００ｍｍｏｌ）、１，２－ジメトキシエタン（ＤＭＥ）２００ｍＬ、純水２００ｍＬを混合し、窒素雰囲気下、４時間加熱還流した。反応液を室温に冷却した後、析出した固体を濾過し、純水、エタノール、ヘキサンで順次洗浄した。得られた固体をエタノールでたき洗いし、乾燥することにより合成中間体Ａを６．４２ｇ（２４．９ｍｍｏｌ）得た（収率６５％）。
　合成中間体Ａ６．４０ｇ（２４．８ｍｍｏｌ）、ビス（ピナコラート）ジボロン７．５７ｇ（２９．８ｍｍｏｌ）、［１，１’－ビス（ジフェニルホスフィノ）フェロセン］パラジウム（ＩＩ）ジクロリド　ジクロロメタン錯体　（１：１）０．６１ｇ（０．７４ｍｍｏｌ）、酢酸カリウム７．３０ｇ（７４．４ｍｍｏｌ）、ジメチルアセトアミド（ＤＭＡｃ）１００ｍＬを混合し、窒素雰囲気下７０℃で４時間混合した。室温に冷却した反応液を氷水に添加し、析出した固体を濾過し、純水、エタノール、ヘキサンで順次洗浄した。得られた固体をエタノールでたき洗いし、乾燥することにより合成中間体Ｂを５．５８ｇ（１８．３ｍｍｏｌ）得た（収率７４％）。
　合成中間体Ｂ５．００ｇ（１６．４ｍｍｏｌ）、１，３，５－トリブロモベンゼン１．６４ｇｇ（５．２１ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（０）０．３６ｇ（０．３９ｍｍｏｌ）、２－ジシクロヘキシルホスフィノ－２’，６’－ジメトキシビフェニル（ＳＰｈｏｓ）０．６４ｇ（１．５６ｍｍｏｌ）、リン酸三カリウム６．６４ｇ（３１．３ｍｍｏｌ）、ベンゾニトリル５０ｍＬ、純水２５ｍＬを混合し、窒素雰囲気下、１２０℃で６時間攪拌した。反応液を室温に放冷後、酢酸エチルを添加して有機層を抽出後、無水硫酸マグネシウムで乾燥した。酢酸エチルを減圧留去してベンゾニトリル溶液とした後、エタノールを加え、析出した沈殿を濾取した。得られた固体をトルエンで再結晶することにより２．２６ｇ（３．７０ｍｍｏｌ）の化合物３を得た（収率７１％）。
　１Ｈ　ＮＭＲ（４００ＭＨｚ，ｉｎ　ＤＭＳＯ－ｄ６）；δ（ｐｐｍ）＝８．５２－８．５１（ｍ、６Ｈ），８．３６（ｓ，３Ｈ），８．２０（ｓ，３Ｈ），７．９１（ｄ，Ｊ＝７．２Ｈｚ，６Ｈ），７．５６－７．４５（ｍ，９Ｈ）．ＭＳ（ＭＡＬＤＩ－ＴＯＦ）：ｍ／ｚ＝６１０．２（［Ｍ＋Ｈ］＋）． 3,5-dibromobenzonitrile 10.0 g (38.3 mmol), phenylboronic acid 4.6 g (38.3 mmol), palladium acetate 0.22 g (1.0 mmol), triphenylphosphine 0.91 g (4.0 mmol) Sodium carbonate 10.6 g (100 mmol), 1,2-dimethoxyethane (DME) 200 mL, and pure water 200 mL were mixed and heated to reflux for 4 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, the precipitated solid was filtered and washed successively with pure water, ethanol and hexane. The obtained solid was washed with ethanol and dried to obtain 6.42 g (24.9 mmol) of synthetic intermediate A (yield 65%).
Synthetic intermediate A 6.40 g (24.8 mmol), bis (pinacolato) diboron 7.57 g (29.8 mmol), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane complex (1: 1) 0.61 g (0.74 mmol), 7.30 g (74.4 mmol) of potassium acetate and 100 mL of dimethylacetamide (DMAc) were mixed and mixed at 70 ° C. for 4 hours under a nitrogen atmosphere. The reaction liquid cooled to room temperature was added to ice water, the precipitated solid was filtered, and washed successively with pure water, ethanol, and hexane. The obtained solid was washed with ethanol and dried to obtain 5.58 g (18.3 mmol) of synthetic intermediate B (yield 74%).
Synthesis intermediate B5.00 g (16.4 mmol), 1,3,5-tribromobenzene 1.64 gg (5.21 mmol), tris (dibenzylideneacetone) dipalladium (0) 0.36 g (0.39 mmol), 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (SPhos) 0.64 g (1.56 mmol), tripotassium phosphate 6.64 g (31.3 mmol), benzonitrile 50 mL, pure water 25 mL were mixed, The mixture was stirred at 120 ° C. for 6 hours under a nitrogen atmosphere. The reaction solution was allowed to cool to room temperature, ethyl acetate was added to extract the organic layer, and then dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure to obtain a benzonitrile solution, ethanol was added, and the deposited precipitate was collected by filtration. The obtained solid was recrystallized from toluene to obtain 2.26 g (3.70 mmol) of Compound 3 (yield 71%).
1 H NMR (400 MHz, in DMSO-d6); δ (ppm) = 8.52-8.51 (m, 6H), 8.36 (s, 3H), 8.20 (s, 3H), 7. 91 (d, J = 7.2 Hz, 6H), 7.56-7.45 (m, 9H). MS (MALDI-TOF): m / z = 610.2 ([M + H] + ).
（合成例２～１１）化合物１、２、４～１１の合成
　以下に示すスキームにより化合物１、２、４～１１を合成した。反応条件や精製操作は合成例１に準ずる。 Synthesis Examples 2 to 11 Synthesis of Compounds 1, 2, 4 to 11 Compounds 1, 2, 4 to 11 were synthesized according to the scheme shown below. Reaction conditions and purification operations are the same as in Synthesis Example 1.
Figure JPOXMLDOC01-appb-C000088
Figure JPOXMLDOC01-appb-C000088
Figure JPOXMLDOC01-appb-C000089
Figure JPOXMLDOC01-appb-C000089
Figure JPOXMLDOC01-appb-C000090
Figure JPOXMLDOC01-appb-C000090
Figure JPOXMLDOC01-appb-C000091
Figure JPOXMLDOC01-appb-C000091
Figure JPOXMLDOC01-appb-C000092
Figure JPOXMLDOC01-appb-C000092
Figure JPOXMLDOC01-appb-C000093
Figure JPOXMLDOC01-appb-C000093
Figure JPOXMLDOC01-appb-C000094
Figure JPOXMLDOC01-appb-C000094
Figure JPOXMLDOC01-appb-C000095
Figure JPOXMLDOC01-appb-C000095
Figure JPOXMLDOC01-appb-C000096
Figure JPOXMLDOC01-appb-C000096
Figure JPOXMLDOC01-appb-C000097
Figure JPOXMLDOC01-appb-C000097
　合成した化合物１、２、４～１１の１Ｈ　ＮＭＲ及び／又はＭＳ（ＭＡＬＤＩ－ＴＯＦ）の測定結果を以下に記載する。
化合物１
　１Ｈ　ＮＭＲ（４００ＭＨｚ，ｉｎ　ＤＭＳＯ－ｄ６）；δ（ｐｐｍ）＝８．３７（ｓ，２Ｈ），８．１９（ｓ，２Ｈ），８．０９（ｓ，４Ｈ），８．０４（ｓ，２Ｈ），７．９８（ｓ，１Ｈ），７．９３－７．８７（ｍ，１２Ｈ），７．５６－７．３７（ｍ，１８Ｈ）．ＭＳ（ＭＡＬＤＩ－ＴＯＦ）：ｍ／ｚ＝７８８．３（［Ｍ＋Ｈ］＋）．
化合物２
　１Ｈ　ＮＭＲ（４００ＭＨｚ，ｉｎ　ＤＭＳＯ－ｄ６）；δ（ｐｐｍ）＝８．１５　（ｓ，３Ｈ），７．９３（ｔ，Ｊ＝７．７Ｈｚ，３Ｈ），７．８２（ｄ，Ｊ＝７．７Ｈｚ，３Ｈ），７．７２－７．６５（ｍ，９Ｈ），７．５８－７．４８（ｍ，９Ｈ）．ＭＳ（ＭＡＬＤＩ－ＴＯＦ）：ｍ／ｚ＝６１０．２（［Ｍ＋Ｈ］＋）． The measurement results of 1 H NMR and / or MS (MALDI-TOF) of the synthesized compounds 1, 2, 4 to 11 are described below.
