JP2013069905A - Organic electroluminescent element, display device, lighting device, and organic electroluminescent material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element excellent in service life.SOLUTION: The organic electroluminescent element according to the present invention includes at least one light-emitting layer and is characterized by containing a compound represented by general formula (1). (In the general formula (1), Czand Czeach represents a substituted or unsubstituted carbazolyl group, Land Leach represents a divalent linking group or a single bond, and A represents general formula (2). In the general formula (2), Aand Aeach represents a substituted or unsubstituted dibenzofuran or dibenzothiophene.)

Description

  The present invention relates to an organic electroluminescence element, a display device and an illumination device including the organic electroluminescence element, and an organic electroluminescence material that can be used for these devices.

  An organic electroluminescence element (hereinafter abbreviated as EL) is composed of a light emitting layer containing a light emitting compound sandwiched between a cathode and an anode, injecting electrons and holes into the light emitting layer, By recombination, excitons (excitons) are generated, and light is emitted using light emission (fluorescence / phosphorescence) when the excitons are deactivated. Such an organic EL element can emit light at a voltage of about several volts to several tens of volts, and is a self-luminous type, so that it has a wide viewing angle, high visibility, and is a thin-film type completely solid element. It attracts attention from the viewpoint of space saving and portability.

  In order to improve the lifetime such as aging stability and / or emission lifetime of the light emitting material used in the organic EL element, the search for the host compound used in the light emitting layer has been made for a long time, and there is a possibility that the structure can withstand practical use. Is being discovered. However, small changes in the structure of the host compound have a large effect on the lifetime, and many problems remain to be solved.

  In the development so far, the usefulness of dibenzofuran and dibenzothiophene has been recognized (Patent Documents 1 and 2), but a structure that has not yet been confirmed when focusing on the introduction of substituents at specific sites. It is a state that remains.

International Publication No. 2011/004639 Pamphlet JP 2009-267255 A

  The present invention has been made in view of the above circumstances, and provides an organic electroluminescence element having excellent lifetime, a display device and an illumination device including the organic electroluminescence element, and an organic electroluminescence material that can be used for these devices. Let it be an issue.

  As a result of diligent research and development to solve the above problems, the present inventors have directly or directly connected a carbazolyl group to a benzene ring on one side of dibenzofuran and dibenzothiophene disclosed in Patent Documents 1 and 2. When the compound has a partial structure substituted by 2 or more, the performance of the organic EL device was found to change specifically, and the present invention was completed.

  The said subject of this invention can be achieved by the following structures.

1. An organic luminescence device comprising at least one light-emitting layer, which contains a compound represented by the following general formula (1).

(In the general formula (1), Cz ¹ and Cz ² represent a substituted or unsubstituted carbazolyl group, L ¹ and L ² represent a divalent linking group or a single bond, and A represents the general formula (2). Represents.
In General Formula (2), A ¹ and A ² represent substituted or unsubstituted dibenzofuran or dibenzothiophene. )

2. ^2. The organic electroluminescence device according to 1 above, wherein at least one of A ¹ and A ² is a substituted or unsubstituted dibenzofuran.

3. ^2. The organic electroluminescence device as described in 1 above, wherein both A ¹ and A ² are substituted or unsubstituted dibenzofuran.

4). 2. The organic electroluminescence device according to 1 above, wherein A is represented by the following general formula (3), (4), (5) or (6).

(However, in general formula (3), (4), (5) or (6), R ¹ and R ² each independently represents a hydrogen atom or a monovalent substituent, and n1 and n2 are 1-6. Represents an integer.)

5. 5. The organic electroluminescence device according to 4 above, wherein R ¹ and R ² are hydrogen atoms.

6). 6. The organic electroluminescence device as described in any one of 1 to 5, wherein the light emitting layer contains a compound represented by the general formula (1).

7). The organic light-emitting device according to any one of 1 to 6, wherein the light-emitting layer contains a metal complex compound having a transition metal as a central metal.

8). The organic electroluminescence element according to any one of 1 to 7 above, which emits white light.

9. A display device comprising the organic electroluminescence element according to any one of 1 to 8 above.

10. A lighting device comprising the organic electroluminescence element according to any one of 1 to 8 above.

11. An organic electroluminescent material represented by the following general formula (1).

(In the general formula (1), Cz ¹ and Cz ² represent a substituted or unsubstituted carbazolyl group, L ¹ and L ² represent a divalent linking group or a single bond, and A represents the general formula (2). Represents.
In General Formula (2), A ¹ and A ² represent substituted or unsubstituted dibenzofuran or dibenzothiophene. )

  ADVANTAGE OF THE INVENTION According to this invention, the organic electroluminescent element which is excellent in lifetime can be provided.

  In addition, a display device and a lighting device provided with the same, and an organic electroluminescent material that can be used for them can be provided.

It is the schematic diagram which showed an example of the display apparatus comprised using the organic EL element of this invention. It is a schematic diagram of the display part A of the display apparatus shown in FIG. FIG. 3 is a schematic diagram of the pixel shown in FIG. 2. It is a schematic diagram of the passive matrix type full color display apparatus comprised using the organic EL element of this invention. It is the schematic of the illuminating device comprised using the organic EL element of this invention. It is a cross-sectional schematic diagram of the illuminating device shown in FIG. The schematic block diagram of the organic electroluminescent full color display apparatus comprised with the organic electroluminescent element of this invention is shown.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments (embodiments) for carrying out the present invention will be described in detail. However, the contents described below are representative examples of embodiments of the present invention, and the present invention is not limited to the gist thereof. It is not limited to the contents.

The organic EL device according to one embodiment is an organic EL device including at least one light emitting layer, and contains a compound represented by the following general formula (1).
It should be noted that the organic EL element is composed of an anode, a cathode, and constituent layers sandwiched between the anode and the cathode (such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer). The organic layer) will be described in detail later.