Compound 1
1 H NMR (400 MHz, in DMSO-d6); δ (ppm) = 8.37 (s, 2H), 8.19 (s, 2H), 8.09 (s, 4H), 8.04 (s, 2H), 7.98 (s, 1H), 7.93-7.87 (m, 12H), 7.56-7.37 (m, 18H). MS (MALDI-TOF): m / z = 788.3 ([M + H] + ).
Compound 2
1 H NMR (400 MHz, in DMSO-d6); δ (ppm) = 8.15 (s, 3H), 7.93 (t, J = 7.7 Hz, 3H), 7.82 (d, J = 7 .7 Hz, 3H), 7.72-7.65 (m, 9H), 7.58-7.48 (m, 9H). MS (MALDI-TOF): m / z = 610.2 ([M + H] + ).
化合物４
　１Ｈ　ＮＭＲ（４００ＭＨｚ，ｉｎ　ＤＭＳＯ－ｄ６）；δ（ｐｐｍ）＝８．５１（ｓ，４Ｈ），８．３６（ｓ，１Ｈ），８．３３（ｄ，Ｊ＝８．４Ｈｚ，４Ｈ），８．１９－８．１８（ｍ，４Ｈ），８．１５（ｓ，２Ｈ），８．００－７．９８（ｍ，２Ｈ），７．８９（ｄ，Ｊ＝８．４Ｈｚ，４Ｈ），７．７４－７．７１（ｍ，４Ｈ），７．６９－７．６６（ｍ，１Ｈ）．ＭＳ（ＭＡＬＤＩ－ＴＯＦ）：ｍ／ｚ＝６３５．２（［Ｍ＋Ｈ］＋）．
化合物５
　ＭＳ（ＭＡＬＤＩ－ＴＯＦ）：ｍ／ｚ＝６６１．３（［Ｍ＋Ｈ］＋）．
化合物６
　ＭＳ（ＭＡＬＤＩ－ＴＯＦ）：ｍ／ｚ＝９３８．３（［Ｍ＋Ｈ］＋）．
化合物７
　ＭＳ（ＭＡＬＤＩ－ＴＯＦ）：ｍ／ｚ＝７２０．４（［Ｍ＋Ｈ］＋）．
化合物８
　ＭＳ（ＭＡＬＤＩ－ＴＯＦ）：ｍ／ｚ＝６４１．３（［Ｍ＋Ｈ］＋）．
化合物９
　ＭＳ（ＭＡＬＤＩ－ＴＯＦ）：ｍ／ｚ＝６９１．３（［Ｍ＋Ｈ］＋）．
化合物１０
　ＭＳ（ＭＡＬＤＩ－ＴＯＦ）：ｍ／ｚ＝６１２．２（［Ｍ＋Ｈ］＋）．
化合物１１
　１Ｈ　ＮＭＲ（４００ＭＨｚ，ｉｎ　ＤＭＳＯ－ｄ６）；δ（ｐｐｍ）＝８．３５（ｓ，３Ｈ），８．２３－８．１６（ｍ，９Ｈ），７．９９（ｄ，Ｊ＝７．６Ｈｚ，３Ｈ），７．８６（ｄ，Ｊ＝７．６Ｈｚ，３Ｈ），７．８１（ｄ，Ｊ＝７．６Ｈｚ，３Ｈ），７．７２－７．６４（ｍ，６Ｈ）．ＭＳ（ＭＡＬＤＩ－ＴＯＦ）：ｍ／ｚ＝６１０．２（［Ｍ＋Ｈ］＋）． Compound 4
1 H NMR (400 MHz, in DMSO-d6); δ (ppm) = 8.51 (s, 4H), 8.36 (s, 1H), 8.33 (d, J = 8.4 Hz, 4H), 8.19-8.18 (m, 4H), 8.15 (s, 2H), 8.00-7.98 (m, 2H), 7.89 (d, J = 8.4 Hz, 4H), 7.74-7.71 (m, 4H), 7.69-7.66 (m, 1H). MS (MALDI-TOF): m / z = 635.2 ([M + H] + ).
Compound 5
MS (MALDI-TOF): m / z = 661.3 ([M + H] + ).
Compound 6
MS (MALDI-TOF): m / z = 938.3 ([M + H] + ).
Compound 7
MS (MALDI-TOF): m / z = 720.4 ([M + H] + ).
Compound 8
MS (MALDI-TOF): m / z = 641.3 ([M + H] + ).
Compound 9
MS (MALDI-TOF): m / z = 691.3 ([M + H] + ).
Compound 10
MS (MALDI-TOF): m / z = 612.2 ([M + H] + ).
Compound 11
1 H NMR (400 MHz, in DMSO-d6); δ (ppm) = 8.35 (s, 3H), 8.23-8.16 (m, 9H), 7.9 (d, J = 7.6 Hz) 3H), 7.86 (d, J = 7.6 Hz, 3H), 7.81 (d, J = 7.6 Hz, 3H), 7.72-7.64 (m, 6H). MS (MALDI-TOF): m / z = 610.2 ([M + H] + ).
　以上のように合成し、実施例で使用した化合物１～１１を、同じく実施例で使用した比較化合物１～１１と共に、以下に示す。 The compounds 1 to 11 synthesized as described above and used in the examples are shown below together with the comparative compounds 1 to 11 used in the examples.
Figure JPOXMLDOC01-appb-C000098
Figure JPOXMLDOC01-appb-C000098
Figure JPOXMLDOC01-appb-C000099
Figure JPOXMLDOC01-appb-C000099
２．素子作製・評価
　素子作製に用いた材料は全て昇華精製を行い、高速液体クロマトグラフィー（東ソーＴＳＫｇｅｌ　ＯＤＳ－１００Ｚ）により純度（２５４ｎｍの吸収強度面積比）が９９．９％以上であることを確認した。なお、比較化合物１０及び比較化合物１１は昇華より先に熱分解が起こってしまったため、昇華精製や真空蒸着による成膜が不可能だった。また、溶媒への溶解性も極めて低く、実施例９の条件では塗布成膜することができなかった。
　なお以下の実施例の見出しの横に記載される括弧書きは、発光色及び本発明の化合物をどの材料として使用したかを示す。ここで「ホスト」はホスト材料、「ＥＴＬ」は電子輸送材料、「ＥＩＬ」は電子注入材料としての使用をそれぞれ意味する。 2. Element fabrication / evaluation All materials used for element fabrication were subjected to sublimation purification, and it was confirmed by high performance liquid chromatography (Tosoh TSKgel ODS-100Z) that purity (254 nm absorption intensity area ratio) was 99.9% or more. . In addition, since the comparative compound 10 and the comparative compound 11 had undergone thermal decomposition prior to sublimation, film formation by sublimation purification or vacuum deposition was impossible. Further, the solubility in a solvent was extremely low, and it was impossible to form a coating film under the conditions of Example 9.
In addition, the parentheses written next to the headings of the following examples indicate the emission color and which material the compound of the present invention was used. Here, “host” means use as a host material, “ETL” means use as an electron transport material, and “EIL” means use as an electron injection material.