However, in the general formula (1), Cz ¹ and Cz ² represent a substituted or unsubstituted carbazolyl group.

  Examples of the unsubstituted carbazolyl group include 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group and the like.

  Examples of the substituted carbazolyl group include a group derived from a 9-phenylcarbazolyl group (N-phenylcarbazolyl group), a dicarbazolylphenyl derivative, or the 1-position, 2-position, 3-position, 4 And those in which an arbitrary substituent is bonded to at least one carbon at the 9th and 9th positions.

  As an optional substituent for substituting the carbazolyl group, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group) Group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), aromatic carbonization Hydrogen group (also called aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl Group, indenyl group, pyrenyl group, biphenylyl group), Aromatic heterocyclic group (for example, furyl, thienyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, pyrazolyl, thiazolyl, quinazolinyl, carbazolyl, carbolinyl, diazacarba A zolyl group (indicating that one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), a phthalazinyl group, etc., a heterocyclic group (eg, a pyrrolidyl group, an imidazolidyl group, a morpholyl group, Oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy) Group), Ally An oxy group (for example, phenoxy group, naphthyloxy group, etc.), an alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), a cycloalkylthio group (for example, cyclopentylthio group) Group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group) Group), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, Dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (For example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), Acyloxy groups (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbyl group) Nyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino) Group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylamino) Carbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl Group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenyl) Ureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, Naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclo Hexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (eg, amino group) , Ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, piperidyl group (also called piperidinyl group), 2, 2,6,6-tetramethylpiperidinyl group), halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), fluorinated hydrocarbon group (for example, fluoromethyl group, trifluoromethyl group, pentafluoro) Ethyl group, pentafluoro Phenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (eg, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), phosphate ester group (eg, dihexyl) Phosphoryl group, etc.), phosphite group (for example, diphenylphosphinyl group, etc.), phosphono group and the like.

  Such optional substituents include alkylene groups (for example, ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, pentamethylene group, hexamethylene group, 2,2,4-trimethylhexamethylene group). , Heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, cyclohexylene group (for example, 1,6-cyclohexanediyl group, etc.), cyclopentylene group (for example, 1,5 -Cyclopentanediyl group etc.), alkenylene group (for example, vinylene group, propenylene group, butenylene group, pentenylene group, 1-methylvinylene group, 1-methylpropenylene group, 2-methylpropenylene group, 1-methyl Pentenylene group, 3-methylpentenylene group, 1-ethyl Vinylene group, 1-ethylpropenylene group, 1-ethylbutenylene group, 3-ethylbutenylene group, etc.), alkynylene group (for example, ethynylene group, 1-propynylene group, 1-butynylene group, 1-pentynylene group, 1-hexynylene group, 2-butynylene group, 2-pentynylene group, 1-methylethynylene group, 3-methyl-1-propynylene group, 3-methyl-1-butynylene group, etc.), arylene group (for example, o-phenylene group, m-phenylene group, p-phenylene group, naphthalenediyl group, anthracenediyl group, naphthacenediyl group, pyrenediyl group, naphthylnaphthalenediyl group, biphenyldiyl group (for example, [1,1′-biphenyl] -4,4′-diyl group, 3,3 '-Biphenyldiyl group, 3,6-biphenyldiyl group, etc.), terphenyl Yl group, quaterphenyldiyl group, kinkphenyldiyl group, sexiphenyldiyl group, septiphenyldiyl group, octiphenyldiyl group, nobiphenyldiyl group, deciphenyldiyl group, etc.), heteroarylene group (for example, carbazole) Ring, carboline ring, diazacarbazole ring (also called monoazacarboline ring, which shows a ring structure in which one of carbon atoms constituting carboline ring is replaced by nitrogen atom), triazole ring, pyrrole ring, pyridine ring, pyrazine Ring, quinoxaline ring, thiophene ring, oxadiazole ring, dibenzofuran ring, dibenzothiophene ring, divalent group derived from the group consisting of indole ring, etc.), chalcogen atom such as oxygen and sulfur, 3 or more rings A group derived from a condensed aromatic heterocycle formed by condensation (where, The condensed aromatic heterocyclic ring formed by condensing three or more rings is preferably an aromatic heterocyclic condensed ring containing a hetero atom selected from N, O and S as an element constituting the condensed ring. Specifically, acridine ring, benzoquinoline ring, carbazole ring, phenazine ring, phenanthridine ring, phenanthroline ring, carboline ring, cyclazine ring, quindrine ring, tepenidine ring, quinindrin ring, triphenodithiazine ring, Triphenodioxazine ring, phenanthrazine ring, anthrazine ring, perimidine ring, diazacarbazole ring (representing any one of carbon atoms constituting carboline ring replaced by nitrogen atom), phenanthroline ring, dibenzofuran ring, dibenzo Thiophene ring, naphthofuran ring, naphthothiophene ring, ben Difuran ring, benzodithiophene ring, naphthodifuran ring, naphthodithiophene ring, anthrafuran ring, anthradifuran ring, anthrathiophene ring, anthradithiophene ring, thianthrene ring, phenoxathiin ring, thiophanthrene ring (naphthothiophene ring) ) Etc.).

  These substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring.