（実施例１）（緑ＥＴＬ、ＥＩＬ）
　厚み０．５ｍｍ、２．５ｃｍ角のＩＴＯ膜を有するガラス基板（ジオマテック社製、表面抵抗１０Ω／□）を洗浄容器に入れ、２－プロパノール中で超音波洗浄した後、３０分間ＵＶ－オゾン処理を行った。この透明陽極（ＩＴＯ膜）上に真空蒸着法にて以下の有機層を順次蒸着した。
第１層：ＧＤ－１　：膜厚１０ｎｍ
第２層：ＮＰＤ　：膜厚２５ｎｍ
第３層：ＨＴ－１　：膜厚３ｎｍ
第４層：ｍＣＢＰ及びＧＤ－１（質量比９０：１０）　：膜厚３０ｎｍ
第５層：比較化合物１　：膜厚５ｎｍ
第６層：Ａｌｑ　：膜厚４５ｎｍ
　この上に、フッ化リチウム０．１ｎｍ及び金属アルミニウム１００ｎｍをこの順に蒸着し陰極とした。
　このものを、大気に触れさせることなく、窒素ガスで置換したグローブボックス内に入れ、ガラス製の封止缶及び紫外線硬化型の接着剤（ＸＮＲ５５１６ＨＶ、長瀬チバ（株）製）を用いて封止し、比較素子１－１を得た。同様に、第５層の材料として比較化合物１の代わりに表１中に示す材料を用い、かつ、第６層の材料として表１中に示す材料を用いることにより、素子１－１～１－１０、比較素子１－２～１－９を得た。これらの素子を以下の方法で効率、駆動電圧、高温保管後の効率変化、高温保管後の色度変化、高温保管後の耐久性の観点で評価した結果を表１に示す。 (Example 1) (Green ETL, EIL)
A glass substrate having a thickness of 0.5 mm and a 2.5 cm square ITO film (manufactured by Geomat Co., Ltd., surface resistance 10 Ω / □) is placed in a cleaning container, subjected to ultrasonic cleaning in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes. Went. The following organic layers were sequentially deposited on the transparent anode (ITO film) by vacuum deposition.
First layer: GD-1: film thickness 10 nm
Second layer: NPD: film thickness 25 nm
Third layer: HT-1: film thickness 3 nm
Fourth layer: mCBP and GD-1 (mass ratio 90:10): film thickness 30 nm
Fifth layer: Comparative compound 1: film thickness 5 nm
Sixth layer: Alq: film thickness 45 nm
On top of this, 0.1 nm of lithium fluoride and 100 nm of metallic aluminum were vapor-deposited in this order to form a cathode.
This is put in a glove box substituted with nitrogen gas without being exposed to the atmosphere, and sealed using a glass sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.). Thus, a comparative element 1-1 was obtained. Similarly, by using the material shown in Table 1 instead of the comparative compound 1 as the material of the fifth layer and using the material shown in Table 1 as the material of the sixth layer, the elements 1-1 to 1- 10. Comparative elements 1-2 to 1-9 were obtained. Table 1 shows the results of evaluating these elements by the following methods from the viewpoints of efficiency, driving voltage, efficiency change after high temperature storage, chromaticity change after high temperature storage, and durability after high temperature storage.
（ａ）　効率
　東陽テクニカ製ソースメジャーユニット２４００を用いて、直流電圧を各素子に印加し発光させ、その輝度をトプコン社製輝度計ＢＭ－８を用いて測定した。発光スペクトルと発光波長は浜松ホトニクス製スペクトルアナライザーＰＭＡ－１１を用いて測定した。これらを元に輝度が１０００ｃｄ／ｍ２付近の外部量子効率を輝度換算法により算出した。効率は数字が大きいほど好ましい。
（ｂ）　駆動電圧
　各素子を輝度が１０００ｃｄ／ｍ２になるように直流電圧を印加して発光させる。この時の印加電圧を駆動電圧評価の指標とした。駆動電圧は数字が小さいほど好ましい。
（ｃ）　高温保管後の効率変化
　各素子を１００℃の恒温槽中で２４時間保管した後、室温で輝度が１０００ｃｄ／ｍ２になるように直流電圧を印加して発光させる。この時の外部量子効率η１００を室温下で発光させた時の外部量子効率ηＲＴと比較し、両者の比（η１００／ηＲＴ）を高輝度駆動時の効率変化の指標とした。この値は大きいほど好ましい。
（ｄ）　高温保管後の色度変化
　各素子を１００℃の恒温槽中で２４時間保管した後、室温で輝度が１０００ｃｄ／ｍ２になるように直流電圧を印加して発光させる。この時の色度（ｘ、ｙ）を室温下で発光させた時の色度（ｘ、ｙ）と比較し、両者のｘ値、ｙ値の差を（Δｘ、Δｙ）の形で表記し、高輝度駆動時の色度変化の指標とした。Δｘ、Δｙの値はそれぞれ小さいほど好ましい。
（ｅ）　高温保管後の耐久性
　各素子を１００℃の恒温槽中で２４時間保管した後、室温で輝度が５０００ｃｄ／ｍ２になるように直流電圧を印加して発光させ続け、輝度が４０００ｃｄ／ｍ２になるまでに要した時間を耐久性の指標とした。以下に記載する表１～９において、各表の一番上に示した素子（即ち、素子１－１、２－１、３－１、４－１、５－１、６－１、７－１、８－１、９－１）の耐久性を１００とした場合の相対値で記載した。耐久性は数字が大きいほど好ましい。 (A) Efficiency Using a source measure unit 2400 manufactured by Toyo Technica, a DC voltage was applied to each element to emit light, and the luminance was measured using a luminance meter BM-8 manufactured by Topcon Corporation. The emission spectrum and emission wavelength were measured using a spectrum analyzer PMA-11 manufactured by Hamamatsu Photonics. Based on these, the external quantum efficiency at a luminance of around 1000 cd / m 2 was calculated by the luminance conversion method. The higher the number, the better the efficiency.
(B) Driving voltage Each element is caused to emit light by applying a DC voltage so that the luminance becomes 1000 cd / m 2 . The applied voltage at this time was used as an index for driving voltage evaluation. The driving voltage is preferably as small as possible.
(C) Change in efficiency after high-temperature storage Each element is stored in a thermostat at 100 ° C. for 24 hours, and then light is emitted by applying a DC voltage so that the luminance becomes 1000 cd / m 2 at room temperature. The external quantum efficiency η 100 at this time was compared with the external quantum efficiency η RT when light was emitted at room temperature, and the ratio between the two (η 100 / η RT ) was used as an index of the efficiency change during high-luminance driving. A larger value is more preferable.
(D) Change in chromaticity after high-temperature storage Each element is stored in a thermostat at 100 ° C. for 24 hours, and then light is emitted by applying a DC voltage so that the luminance becomes 1000 cd / m 2 at room temperature. The chromaticity (x, y) at this time is compared with the chromaticity (x, y) when light is emitted at room temperature, and the difference between the x value and y value is expressed in the form of (Δx, Δy). It was used as an index of chromaticity change during high brightness driving. Smaller values of Δx and Δy are preferable.
(E) Durability after high-temperature storage Each element was stored in a constant temperature bath at 100 ° C. for 24 hours, and then the device was made to emit light by applying a DC voltage so that the luminance was 5000 cd / m 2 at room temperature, and the luminance was 4000 cd. The time required to reach / m 2 was used as an index of durability. In Tables 1 to 9 described below, the elements shown at the top of each table (ie, the elements 1-1, 2-1, 3-1, 4-1, 5-1, 6-1, 7- The relative values are shown when the durability of 1,8-1, 9-1) is 100. The larger the number, the better the durability.
　なお、表１～９中、高温保管後の色度変化、耐久性の評価における記号「＜」及び「＞」は不等号を意味し、例えば高温保管後の色度変化における「＜０．００５」は、色度変化が０．００５未満であったことを意味する。 In Tables 1 to 9, the symbols “<” and “>” in the evaluation of chromaticity change and durability after high-temperature storage mean inequality signs, for example “<0.005” in chromaticity change after high-temperature storage. Means that the change in chromaticity was less than 0.005.
Figure JPOXMLDOC01-appb-T000100
Figure JPOXMLDOC01-appb-T000100
（実施例２）（緑ＥＴＬ）
　層構成を以下に示すものに変えた以外は実施例１と同様にして素子を作製し、表２に記載の項目について、実施例１と同様の評価を行った結果を表２に示す。
第１層：２－ＴＮＡＴＡ及びＦ４－ＴＣＮＱ（質量比９９．７：０．３）　：膜厚１６０ｎｍ
第２層：ＮＰＤ　：膜厚５ｎｍ
第３層：ＨＴ－２　：膜厚３ｎｍ
第４層：Ｈ－１及びＧＤ－２（質量比８５：１５）　：膜厚３０ｎｍ
第５層：表２中に記載の材料　：膜厚５ｎｍ
第６層：ＢＣＰ及びＬｉ（質量比９９．４：０．６）　：膜厚２５ｎｍ (Example 2) (Green ETL)
A device was fabricated in the same manner as in Example 1 except that the layer configuration was changed to the one shown below, and the results of performing the same evaluation as in Example 1 for the items described in Table 2 are shown in Table 2.
First layer: 2-TNATA and F 4 -TCNQ (mass ratio 99.7: 0.3): film thickness 160 nm
Second layer: NPD: film thickness 5 nm
Third layer: HT-2: film thickness 3 nm
Fourth layer: H-1 and GD-2 (mass ratio 85:15): film thickness 30 nm
Fifth layer: Materials listed in Table 2: Film thickness 5 nm
Sixth layer: BCP and Li (mass ratio 99.4: 0.6): film thickness 25 nm
Figure JPOXMLDOC01-appb-T000101
Figure JPOXMLDOC01-appb-T000101
　（実施例３）（青ＥＴＬ）
　層構成を以下に示すものに変えた以外は実施例１と同様にして素子を作製し、表３に記載の項目について、実施例１と同様の評価を行った結果を表３に示す。
第１層：ＣｕＰｃ　：膜厚１０ｎｍ
第２層：ＴＰＡＣ　：膜厚３０ｎｍ
第３層：Ｈ－２及びＢＤ－１（質量比９０：１０）　：膜厚３０ｎｍ
第４層：表３中に記載の材料　：膜厚５ｎｍ
第５層：ＥＴ－２　：膜厚２５ｎｍ (Example 3) (Blue ETL)
A device was fabricated in the same manner as in Example 1 except that the layer configuration was changed to the one shown below, and the results of the same evaluation as in Example 1 for the items shown in Table 3 are shown in Table 3.
First layer: CuPc: film thickness 10 nm
Second layer: TPAC: film thickness 30 nm
Third layer: H-2 and BD-1 (mass ratio 90:10): film thickness 30 nm
Fourth layer: Materials described in Table 3: Film thickness 5 nm
5th layer: ET-2: film thickness 25 nm
Figure JPOXMLDOC01-appb-T000102
Figure JPOXMLDOC01-appb-T000102
（実施例４）（青ＥＴＬ）
　層構成を以下に示すものに変えた以外は実施例１と同様にして素子を作製し、表４に記載の項目について、実施例１と同様の評価を行った結果を表４に示す。
第１層：２－ＴＮＡＴＡ及びＦ４－ＴＣＮＱ（質量比９９．７：０．３）　：膜厚１２０ｎｍ
第２層：ＮＰＤ　：膜厚７ｎｍ
第３層：ＨＴ－１　：膜厚３ｎｍ
第４層：Ｈ－３及びＢＤ－２（質量比８５：１５）　：膜厚３０ｎｍ
第５層：表４中に記載の材料　：膜厚５ｎｍ
第６層：ＢＡｌｑ　：膜厚２５ｎｍ (Example 4) (Blue ETL)
A device was fabricated in the same manner as in Example 1 except that the layer configuration was changed to the one shown below, and the results of the same evaluation as in Example 1 for the items shown in Table 4 are shown in Table 4.
First layer: 2-TNATA and F 4 -TCNQ (mass ratio 99.7: 0.3): film thickness 120 nm
Second layer: NPD: film thickness 7 nm
Third layer: HT-1: film thickness 3 nm
Fourth layer: H-3 and BD-2 (mass ratio 85:15): film thickness 30 nm
Fifth layer: Materials listed in Table 4: Film thickness 5 nm
Sixth layer: BAlq: film thickness 25 nm
Figure JPOXMLDOC01-appb-T000103
Figure JPOXMLDOC01-appb-T000103
（実施例５）（赤ＥＴＬ、ＥＩＬ）
　層構成を以下に示すものに変えた以外は実施例１と同様にして素子を作製し、実施例１と同様の評価を行った結果を表５に示す。
第１層：ＴＣＴＡ　：膜厚３０ｎｍ
第２層：ＤＴＡＳｉ　：膜厚１２ｎｍ
第３層：Ｈ－４及びＲＤ－１（質量比９０：１０）　：膜厚３０ｎｍ
第４層：表５中に記載の材料　：膜厚５ｎｍ
第５層：表５中に記載の材料　：膜厚５０ｎｍ (Example 5) (Red ETL, EIL)
Table 5 shows the results of fabricating the device in the same manner as in Example 1 except that the layer configuration was changed to the following, and performing the same evaluation as in Example 1.
First layer: TCTA: film thickness 30 nm
Second layer: DTASi: film thickness 12 nm
Third layer: H-4 and RD-1 (mass ratio 90:10): film thickness 30 nm
Fourth layer: Materials described in Table 5: Film thickness 5 nm
Fifth layer: Materials listed in Table 5: Film thickness 50 nm
Figure JPOXMLDOC01-appb-T000104
Figure JPOXMLDOC01-appb-T000104
　本発明の電荷輸送材料は電子注入及び輸送性、励起子及び電子に対する安定性、並びに、耐熱性に優れるため、電子輸送材料として用いると高効率、低電圧で、かつ、高温保管後の効率、色度、耐久性に優れた素子が得られることが分かった。 Since the charge transport material of the present invention is excellent in electron injection and transport properties, stability to excitons and electrons, and heat resistance, when used as an electron transport material, high efficiency, low voltage, and efficiency after high-temperature storage, It was found that an element excellent in chromaticity and durability can be obtained.
（実施例６）（緑ホスト、ＥＴＬ）
　層構成を以下に示すものに変えた以外は実施例１と同様にして素子を作製し、表６に記載の項目について、実施例１と同様の方法で評価した結果を表６に示す。
第１層：ＣｕＰｃ　：膜厚１０ｎｍ
第２層：ＮＰＤ　：膜厚２５ｎｍ
第３層：表６中に記載の材料　：膜厚５ｎｍ
第４層：表６中に記載のホスト材料及びＧＤ－３（質量比９０：１０）　：膜厚３０ｎｍ
第５層：表６中に記載の材料　：膜厚５ｎｍ
第６層：ＥＴ－３　：膜厚４０ｎｍ Example 6 (Green Host, ETL)
A device was produced in the same manner as in Example 1 except that the layer configuration was changed to the one shown below, and the results of evaluating the items described in Table 6 by the same method as in Example 1 are shown in Table 6.