L ¹ and L ² represent a divalent linking group or a single bond.
Examples of the divalent linking group include an alkylene group (for example, ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, pentamethylene group, hexamethylene group, 2,2,4-trimethylhexamethylene group). , Heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, cyclohexylene group (for example, 1,6-cyclohexanediyl group, etc.), cyclopentylene group (for example, 1,5 -Cyclopentanediyl group etc.), alkenylene group (for example, vinylene group, propenylene group, butenylene group, pentenylene group, 1-methylvinylene group, 1-methylpropenylene group, 2-methylpropenylene group, 1-methyl Pentenylene group, 3-methylpentenylene group, 1-ethylbiphenyl Ene group, 1-ethylpropenylene group, 1-ethylbutenylene group, 3-ethylbutenylene group, etc.), alkynylene group (for example, ethynylene group, 1-propynylene group, 1-butynylene group, 1-pentynylene group, 1-hexynylene group, 2-butynylene group, 2-pentynylene group, 1-methylethynylene group, 3-methyl-1-propynylene group, 3-methyl-1-butynylene group, etc.), arylene group (for example, o-phenylene group, m-phenylene group, p-phenylene group, naphthalenediyl group, anthracenediyl group, naphthacenediyl group, pyrenediyl group, naphthylnaphthalenediyl group, biphenyldiyl group (for example, [1,1′-biphenyl] -4,4′-diyl group, 3,3 '-Biphenyldiyl group, 3,6-biphenyldiyl group, etc.), terphenyldiyl group Quaterphenyldiyl group, kinkphenyldiyl group, sexiphenyldiyl group, septiphenyldiyl group, octiphenyldiyl group, nobiphenyldiyl group, deciphenyldiyl group, etc.), heteroarylene group (for example, carbazole ring, carboline) Ring, diazacarbazole ring (also called monoazacarboline ring, which shows a ring structure in which one of carbon atoms constituting carboline ring is replaced by nitrogen atom), triazole ring, pyrrole ring, pyridine ring, pyrazine ring, quinoxaline Ring, thiophene ring, oxadiazole ring, dibenzofuran ring, dibenzothiophene ring, divalent group derived from the group consisting of indole ring, etc.), chalcogen atoms such as oxygen and sulfur, and three or more rings are condensed A group derived from a condensed aromatic heterocycle (eg, 3 or more rings) The condensed aromatic heterocycle formed by condensation of the ring is preferably an aromatic heterofused ring containing a hetero atom selected from N, O and S as an element constituting the condensed ring, Specifically, acridine ring, benzoquinoline ring, carbazole ring, phenazine ring, phenanthridine ring, phenanthroline ring, carboline ring, cyclazine ring, kindrin ring, tepenidine ring, quinindrine ring, triphenodithiazine ring, triphenodioxazine Ring, phenanthrazine ring, anthrazine ring, perimidine ring, diazacarbazole ring (representing any one of carbon atoms constituting carboline ring replaced by nitrogen atom), phenanthroline ring, dibenzofuran ring, dibenzothiophene ring, Naphthofuran ring, naphthothiophene ring, benzodifura Ring, benzodithiophene ring, naphthodifuran ring, naphthodithiophene ring, anthracfuran ring, anthradifuran ring, anthrathiophene ring, anthradithiophene ring, thianthrene ring, phenoxathiin ring, thiophanthrene ring (naphthothiophene ring) Etc.). The divalent linking group may be one in which one or two or more selected from these are linked.

And A in General formula (1) represents General formula (2).
In General Formula (2), A ¹ and A ² represent substituted or unsubstituted dibenzofuran or dibenzothiophene.
In addition, it is preferable that at least one of A ¹ and A ² is substituted or unsubstituted dibenzofuran, and it is preferable that both A ¹ and A ² are substituted or unsubstituted dibenzofuran.

  Unsubstituted dibenzofuran or dibenzothiophene means that a hydrogen atom is bonded to carbons at the 1-position, 2-position, 3-position, 4-position, 6-position, 7-position, 8-position and 9-position.

  Examples of the substituted dibenzofuran or dibenzothiophene include, for example, any substitution in at least one of the 1-position, 2-position, 3-position, 4-position, 6-position, 7-position, 8-position and 9-position. The thing which group couple | bonded can be mentioned.

  As an optional substituent for substituting dibenzofuran or dibenzothiophene, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group) , Tetradecyl group, pentadecyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg ethynyl group, propargyl group etc.), aromatic Aromatic hydrocarbon group (also called aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group , Phenanthryl group, indenyl group, pyreni Group, biphenylyl group), aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, carbazolyl group, Phenylcarbazolyl group (for example, 9-phenylcarbazolyl group), dibenzofuryl group, dibenzothienyl group, carbolinyl group, diazacarbazolyl group (one of any carbon atoms constituting the carboline ring of the carbolinyl group) One is replaced by a nitrogen atom), a phthalazinyl group, etc.), a heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), an alkoxy group (eg, methoxy group, ethoxy group, propyloxy group) , Pentyloxy group, hexyloxy group, Tiloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group). Propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (for example, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (For example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenyl Oxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, Dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group) 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy Groups (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide groups (for example, methylcarbonylamino group, ethylcarbonylamino group, Dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group), carbamoyl Group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group) Cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethyl) Ureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl) Group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2- Pyridylsulfinyl group etc.), alkylsulfonyl group (eg methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group etc.), arylsulfonyl group or heteroarylsulfonyl group (eg , Phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group) , Anilino group, naphthylamino group, 2-pyridylamino group, piperidyl group (also referred to as piperidinyl group), 2,2,6,6-tetramethylpiperidinyl group, etc., halogen atom (for example, fluorine atom, chlorine Element, bromine atom, etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (For example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), phosphate ester group (for example, dihexyl phosphoryl group, etc.), phosphite group (for example, diphenylphosphinyl group, etc.) And phosphono group.

  Such optional substituents include alkylene groups (for example, ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, pentamethylene group, hexamethylene group, 2,2,4-trimethylhexamethylene group). , Heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, cyclohexylene group (for example, 1,6-cyclohexanediyl group, etc.), cyclopentylene group (for example, 1,5 -Cyclopentanediyl group etc.), alkenylene group (for example, vinylene group, propenylene group, butenylene group, pentenylene group, 1-methylvinylene group, 1-methylpropenylene group, 2-methylpropenylene group, 1-methyl Pentenylene group, 3-methylpentenylene group, 1-ethyl Vinylene group, 1-ethylpropenylene group, 1-ethylbutenylene group, 3-ethylbutenylene group, etc.), alkynylene group (for example, ethynylene group, 1-propynylene group, 1-butynylene group, 1-pentynylene group, 1-hexynylene group, 2-butynylene group, 2-pentynylene group, 1-methylethynylene group, 3-methyl-1-propynylene group, 3-methyl-1-butynylene group, etc.), arylene group (for example, o-phenylene group, m-phenylene group, p-phenylene group, naphthalenediyl group, anthracenediyl group, naphthacenediyl group, pyrenediyl group, naphthylnaphthalenediyl group, biphenyldiyl group (for example, [1,1′-biphenyl] -4,4′-diyl group, 3,3 '-Biphenyldiyl group, 3,6-biphenyldiyl group, etc.), terphenyl Yl group, quaterphenyldiyl group, kinkphenyldiyl group, sexiphenyldiyl group, septiphenyldiyl group, octiphenyldiyl group, nobiphenyldiyl group, deciphenyldiyl group, etc.), heteroarylene group (for example, carbazole) Ring, carboline ring, diazacarbazole ring (also called monoazacarboline ring, which shows a ring structure in which one of carbon atoms constituting carboline ring is replaced by nitrogen atom), triazole ring, pyrrole ring, pyridine ring, pyrazine Ring, quinoxaline ring, thiophene ring, oxadiazole ring, dibenzofuran ring, dibenzothiophene ring, divalent group derived from the group consisting of indole ring, etc.), chalcogen atom such as oxygen and sulfur, 3 or more rings A group derived from a condensed aromatic heterocycle formed by condensation (where, The condensed aromatic heterocyclic ring formed by condensing three or more rings is preferably an aromatic heterocyclic condensed ring containing a hetero atom selected from N, O and S as an element constituting the condensed ring. Specifically, acridine ring, benzoquinoline ring, carbazole ring, phenazine ring, phenanthridine ring, phenanthroline ring, carboline ring, cyclazine ring, quindrine ring, tepenidine ring, quinindrin ring, triphenodithiazine ring, Triphenodioxazine ring, phenanthrazine ring, anthrazine ring, perimidine ring, diazacarbazole ring (representing any one of carbon atoms constituting carboline ring replaced by nitrogen atom), phenanthroline ring, dibenzofuran ring, dibenzo Thiophene ring, naphthofuran ring, naphthothiophene ring, ben Difuran ring, benzodithiophene ring, naphthodifuran ring, naphthodithiophene ring, anthrafuran ring, anthradifuran ring, anthrathiophene ring, anthradithiophene ring, thianthrene ring, phenoxathiin ring, thiophanthrene ring (naphthothiophene ring) ) Etc.).

  These substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring.

  Among the compounds represented by A in the general formula (1), a compound represented by the general formula (3), (4), (5) or (6) is further preferable. That is, it is preferably a compound represented by the general formula (3), (4), (5) or (6) instead of the general formula (2).

However, in General Formula (3), (4), (5) or (6), R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent, and n1 and n2 are integers of 1 to 6 Represents. R ¹ and R ² are preferably hydrogen atoms.

Examples of the monovalent substituent represented by R ¹ or R ² include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group). , Tridecyl group, tetradecyl group, pentadecyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg ethynyl group, propargyl group etc.) ), Aromatic hydrocarbon group (also called aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group Fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group), Heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, carbazolyl group, phenylcarbazolyl group (for example, 9-phenylcarbazolyl group), dibenzofuryl group, dibenzothienyl group, carbolinyl group, diazacarbazolyl group (in which one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom) ), Phthalazinyl group, etc.), heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group) Group, octyloxy group, dodecylo group Si group etc.), cycloalkoxy group (eg cyclopentyloxy group, cyclohexyloxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), alkylthio group (eg methylthio group, ethylthio group, propylthio group, Pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyl Oxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenyloxycarbonyl group, naphthi) Ruoxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group) Phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexyl) Carbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group) Group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propyl) Carbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl) Group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl Nyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group) Pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, (Cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.) , Alkylsulfonyl groups (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl groups or heteroarylsulfonyl groups (for example, phenylsulfonyl group, Naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthyl) An amino group, a 2-pyridylamino group, a piperidyl group (also called a piperidinyl group), a 2,2,6,6-tetramethylpiperidinyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), Fluoride Hydrogen halide group (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (eg, trimethylsilyl group, triisopropylsilyl group) Group, triphenylsilyl group, phenyldiethylsilyl group and the like), phosphoric acid ester group (for example, dihexyl phosphoryl group and the like), phosphite group (for example, diphenylphosphinyl group and the like), phosphono group and the like.

  Specific examples of the compound represented by the general formula (1), (2), (3), (4), (5) or (6) are shown below, but are not limited thereto. .

  Specific examples of the synthesis of compound 1-1 are shown below as examples of typical compounds.

  Compound 1-1a (1.0 g), carbazole (3.0 g), copper powder (0.4 g), potassium carbonate (1.4 g) and DMAc (30 ml) were placed in a 100 ml eggplant-shaped flask, and the system was purged with nitrogen And stirred at 150 ° C. for 10 hours. After completion of the reaction, purification by column chromatography gave 0.7 g of white solid. The obtained compound was confirmed to be compound 1-1 by NMR spectrum and Mass spectrum.

  The compound represented by the general formula (1), (2), (3), (4), (5) or (6) described above is a light emitting layer of an organic EL device, specifically a host compound ( It can be suitably used as a luminescent host compound.

<< Constituent layers of organic EL elements >>
The constituent layers of the organic EL element of the present invention will be described. In this invention, although the preferable specific example of the layer structure of an organic EL element is shown below, this invention is not limited to these.