First layer: CuPc: film thickness 10 nm
Second layer: NPD: film thickness 25 nm
Third layer: Materials listed in Table 6: Film thickness 5 nm
Fourth layer: Host material described in Table 6 and GD-3 (mass ratio 90:10): film thickness 30 nm
Fifth layer: Materials listed in Table 6: Film thickness 5 nm
Sixth layer: ET-3: film thickness 40 nm
Figure JPOXMLDOC01-appb-T000105
Figure JPOXMLDOC01-appb-T000105
（実施例７）（水色ホスト、ＥＴＬ）
　層構成を以下に示すものに変えた以外は実施例１と同様にして素子を作製し、表７に記載の項目について、実施例１と同様の方法で評価した結果を表７に示す。
第１層：ＬＧ１０１　：膜厚１０ｎｍ
第２層：ＮＰＤ　：膜厚１１５ｎｍ
第３層：表７中に記載の材料　：膜厚５ｎｍ
第４層：表７中に記載のホスト材料及びＦｉｒｐｉｃ（質量比９０：１０）　：膜厚３０ｎｍ
第５層：表７中に記載の材料　：膜厚５ｎｍ
第６層：ＥＴ－１　：膜厚２５ｎｍ (Example 7) (Light blue host, ETL)
A device was produced in the same manner as in Example 1 except that the layer configuration was changed to the one shown below, and the results of evaluating the items described in Table 7 by the same method as in Example 1 are shown in Table 7.
First layer: LG101: film thickness 10 nm
Second layer: NPD: film thickness 115 nm
Third layer: Materials described in Table 7: Film thickness 5 nm
Fourth layer: Host material and Firpic (mass ratio 90:10) described in Table 7: Film thickness 30 nm
Fifth layer: Materials listed in Table 7: Film thickness 5 nm
Sixth layer: ET-1: film thickness 25 nm
Figure JPOXMLDOC01-appb-T000106
Figure JPOXMLDOC01-appb-T000106
（実施例８）（赤ホスト、ＥＴＬ）
　層構成を以下に示すものに変えた以外は実施例１と同様にして素子を作製し、表８に記載の項目について、実施例１と同様の方法で評価した結果を表８に示す。
第１層：ＬＧ１０１　：膜厚１０ｎｍ
第２層：ＮＰＤ　：膜厚２７ｎｍ
第３層：表８中に記載の材料　：膜厚５ｎｍ
第４層：表８中に記載のホスト材料及びＲＤ－２（質量比９３：７）　：膜厚３０ｎｍ
第５層：表８中に記載の材料　：膜厚５ｎｍ
第６層：ＥＴ－４　：膜厚４９ｎｍ
第７層：ＢＣＰ　：１ｎｍ Example 8 (Red host, ETL)
A device was fabricated in the same manner as in Example 1 except that the layer configuration was changed to the one shown below, and the results of evaluating the items described in Table 8 by the same method as in Example 1 are shown in Table 8.
First layer: LG101: film thickness 10 nm
Second layer: NPD: film thickness 27 nm
Third layer: Materials listed in Table 8: Film thickness 5 nm
Fourth layer: host material described in Table 8 and RD-2 (mass ratio 93: 7): film thickness 30 nm
Fifth layer: Materials listed in Table 8: Film thickness 5 nm
Sixth layer: ET-4: film thickness 49 nm
7th layer: BCP: 1 nm
Figure JPOXMLDOC01-appb-T000107
Figure JPOXMLDOC01-appb-T000107
　本発明の電荷輸送材料は電子注入及び輸送性、励起子及び電子に対する安定性、並びに、耐熱性に優れるため、ホスト材料として用いると高効率、かつ、高温保管後の効率、色度、耐久性に優れた素子が得られる。 Since the charge transport material of the present invention is excellent in electron injection and transport properties, exciton and electron stability, and heat resistance, it is highly efficient when used as a host material, and efficiency, chromaticity and durability after storage at high temperatures. A device excellent in the above can be obtained.
（実施例９）（塗布、緑ホスト）
　厚み０．５ｍｍ、２．５ｃｍ角のＩＴＯ膜を有するガラス基板（ジオマテック社製、表面抵抗１０Ω／□）を洗浄容器に入れ、２－プロパノール中で超音波洗浄した後、３０分間ＵＶ－オゾン処理を行った。この透明陽極（ＩＴＯ膜）上にＰＥＤＯＴ（ポリ（３，４－エチレンジオキシチオフェン））／ＰＳＳ（ポリスチレンスルホン酸）水溶液（ＢａｙｔｒｏｎＰ（標準品））をスピンコート（４０００ｒｐｍ、６０秒間）し、１２０℃で１０分間乾燥することにより、膜厚約５０ｎｍのホール輸送性バッファ層を形成させた。
　次いで、ホスト材料として化合物１を１質量％、及びＧＤ－１を０．０５質量％含有するトルエン溶液を先のバッファ層上にスピンコート（２０００ｒｐｍ、６０秒間）し、膜厚約５０ｎｍの発光層を形成させた。
　この発光層の上に、ＥＴ－３を真空蒸着法により５０ｎｍ蒸着して電子輸送層とし、更にフッ化リチウム０．１ｎｍ及び金属アルミニウム１００ｎｍをこの順に蒸着し陰極とした。
　このものを、大気に触れさせること無く、窒素ガスで置換したグローブボックス内に入れ、ガラス製の封止缶及び紫外線硬化型の接着剤（ＸＮＲ５５１６ＨＶ、長瀬チバ（株）製）を用いて封止し、有機電界発光素子９－１を得た。また、発光層を構成するホスト材料を表９中に記載の材料に変更する以外は同様にして、素子９－２～９－４、比較素子９－１～９－３を得た。表９に記載の項目について、実施例１と同様の方法で評価した結果を表９に示す。 Example 9 (Coating, green host)
A glass substrate having a thickness of 0.5 mm and a 2.5 cm square ITO film (manufactured by Geomat Co., Ltd., surface resistance 10 Ω / □) is placed in a cleaning container, subjected to ultrasonic cleaning in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes. Went. On this transparent anode (ITO film), PEDOT (poly (3,4-ethylenedioxythiophene)) / PSS (polystyrene sulfonic acid) aqueous solution (BaytronP (standard product)) was spin-coated (4000 rpm, 60 seconds), 120 By drying at a temperature of 10 ° C. for 10 minutes, a hole transporting buffer layer having a film thickness of about 50 nm was formed.
Next, a toluene solution containing 1% by mass of Compound 1 as a host material and 0.05% by mass of GD-1 was spin-coated (2000 rpm, 60 seconds) on the previous buffer layer, and a light-emitting layer having a thickness of about 50 nm Formed.
On this light emitting layer, ET-3 was deposited to 50 nm by vacuum deposition to form an electron transport layer, and further, 0.1 nm of lithium fluoride and 100 nm of metallic aluminum were deposited in this order to form a cathode.
This product is put in a glove box substituted with nitrogen gas without being exposed to the atmosphere, and sealed with a glass sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.). Thus, an organic electroluminescent element 9-1 was obtained. Similarly, devices 9-2 to 9-4 and comparative devices 9-1 to 9-3 were obtained except that the host material constituting the light emitting layer was changed to the materials shown in Table 9. Table 9 shows the results of evaluating the items described in Table 9 by the same method as in Example 1.
Figure JPOXMLDOC01-appb-T000108
Figure JPOXMLDOC01-appb-T000108
　以上のように、本発明の電荷輸送材料は、湿式成膜法で成膜しても良好な膜質の膜が得られ、性能の良好な素子が得られることが分かった。 As described above, it has been found that the charge transport material of the present invention can provide a film having a good film quality even when formed by a wet film formation method, and an element having a good performance.
　表１～９の結果から、本発明の一般式（１）～（３）のいずれかで表される化合物を用いた本発明の素子は、比較例の素子と比べて、高温保管後の効率の変化及び色度の変化が小さく、かつ、高温保管後の耐久性に優れることが分かる。　 From the results in Tables 1 to 9, the device of the present invention using the compound represented by any one of the general formulas (1) to (3) of the present invention has an efficiency after high temperature storage as compared with the device of the comparative example. It can be seen that the change in color and the change in chromaticity are small and the durability after high temperature storage is excellent. *
　発光装置、表示装置、照明装置の場合、各画素部で高い電流密度を通じて瞬間的に高輝度発光させる必要があり、本発明の発光素子はそのような場合に発光効率が高くなるように設計されているため、有利に利用することができる。
　また、本発明の素子は車載用途などの高温環境で使用する際においても発光効率や耐久性にも優れ、発光装置、表示装置、照明装置に好適である。 In the case of a light emitting device, a display device, and a lighting device, it is necessary to instantaneously emit light with high brightness through a high current density in each pixel portion, and the light emitting element of the present invention is designed to increase the light emission efficiency in such a case. Therefore, it can be used advantageously.