(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode (vi) anode / hole transport layer / anode buffer layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (vii) anode / anode buffer Layer / hole transport layer / light emitting layer / electron transport layer / cathode buffer layer / cathode The light emitting layer may form a unit to form a light emitting layer unit.

  Further, a non-light emitting intermediate layer may be provided between the light emitting layers, and the intermediate layer may include a charge generation layer. The organic EL element of the present invention is preferably a white light emitting layer, and is preferably a lighting device using these.

  Each layer which comprises the organic EL element of this invention is demonstrated.

《Electron transport layer》
The electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided with a single layer or a plurality of layers.

  An electron transport material (including a hole blocking material and an electron injection material) used for the electron transport layer only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer. Can be selected and used from conventionally known compounds.

  Examples of conventionally known materials used for the electron transport layer (hereinafter referred to as electron transport materials) include heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, And azacarbazole derivatives including carbodiimide, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, carboline derivatives, and the like.

  Here, the azacarbazole derivative refers to one in which one or more carbon atoms constituting the carbazole ring are replaced with a nitrogen atom.

  Furthermore, in the oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as an electron transport material.

  It is also possible to use a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain.

  In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material.

  In addition, metal-free or metal phthalocyanine, or those having the terminal substituted with an alkyl group or a sulfonic acid group can also be used as the electron transport material.

  Further, similarly to the hole injection layer and the hole transport layer, inorganic semiconductors such as n-type-Si and n-type-SiC can also be used as the electron transport material.

  The electron transport layer is made of an electron transport material such as a vacuum deposition method, a wet method (also referred to as a wet process, such as a spin coating method, a casting method, a die coating method, a blade coating method, a roll coating method, an ink jet method, a printing method, or a spraying method. It is preferable to form the film by a coating method, a curtain coating method, an LB method (such as Langmuir-Blodgett method)).

  The method for forming the constituent layers of the organic EL element will be described in detail in the section of the method for manufacturing the organic EL element.

  Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, about 5 nm-5000 nm, Preferably it is 5 nm-200 nm. This electron transport layer may have a single layer structure composed of one or more of the above materials.

  Further, an electron transport layer having a high n property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

  Hereinafter, although the specific example of the conventionally well-known compound (electron transport material) preferably used for formation of the electron carrying layer of the white organic EL element of this invention is given, this invention is not limited to these.

<Light emitting layer>
The light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.

  The total film thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the uniformity of the film, preventing unnecessary application of high voltage during light emission, and improving the stability of the emission color with respect to the drive current. It is preferable to adjust in the range of 2 nm to 5 μm, more preferably in the range of 2 nm to 200 nm, and particularly preferably in the range of 5 nm to 100 nm.

  For the production of the light emitting layer, a light emitting dopant or host compound described later is used, for example, a vacuum deposition method, a wet method (also referred to as a wet process, such as a spin coating method, a casting method, a die coating method, a blade coating method, a roll coating method, An ink-jet method, a printing method, a spray coating method, a curtain coating method, an LB method (a Langmuir-Blodgett method and the like can be used)) and the like can be formed. When using the compound of this invention for a light emitting layer, producing by a wet process is preferable.

  The light emitting layer of the organic EL device of the present invention contains a light emitting dopant (phosphorescent dopant (also referred to as phosphorescent dopant, phosphorescent dopant group) or fluorescent dopant) compound and a light emitting host compound. Is preferred.

(Luminescent dopant compound)
A light-emitting dopant compound (also referred to as a light-emitting dopant) will be described.

  As the light-emitting dopant, a fluorescent dopant (also referred to as a fluorescent compound) or a phosphorescent dopant (also referred to as a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like) can be used.

(Phosphorescent dopant (also called phosphorescent dopant))
The phosphorescent dopant according to the present invention will be described.

  The phosphorescent dopant compound according to the present invention is a compound in which light emission from an excited triplet is observed, specifically, a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescence quantum yield of 25. Although it is defined as a compound of 0.01 or more at ° C., a preferable phosphorescence quantum yield is 0.1 or more.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence dopant according to the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. That's fine.

  There are two types of light emission of the phosphorescent dopant in principle. One is the recombination of carriers on the host compound to which carriers are transported to generate an excited state of the luminescent host compound, and this energy is used as the phosphorescent dopant. The energy transfer type in which light emission from the phosphorescent dopant is obtained by moving to the other, and the other is that the phosphorescent dopant becomes a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant compound occurs. In any case, the excited state energy of the phosphorescent dopant is required to be lower than the excited state energy of the host compound.

  Moreover, you may use together the compound etc. which are described in the following patent gazettes in the light emitting layer which concerns on this invention.

  For example, International Publication No. 00/70655 pamphlet, Japanese Patent Application Laid-Open No. 2002-280178, Japanese Patent Application Laid-Open No. 2001-181616, Japanese Patent Application Laid-Open No. 2002-280179, Japanese Patent Application Laid-Open No. 2001-181617, and Japanese Patent Application Laid-Open No. 2002-280180. JP, 2001-247859, JP, 2002-299060, JP, 2001-313178, JP, 2002-302671, JP, 2001-345183, JP, 2002-324679, International, Publication No. 02/15645, JP 2002-332291 A, JP 2002-50484 A, JP 2002-332292 A, JP 2002-83684 A, JP 2002-540572 A, JP 2002-117978, JP 2002-338588, JP 2002-170684, JP 2002-352960, WO 01/93642, JP 2002-50483, JP 2002-1000047, JP JP 2002-173684 A, JP 2002-359082 A, JP 2002-17584 A, JP 2002-363552 A, JP 2002-184582 A, JP 2003-7469 A, Special Table 2002. No. 525808, JP 2003-7471, JP 2002-525833, JP 2003-31366, JP 2002-226495, JP 2002-234894, JP 2002-233506 Japanese Patent Laid-Open No. 2002-24175 JP, JP 2001-319779, JP 2001-319780, JP 2002-62824, JP 2002-1000047, JP 2002-203679, 2002-343572. JP-A-2002-203678.