Further, the element of the present invention is excellent in luminous efficiency and durability even when used in a high temperature environment such as in-vehicle use, and is suitable for a light emitting device, a display device, and a lighting device.
　以下に実施例１～９で用いた、前掲の化合物１～１１及び比較化合物１～１１以外の化合物の構造を示す。 The structures of compounds other than the above-mentioned compounds 1 to 11 and comparative compounds 1 to 11 used in Examples 1 to 9 are shown below.
Figure JPOXMLDOC01-appb-C000109
Figure JPOXMLDOC01-appb-C000109
Figure JPOXMLDOC01-appb-C000110
Figure JPOXMLDOC01-appb-C000110
　本発明によれば、素子の高温保管後の発光効率の低下の抑制、色度変化の抑制、及び耐久性の向上の全てを、高い水準で満足する有機電界発光素子を提供することができる。 According to the present invention, it is possible to provide an organic electroluminescent device that satisfies all of the suppression of a decrease in luminous efficiency after storage of the device at a high temperature, the suppression of chromaticity change, and the improvement of durability at a high level.
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
　本出願は、２０１０年４月２３日出願の日本特許出願（特願２０１０－１００３９８）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on April 23, 2010 (Japanese Patent Application No. 2010-1000039), the contents of which are incorporated herein by reference.
　２・・・基板
　３・・・陽極
　４・・・正孔注入層
　５・・・正孔輸送層
　６・・・発光層
　７・・・正孔ブロック層
　８・・・電子輸送層
　９・・・陰極
　１０・・・有機電界発光素子（有機ＥＬ素子）
　１１・・・有機層
　１２・・・保護層
　１４・・・接着層
　１６・・・封止容器
　２０・・・発光装置
　３０・・・光散乱部材
　３０Ａ・・・光入射面
　３０Ｂ・・・光出射面
　３１・・・透明基板
　３２・・・微粒子
　４０・・・照明装置 DESCRIPTION OF SYMBOLS 2 ... Substrate 3 ... Anode 4 ... Hole injection layer 5 ... Hole transport layer 6 ... Light emitting layer 7 ... Hole block layer 8 ... Electron transport layer 9 ... -Cathode 10 ... Organic electroluminescent device (organic EL device)
DESCRIPTION OF SYMBOLS 11 ... Organic layer 12 ... Protective layer 14 ... Adhesive layer 16 ... Sealing container 20 ... Light emitting device 30 ... Light scattering member 30A ... Light incident surface 30B ... Light Outgoing surface 31 ... Transparent substrate 32 ... Fine particles 40 ... Illumination device

Claims (22)

  1. 　基板上に、陽極及び陰極からなる一対の電極と、該電極間に発光層を含む少なくとも一層の有機層とを有する有機電界発光素子であって、
    　前記発光層に燐光発光材料を少なくとも一種含み、かつ、前記少なくとも一層の有機層のいずれか少なくとも一層に下記一般式（１）で表される、ｍ－キンクフェニル構造を有する化合物を含む有機電界発光素子。
    Figure JPOXMLDOC01-appb-C000001
     　一般式（１）中、Ｒ１はアルキル基又はアリール基を表す。但し、Ｒ１で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ１が複数存在する時、複数のＲ１は同一でも異なってもよい。
    　ｍ１は、一般式（１）中のｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１０以下の整数を表す。
    　ｎ１は、一般式（１）中のｍ－キンクフェニル構造に置換したＲ１の数であり、０以上２２以下の整数を表す。ここで、ｍ１＋ｎ１は１以上２２以下の整数である。
    　但し、一般式（１）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ１を有する。     An organic electroluminescent device having a pair of electrodes consisting of an anode and a cathode on a substrate, and at least one organic layer including a light emitting layer between the electrodes,
    Organic electroluminescence comprising at least one phosphorescent material in the light emitting layer, and at least one of the at least one organic layer comprising a compound having an m-kinkphenyl structure represented by the following general formula (1) element.
    Figure JPOXMLDOC01-appb-C000001
     In general formula (1), R 1 represents an alkyl group or an aryl group. However, the aryl group represented by R 1 does not have a condensed ring and may have an alkyl group or a cyano group. When R 1 there are a plurality, the plurality of R 1 may be the same or different.
    m 1 is the number of cyano groups substituted in the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 10 or less.
    n 1 is the number of R 1 substituted with the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 22 or less. Here, m 1 + n 1 is an integer of 1 or more and 22 or less.
    However, the compound represented by the general formula (1) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 1 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  2. 　前記一般式（１）で表される化合物が下記一般式（２）で表される、請求項１に記載の有機電界発光素子。
    Figure JPOXMLDOC01-appb-C000002
     　一般式（２）中、Ｒ２はアルキル基又はアリール基を表す。但し、Ｒ２で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ２が複数存在する時、複数のＲ２は同一でも異なってもよい。
    　ｍ２は、一般式（２）中のビフェニル－ｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１４以下の整数を表す。
    　ｎ２は、一般式（２）中のビフェニル－ｍ－キンクフェニル構造に置換したＲ２の数であり、０以上３０以下の整数を表す。ここで、ｍ２＋ｎ２は１以上３０以下の整数である。
    　但し、一般式（２）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ２を有する。     The organic electroluminescent element according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (2).
    Figure JPOXMLDOC01-appb-C000002
     In general formula (2), R 2 represents an alkyl group or an aryl group. However, the aryl group represented by R 2 does not have a condensed ring and may have an alkyl group or a cyano group. When R 2 there are a plurality, the plurality of R 2 may be the same or different.
    m 2 is the number of cyano groups substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 14 or less.
    n 2 is the number of R 2 substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 30 or less. Here, m 2 + n 2 is 1 to 30 integer.
    However, the compound represented by the general formula (2) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 2 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  3. 　前記一般式（１）で表される化合物が下記一般式（３）で表される、請求項１に記載の有機電界発光素子。
    Figure JPOXMLDOC01-appb-C000003
     　一般式（３）中、Ｒ３はアルキル基又はアリール基を表す。但し、Ｒ３で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ３が複数存在する時、複数のＲ３は同一でも異なってもよい。
    　ｍ３は、一般式（３）中のジフェニル－ｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１４以下の整数を表す。
    　ｎ３は、一般式（３）中のジフェニル－ｍ－キンクフェニル構造に置換したＲ３の数であり、０以上３０以下の整数を表す。ここで、ｍ３＋ｎ３は１以上３０以下の整数である。
    　但し、一般式（３）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ３を有する。     The organic electroluminescent element according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (3).
    Figure JPOXMLDOC01-appb-C000003
     In general formula (3), R 3 represents an alkyl group or an aryl group. However, the aryl group represented by R 3 does not have a condensed ring and may have an alkyl group or a cyano group. When R 3 there are a plurality, the plurality of R 3 may be the same or different.
    m 3 is the number of cyano groups substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 14 or less.
    n 3 is the number of R 3 substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 30 or less. Here, m 3 + n 3 is an integer of 1 or more and 30 or less.
    However, the compound represented by the general formula (3) does not have a benzene ring substituted with 3 or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 3 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  4. 　前記燐光発光材料が、下記一般式（Ｅ－１）で表されるイリジウム錯体である、請求項１～３のいずれか一項に記載の有機電界発光素子。
    Figure JPOXMLDOC01-appb-C000004
     　一般式（Ｅ－１）中、Ｚ１及びＺ２はそれぞれ独立に、炭素原子又は窒素原子を表す。
    　Ａ１はＺ１と窒素原子と共に５又は６員のヘテロ環を形成する原子群を表す。
    　Ｂ１はＺ２と炭素原子と共に５又は６員環を形成する原子群を表す。
    　（Ｘ－Ｙ）はモノアニオン性の二座配位子を表す。
    　ｎＥ１は１～３の整数を表す。     The organic electroluminescent element according to any one of claims 1 to 3, wherein the phosphorescent material is an iridium complex represented by the following general formula (E-1).