(Fluorescent dopant (also called fluorescent compound))
Fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes , Polythiophene dyes, rare earth complex phosphors, and the like, and compounds having a high fluorescence quantum yield such as laser dyes.

  In addition, the light-emitting dopant according to the present invention may be used in combination of a plurality of types of compounds, or may be a combination of phosphorescent dopants having different structures, or a combination of a phosphorescent dopant and a fluorescent dopant.

  In the present invention, the dopant compound is preferably a compound represented by the following general formula (7), more preferably a compound represented by the following general formula (8), particularly represented by the following general formula (9). Are preferred.

In the general formula (7), P and Q each represent a carbon atom or a nitrogen atom, and A ₁ represents an atomic group that forms an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with P—C. A ₂ represents an atomic group that forms an aromatic heterocycle with QN. P ₁ -L ₁ -P ₂ represents a bidentate ligand, and P ₁ and P ₂ each independently represent a carbon atom, a nitrogen atom or an oxygen atom. L ₁ represents an atomic group that forms a bidentate ligand with P ₁ and P ₂ . j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, and j1 + j2 is 2 or 3. M ₁ represents a group 8-10 transition metal element in the periodic table.

In the general formula (7), the aromatic hydrocarbon ring formed by A ₁ together with P—C includes benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring , Triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring , Pyrene ring, pyranthrene ring, anthraanthrene ring and the like.

  These rings may further have an arbitrary substituent for substituting the carbazolyl group in the general formula (1).

In the general formula (7), the aromatic heterocycle formed by A ₁ together with P—C includes a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine ring. , Benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, aza And a carbazole ring.

  Here, the azacarbazole ring refers to one in which one or more carbon atoms constituting the carbazole ring are replaced with a nitrogen atom.

  These rings may further have an arbitrary substituent for substituting the carbazolyl group in the general formula (1).

In the general formula (7), examples of the aromatic heterocycle formed by A ₂ together with QN include an oxazole ring, an oxadiazole ring, an oxatriazole ring, an isoxazole ring, a tetrazole ring, a thiadiazole ring, a thiatriazole ring, Examples include isothiazole ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, pyrazole ring, and triazole ring.

  These rings may further have an arbitrary substituent for substituting the carbazolyl group in the general formula (1).

In the general formula (7), specific examples of the bidentate ligand represented by P ₁ -L ₁ -P ₂ include phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabol, acetylacetone, Examples include picolinic acid.

  In the general formula (7), j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, j1 + j2 represents 2 or 3, and j2 is preferably 0.

In the general formula (7), M ₁ is a transition metal element of Group 8 to Group 10 (also simply referred to as a transition metal) in the periodic table, and iridium is particularly preferable.

  Among the compounds represented by the general formula (7) according to the present invention, the compounds represented by the general formula (8) are preferable.

In General formula (8), Z represents a hydrocarbon ring group or a heterocyclic group. _{P, Q, A 1, P} 1, P 2, j1, j2 and _{M 1} has the same meaning _P in formula (7), _Q, and _{A 1, P 1, P 2} , j1, j2 and _{M 1} , P ₁ -L ₁ -P ₂ represents a bidentate ligand, and j 1 + j 2 is 2 or 3. A ₃ represents -C (R ₀₁ ) = C (R ₀₂ )-, -N = C (R ₀₂ )-, -C (R ₀₁ ) = N- or -N = N-, and R ₀₁ , R ₀₂ Each represents a hydrogen atom or a substituent.

  In the general formula (8), examples of the hydrocarbon ring group represented by Z include a non-aromatic hydrocarbon ring group and an aromatic hydrocarbon ring group, and examples of the non-aromatic hydrocarbon ring group include a cyclopropyl group. , Cyclopentyl group, cyclohexyl group and the like. These groups may be unsubstituted or have a substituent described later.

  Examples of the aromatic hydrocarbon ring group (also referred to as aromatic hydrocarbon group, aryl group, etc.) include, for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl. Group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group and the like.

  These groups may be unsubstituted or may have an arbitrary substituent for substituting the carbazolyl group in the general formula (1).

  In the general formula (8), examples of the heterocyclic group represented by Z include a non-aromatic heterocyclic group and an aromatic heterocyclic group. Examples of the non-aromatic heterocyclic group include an epoxy ring and an aziridine group. Ring, thiirane ring, oxetane ring, azetidine ring, thietane ring, tetrahydrofuran ring, dioxolane ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, oxazolidine ring, tetrahydrothiophene ring, sulfolane ring, thiazolidine ring, ε-caprolactone ring, ε- Caprolactam ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, morpholine ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, trioxane ring, tetrahydrothiopyran ring, thiomorpholine Ring, thiomorpholine-1,1-dioxide And groups derived from a ring, a pyranose ring, a diazabicyclo [2,2,2] -octane ring, and the like.

  These groups may be unsubstituted or may have an arbitrary substituent for substituting the carbazolyl group in the general formula (1).

  Examples of the aromatic heterocyclic group include pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl). Group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group , Benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, azacarbazolyl group (here, azacarbazolyl group is a group in which one or more carbon atoms constituting the carbazolyl group are replaced by nitrogen atoms). Quinoxalinyl group, pyridazinyl group, triazinyl , Quinazolinyl group, phthalazinyl group, and the like.

  These groups may be unsubstituted or may have an arbitrary substituent for substituting the carbazolyl group in the general formula (1).