    Figure JPOXMLDOC01-appb-C000004
     In general formula (E-1), Z 1 and Z 2 each independently represent a carbon atom or a nitrogen atom.
    A 1 represents an atomic group that forms a 5- or 6-membered heterocycle with Z 1 and a nitrogen atom.
    B 1 represents an atomic group that forms a 5- or 6-membered ring with Z 2 and a carbon atom.
    (XY) represents a monoanionic bidentate ligand.
    n E1 represents an integer of 1 to 3.
  5. 　前記一般式（Ｅ－１）で表されるイリジウム錯体が下記一般式（Ｅ－２）で表される、請求項４に記載の有機電界発光素子。
    Figure JPOXMLDOC01-appb-C000005
     　一般式（Ｅ－２）中、ＡＥ１～ＡＥ８はそれぞれ独立に、窒素原子又はＣ－ＲＥを表す。
    　ＲＥは水素原子又は置換基を表す。
    　（Ｘ－Ｙ）はモノアニオン性の二座配位子を表す。
    　ｎＥ２は１～３の整数を表す。     The organic electroluminescent element according to claim 4, wherein the iridium complex represented by the general formula (E-1) is represented by the following general formula (E-2).
    Figure JPOXMLDOC01-appb-C000005
     In general formula (E-2), A E1 to A E8 each independently represents a nitrogen atom or C—R E.
    R E represents a hydrogen atom or a substituent.
    (XY) represents a monoanionic bidentate ligand.
    n E2 represents an integer of 1 to 3.
  6. 　前記一般式（Ｅ－１）で表されるイリジウム錯体が下記一般式（Ｅ－６）で表される、請求項４に記載の有機電界発光素子。
    Figure JPOXMLDOC01-appb-C000006
     　一般式（Ｅ－６）中、Ｒ１ａ～Ｒ１ｋは、それぞれ独立に水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、－ＣＮ、ペルフルオロアルキル基、トリフルオロビニル基、－ＣＯ２Ｒ、－Ｃ（Ｏ）Ｒ、－ＮＲ２、－ＮＯ２、－ＯＲ、ハロゲン原子、アリール基又はヘテロアリール基を表し、更に置換基Ｚを有していてもよい。Ｒはそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。
    　Ｒ１ａ～Ｒ１ｋは、任意の２つが互いに結合して縮合４～７員環を形成してもよく、該縮合４～７員環は更に置換基Ｚを有していてもよい。
    　Ｚはそれぞれ独立に、ハロゲン原子、－Ｒ”、－ＯＲ”、－Ｎ（Ｒ”）２、－ＳＲ”、－Ｃ（Ｏ）Ｒ”、－Ｃ（Ｏ）ＯＲ”、－Ｃ（Ｏ）Ｎ（Ｒ”）２、－ＣＮ、－ＮＯ２、－ＳＯ２、－ＳＯＲ”、－ＳＯ２Ｒ”、又は－ＳＯ３Ｒ”を表し、Ｒ”はそれぞれ独立に、水素原子、アルキル基、ペルハロアルキル基、アルケニル基、アルキニル基、ヘテロアルキル基、アリール基又はヘテロアリール基を表す。
    　（Ｘ－Ｙ）は、モノアニオン性の二座配位子を表す。
    　ｎＥ６は１～３の整数を表す。     The organic electroluminescence device according to claim 4, wherein the iridium complex represented by the general formula (E-1) is represented by the following general formula (E-6).
    Figure JPOXMLDOC01-appb-C000006
     In general formula (E-6), R 1a to R 1k each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, —CN, a perfluoroalkyl group, a trifluorovinyl group, —CO 2 R, —C (O) R, —NR 2 , —NO 2 , —OR, a halogen atom, an aryl group, or a heteroaryl group, which may further have a substituent Z. Each R independently represents a hydrogen atom, an alkyl group, a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
    Any two of R 1a to R 1k may be bonded to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring may further have a substituent Z.
    Z is each independently a halogen atom, —R ″, —OR ″, —N (R ″) 2 , —SR ″, —C (O) R ″, —C (O) OR ″, —C (O) N (R ") 2, -CN , -NO 2, -SO 2, -SOR", - SO 2 R ", or -SO 3 R" represents, R "are each independently a hydrogen atom, an alkyl group, A perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group is represented.
    (XY) represents a monoanionic bidentate ligand.
    n E6 represents an integer of 1 to 3.
  7. 　前記発光層と陰極との間に、前記発光層に隣接する有機層を有し、該有機層が前記一般式（１）～（３）のいずれかで表される化合物を含有する、請求項１～６のいずれか一項に記載の有機電界発光素子。 An organic layer adjacent to the light emitting layer is provided between the light emitting layer and the cathode, and the organic layer contains a compound represented by any one of the general formulas (1) to (3). 7. The organic electroluminescence device according to any one of 1 to 6.
  8. 　前記発光層が前記一般式（１）～（３）のいずれかで表される化合物を含有する、請求項１～７のいずれか一項に記載の有機電界発光素子。 The organic electroluminescence device according to any one of claims 1 to 7, wherein the light emitting layer contains a compound represented by any one of the general formulas (1) to (3).
  9. 　前記一対の電極間に、前記陰極に隣接する電子注入層を有し、該電子注入層が前記一般式（１）～（３）のいずれかで表される化合物を含有する、請求項１～８のいずれか一項に記載の有機電界発光素子。 An electron injection layer adjacent to the cathode is provided between the pair of electrodes, and the electron injection layer contains a compound represented by any one of the general formulas (1) to (3). The organic electroluminescent element according to any one of 8.
  10. 　前記電子注入層が、更に電子供与性ドーパントを含有する、請求項９に記載の有機電界発光素子。 The organic electroluminescence device according to claim 9, wherein the electron injection layer further contains an electron donating dopant.
  11. 　前記一対の電極間にある有機層の少なくとも一層が、溶液塗布法により形成されることを特徴とする請求項１～１０のいずれか一項に記載の有機電界発光素子。 11. The organic electroluminescence device according to claim 1, wherein at least one organic layer between the pair of electrodes is formed by a solution coating method.
  12. 　請求項１～１１のいずれか一項に記載の有機電界発光素子を用いた発光装置。 A light emitting device using the organic electroluminescent element according to any one of claims 1 to 11.
  13. 　請求項１～１１のいずれか一項に記載の有機電界発光素子を用いた表示装置。 A display device using the organic electroluminescent element according to any one of claims 1 to 11.
  14. 　請求項１～１１のいずれか一項に記載の有機電界発光素子を用いた照明装置。 An illumination device using the organic electroluminescent element according to any one of claims 1 to 11.
  15. 　下記一般式（１）で表される電荷輸送材料。
    Figure JPOXMLDOC01-appb-C000007
     　一般式（１）中、Ｒ１はアルキル基又はアリール基を表す。但し、Ｒ１で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ１が複数存在する時、複数のＲ１は同一でも異なってもよい。
    　ｍ１は、一般式（１）中のｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１０以下の整数を表す。
    　ｎ１は、一般式（１）中のｍ－キンクフェニル構造に置換したＲ１の数であり、０以上２２以下の整数を表す。ここで、ｍ１＋ｎ１は１以上２２以下の整数である。
    　但し、一般式（１）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ１を有する。     A charge transport material represented by the following general formula (1).
    Figure JPOXMLDOC01-appb-C000007
     In general formula (1), R 1 represents an alkyl group or an aryl group. However, the aryl group represented by R 1 does not have a condensed ring and may have an alkyl group or a cyano group. When R 1 there are a plurality, the plurality of R 1 may be the same or different.
    m 1 is the number of cyano groups substituted in the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 10 or less.
    n 1 is the number of R 1 substituted with the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 22 or less. Here, m 1 + n 1 is an integer of 1 or more and 22 or less.