  Preferably, the group represented by Z is an aromatic hydrocarbon ring group or an aromatic heterocyclic group.

  Although the preferable example of Z in General formula (8) is given to the following, Z may be unsubstituted other than the following illustration, may have a substituent further, and is not limited to these examples. Note that * represents a bonding position.

  One preferred embodiment of the compound represented by the general formula (8) is a compound represented by the general formula (9).

In General Formula (9), R ₀₃ represents a substituent, R ₀₄ represents a hydrogen atom or a substituent, and a plurality of R ₀₄ may be bonded to each other to form a ring. n ₀₁ represents an integer of 1 to 4. R ₀₅ represents a hydrogen atom or a substituent, and a plurality of R ₀₅ may be bonded to each other to form a ring. _n02 represents an integer of 1 to 2. R ₀₆ represents a hydrogen atom or a substituent, and may combine with each other to form a ring. n ₀₃ represents an integer of 1 to 4. Z ₁ represents an atomic group necessary for forming a 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocycle together with C—C. Z ₂ represents an atomic group necessary for forming a hydrocarbon ring group or a heterocyclic group. P ₁ , P ₂ , j ₁ , j ₂ and M ₁ are synonymous with P ₁ , P ₂ , j ₁ , j ₂ and M ₁ in the general formula (7), and P ₁ -L ₁ -P ₂ is a bidentate arrangement. Represents a rank, and j1 + j2 is 2 or 3. R ₀₃ and R ₀₆ , R ₀₄ and R _06, and R ₀₅ and R ₀₆ may be bonded to each other to form a ring.

In the general formula (9), each of the substituents represented by R ₀₃ , R ₀₄ , R ₀₅ , and R ₀₆ may be further substituted with any substituent that replaces the carbazolyl group in the general formula (1). Good.

In the general formula (9), the 6-membered aromatic hydrocarbon ring formed by Z ₁ together with C—C is preferably a benzene ring. These rings may further have an arbitrary substituent for substituting the carbazolyl group in the general formula (1).

In the general formula (9), examples of the 5-membered or 6-membered aromatic heterocycle formed by Z ₁ together with C—C include an oxazole ring, an oxadiazole ring, an oxatriazole ring, an isoxazole ring, a tetrazole ring, Examples include thiadiazole ring, thiatriazole ring, isothiazole ring, thiophene ring, furan ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, pyrazole ring, triazole ring and the like.

  These rings may further have an arbitrary substituent for substituting the carbazolyl group in the general formula (1).

In the general formula _(9), bidentate ligand represented by P 1 _-L 1 -P ₂ are the compounds of formula _(7), coordination of bidentate represented by P 1 _-L 1 -P ₂ Synonymous with rank.

In the general formula (9), transition metal elements of group 8-10 of the periodic table represented by _{M 1} are the compounds of formula (7), group 8-10 of the periodic table represented by _{M 1} It is synonymous with the transition metal element.

  The compounds represented by the general formula (7), (8) or (9) according to the present invention are described in Eur. J. et al. Chem. 2005, 1637-1643 or the like, or a halogen compound corresponding to a nitrogen-containing ring compound or an imidazole compound is reacted, or the corresponding amine, glyoxal, and aldehyde described in SYNTHESIS 2003, 17, 2661-2666, or the like It can be synthesized by referring to the reaction of ammonium chloride with ammonium chloride.

  Specific examples of dopant compounds that can be preferably used in the present invention are given below. Of course, the present invention is not limited to these.

(Host compound (also referred to as luminescent host compound, luminescent host, etc.))
As described above, the compound represented by the general formula (1), (2), (3), (4), (5) or (6) can be used as the host compound.
The compound represented by the general formula (1), (2), (3), (4), (5) or (6) can be used alone or in combination with a known host compound. You can also.

  Even when the above-described compound is used alone or in combination with a known host compound, the host compound includes a mass ratio in the layer among the compounds contained in the light emitting layer. Is a compound having a phosphorescence quantum yield of phosphorescence emission of less than 0.1 at room temperature (25 ° C.). The phosphorescence quantum yield is preferably less than 0.01. Moreover, it is preferable that the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.

  Known host compounds typically include those having a basic skeleton such as carbazole derivatives, triarylamine derivatives, aromatic derivatives, nitrogen-containing heterocyclic compounds, thiophene derivatives, furan derivatives, oligoarylene compounds, or carboline derivatives. And diazacarbazole derivatives (herein, diazacarbazole derivatives are those in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom). .

  As the known light-emitting host that can be used in the present invention, a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from becoming longer, and has a high Tg (glass transition temperature) is preferable.

  In addition, when the compound represented by the general formula (1), (2), (3), (4), (5) or (6) and a known host compound are used in combination, the movement of charge is adjusted. It is possible to increase the efficiency of the organic EL element.

  Moreover, it becomes possible to mix different light emission by using multiple types of well-known compounds used as the said phosphorescence dopant, and, thereby, arbitrary luminescent colors can be obtained.

  The host compound used in the present invention may be a low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (polymerizable light emitting host). Of course, one or more of such compounds may be used.

  Specific examples of known host compounds include compounds described in the following documents.

  JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, and the like.

  Hereinafter, although the specific example of the conventionally well-known compound used as a host compound of the light emitting layer of the organic EL element of this invention is given, this invention is not limited to these.

  Particularly preferred as the host compound of the organic EL device of the present invention is the compound represented by the general formula (1) of the present invention described above, and specific examples thereof include the compound examples 1-1 to 3-60. Can be mentioned.

《Hole transport layer》
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

  The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and also two of those described in US Pat. No. 5,061,569. Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-3086 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 8 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material as described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, these materials are preferably used because a light-emitting element with higher efficiency can be obtained.

  The hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can.

  Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5 nm-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

  Alternatively, a hole transport layer having a high p property doped with impurities can be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.