    However, the compound represented by the general formula (1) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 1 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  16. 　下記一般式（２）で表される、請求項１５に記載の電荷輸送材料。
    Figure JPOXMLDOC01-appb-C000008
     　一般式（２）中、Ｒ２はアルキル基又はアリール基を表す。但し、Ｒ２で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ２が複数存在する時、複数のＲ２は同一でも異なってもよい。
    　ｍ２は、一般式（２）中のビフェニル－ｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１４以下の整数を表す。
    　ｎ２は、一般式（２）中のビフェニル－ｍ－キンクフェニル構造に置換したＲ２の数であり、０以上３０以下の整数を表す。ここで、ｍ２＋ｎ２は１以上３０以下の整数である。
    　但し、一般式（２）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ２を有する。     The charge transport material according to claim 15, which is represented by the following general formula (2).
    Figure JPOXMLDOC01-appb-C000008
     In general formula (2), R 2 represents an alkyl group or an aryl group. However, the aryl group represented by R 2 does not have a condensed ring and may have an alkyl group or a cyano group. When R 2 there are a plurality, the plurality of R 2 may be the same or different.
    m 2 is the number of cyano groups substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 14 or less.
    n 2 is the number of R 2 substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 30 or less. Here, m 2 + n 2 is 1 to 30 integer.
    However, the compound represented by the general formula (2) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 2 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  17. 　下記一般式（３）で表される、請求項１５に記載の電荷輸送材料。
    Figure JPOXMLDOC01-appb-C000009
    　一般式（３）中、Ｒ３はアルキル基又はアリール基を表す。但し、Ｒ３で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ３が複数存在する時、複数のＲ３は同一でも異なってもよい。
    　ｍ３は、一般式（３）中のジフェニル－ｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１４以下の整数を表す。
    　ｎ３は、一般式（３）中のジフェニル－ｍ－キンクフェニル構造に置換したＲ３の数であり、０以上３０以下の整数を表す。ここで、ｍ３＋ｎ３は１以上３０以下の整数である。
    　但し、一般式（３）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ３を有する。     The charge transport material according to claim 15, which is represented by the following general formula (3).
    Figure JPOXMLDOC01-appb-C000009
    In general formula (3), R 3 represents an alkyl group or an aryl group. However, the aryl group represented by R 3 does not have a condensed ring and may have an alkyl group or a cyano group. When R 3 there are a plurality, the plurality of R 3 may be the same or different.
    m 3 is the number of cyano groups substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 14 or less.
    n 3 is the number of R 3 substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 30 or less. Here, m 3 + n 3 is an integer of 1 or more and 30 or less.
    However, the compound represented by the general formula (3) does not have a benzene ring substituted with 3 or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 3 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  18. 　請求項１５～１７のいずれか一項に記載の電荷輸送材料を含む組成物。 A composition comprising the charge transport material according to any one of claims 15 to 17.
  19. 　請求項１５～１７のいずれか一項に記載の電荷輸送材料を含む薄膜。 A thin film comprising the charge transport material according to any one of claims 15 to 17.
  20. 　下記一般式（１）で表される化合物。
    Figure JPOXMLDOC01-appb-C000010
     　一般式（１）中、Ｒ１はアルキル基又はアリール基を表す。但し、Ｒ１で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ１が複数存在する時、複数のＲ１は同一でも異なってもよい。
    　ｍ１は、一般式（１）中のｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１０以下の整数を表す。
    　ｎ１は、一般式（１）中のｍ－キンクフェニル構造に置換したＲ１の数であり、０以上２２以下の整数を表す。ここで、ｍ１＋ｎ１は１以上２２以下の整数である。
    　但し、一般式（１）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ１を有する。     A compound represented by the following general formula (1).
    Figure JPOXMLDOC01-appb-C000010
     In general formula (1), R 1 represents an alkyl group or an aryl group. However, the aryl group represented by R 1 does not have a condensed ring and may have an alkyl group or a cyano group. When R 1 there are a plurality, the plurality of R 1 may be the same or different.
    m 1 is the number of cyano groups substituted in the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 10 or less.
    n 1 is the number of R 1 substituted with the m-kinkphenyl structure in the general formula (1), and represents an integer of 0 or more and 22 or less. Here, m 1 + n 1 is an integer of 1 or more and 22 or less.
    However, the compound represented by the general formula (1) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 1 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  21. 　下記一般式（２）で表される、請求項２０に記載の化合物。
    Figure JPOXMLDOC01-appb-C000011
     　一般式（２）中、Ｒ２はアルキル基又はアリール基を表す。但し、Ｒ２で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ２が複数存在する時、複数のＲ２は同一でも異なってもよい。
    　ｍ２は、一般式（２）中のビフェニル－ｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１４以下の整数を表す。
    　ｎ２は、一般式（２）中のビフェニル－ｍ－キンクフェニル構造に置換したＲ２の数であり、０以上３０以下の整数を表す。ここで、ｍ２＋ｎ２は１以上３０以下の整数である。
    　但し、一般式（２）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ２を有する。     The compound of Claim 20 represented by following General formula (2).
    Figure JPOXMLDOC01-appb-C000011
     In general formula (2), R 2 represents an alkyl group or an aryl group. However, the aryl group represented by R 2 does not have a condensed ring and may have an alkyl group or a cyano group. When R 2 there are a plurality, the plurality of R 2 may be the same or different.
    m 2 is the number of cyano groups substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 14 or less.
    n 2 is the number of R 2 substituted on the biphenyl-m-kinkphenyl structure in the general formula (2), and represents an integer of 0 or more and 30 or less. Here, m 2 + n 2 is 1 to 30 integer.
    However, the compound represented by the general formula (2) does not have a benzene ring substituted with three or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 2 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
  22. 　下記一般式（３）で表される、請求項２０に記載の化合物。
    Figure JPOXMLDOC01-appb-C000012
     　一般式（３）中、Ｒ３はアルキル基又はアリール基を表す。但し、Ｒ３で表されるアリール基は縮合環を有さず、アルキル基又はシアノ基を有していてもよい。Ｒ３が複数存在する時、複数のＲ３は同一でも異なってもよい。
    　ｍ３は、一般式（３）中のジフェニル－ｍ－キンクフェニル構造に置換したシアノ基の数であり、０以上１４以下の整数を表す。
    　ｎ３は、一般式（３）中のジフェニル－ｍ－キンクフェニル構造に置換したＲ３の数であり、０以上３０以下の整数を表す。ここで、ｍ３＋ｎ３は１以上３０以下の整数である。
    　但し、一般式（３）で表される化合物は、シアノ基が３個以上置換したベンゼン環を有することは無く、ベンゼン環に置換したシアノ基を少なくとも１個有し、かつ、該化合物中のベンゼン環の数と、ベンゼン環に置換したシアノ基の数との和が９以上２０以下となるようにシアノ基及びＲ３を有する。     The compound of Claim 20 represented by following General formula (3).
    Figure JPOXMLDOC01-appb-C000012
     In general formula (3), R 3 represents an alkyl group or an aryl group. However, the aryl group represented by R 3 does not have a condensed ring and may have an alkyl group or a cyano group. When R 3 there are a plurality, the plurality of R 3 may be the same or different.
    m 3 is the number of cyano groups substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 14 or less.
    n 3 is the number of R 3 substituted on the diphenyl-m-kinkphenyl structure in the general formula (3), and represents an integer of 0 or more and 30 or less. Here, m 3 + n 3 is an integer of 1 or more and 30 or less.
    However, the compound represented by the general formula (3) does not have a benzene ring substituted with 3 or more cyano groups, has at least one cyano group substituted on the benzene ring, and It has a cyano group and R 3 so that the sum of the number of benzene rings and the number of cyano groups substituted on the benzene ring is 9 or more and 20 or less.
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