  In the present invention, it is preferable to use a hole transport layer having such a high p property because a device with lower power consumption can be produced.

  Hereinafter, although the specific example of the compound preferably used for formation of the positive hole transport layer of the organic EL element of this invention is given, this invention is not limited to these.

<Blocking layer: hole blocking layer, electron blocking layer>
The blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

  The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material having a function of transporting electrons but having a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking.

  Moreover, the structure of the above-mentioned electron carrying layer can be used as a hole-blocking layer concerning this invention as needed.

  The hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.

  In the hole blocking layer, the compound represented by the general formula (1), (2), (3), (4), (5) or (6), carbazole derivative, aza, which are exemplified as the host compound described above. It is preferable to contain a carbazole derivative (here, an azacarbazole derivative indicates one in which one or more carbon atoms constituting the carbazole ring are replaced with a nitrogen atom).

  In the present invention, when a plurality of light emitting layers having different light emission colors are provided, the light emitting layer having the shortest wavelength of light emission is preferably closest to the anode among all the light emitting layers. In this case, it is preferable to additionally provide a hole blocking layer between the shortest wave layer and the light emitting layer next to the anode next to the anode. Furthermore, it is preferable that 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.

  The ionization potential is defined by the energy required to emit electrons at the HOMO (highest occupied orbital) level of the compound to the vacuum level, and can be determined by, for example, the following method.

  (1) Using Gaussian 98 (Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.), a molecular orbital calculation software manufactured by Gaussian, USA As a value (eV unit converted value) calculated by performing structure optimization using B3LYP / 6-31G *. This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.

  (2) The ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy. For example, a method known as ultraviolet photoelectron spectroscopy can be suitably used by using a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd.

  On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material having a function of transporting holes and a remarkably small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved.

  Moreover, the structure of the above-mentioned hole transport layer can be used as an electron blocking layer as needed. The film thickness of the hole blocking layer and the electron blocking layer according to the present invention is preferably 3 nm to 100 nm, more preferably 3 nm to 30 nm.

<< Injection layer: electron injection layer (cathode buffer layer), hole injection layer >>
The injection layer can be provided as necessary. The injection layer includes an electron injection layer and a hole injection layer, and may be present between the anode and the light emitting layer or the hole transport layer and between the cathode and the light emitting layer or the electron transport layer as described above.

  An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166), and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

  The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. Examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by, alkali metal compound buffer layer typified by lithium fluoride, sodium fluoride and potassium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, and aluminum oxide And an oxide buffer layer. The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm although it depends on the material.

  In addition, the materials used for the anode buffer layer and the cathode buffer layer can be used in combination with other materials. For example, the materials can be mixed in the hole transport layer or the electron transport layer.

"anode"
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO.

Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 μm or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.

  Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1000 nm, preferably 10 nm to 200 nm.

"cathode"
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.

Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.

  The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as a cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 nm to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

  Moreover, after producing the said metal by the film thickness of 1 nm-20 nm to a cathode, the transparent or semi-transparent cathode can be produced by producing the electroconductive transparent material quoted by description of the anode on it, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

《Support substrate》
Examples of the support substrate (hereinafter also referred to as a substrate, a substrate, a base material, a support, etc.) that can be used in the organic EL element of the present invention include glass and plastic. These types are not particularly limited, and may be transparent or opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.

  Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Can be mentioned.

On the surface of the resin film, an inorganic film, an organic film, or a hybrid film of both may be formed. Water vapor permeability (25 ± 0.5 ° C.) measured by a method according to JIS K 7129-1992. , Relative humidity (90 ± 2)% RH) is preferably 0.01 g / (m ² · 24 h) or less, and further, oxygen measured by a method according to JIS K 7126-1987. A high barrier film having a permeability of 10 ⁻³ ml / (m ² · 24 h · atm) or less and a water vapor permeability of 10 ⁻⁵ g / (m ² · 24 h) or less is preferable.

  As a material for forming the barrier film, any material may be used as long as it has a function of suppressing entry of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and organic material layers. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

  The method for forming the barrier film is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma polymerization A plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.

  Examples of the opaque support substrate include metal plates such as aluminum and stainless steel, films, opaque resin substrates, and ceramic substrates.

  The external extraction quantum efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more.

  Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

  In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination. In the case of using a color conversion filter, the λmax of light emission of the organic EL element is preferably 480 nm or less.

<< Method for Manufacturing Organic EL Element >>
As an example of a method for producing an organic EL device, a device comprising an anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode Will be described.

  First, a desired electrode material, for example, a thin film made of a material for an anode is formed on a suitable substrate so as to have a thickness of 1 μm or less, preferably 10 nm to 200 nm, thereby producing an anode.

  Next, a thin film containing an organic compound such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, or a cathode buffer layer, which is an element material, is formed thereon.

  In the phosphorescent organic EL device of the present invention, at least the cathode and the electron transport layer adjacent to the cathode are applied and formed by a wet method.

  Wet methods include spin coating, casting, die coating, blade coating, roll coating, ink jet, printing, spray coating, curtain coating, and LB, but precise thin films can be formed. In view of high productivity, a method having high suitability for a roll-to-roll method such as a die coating method, a roll coating method, an ink jet method, or a spray coating method is preferable. Different film forming methods may be applied for each layer.

  Examples of the liquid medium for dissolving or dispersing the organic EL material according to the present invention include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, and mesitylene. Aromatic hydrocarbons such as cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as DMF and DMSO can be used.

  Moreover, as a dispersion method, it can disperse | distribute by dispersion methods, such as an ultrasonic wave, high shear force dispersion | distribution, and media dispersion | distribution.

  After the formation of these layers, a thin film made of a cathode material is formed thereon so as to have a thickness of 1 μm or less, preferably in the range of 50 to 200 nm, and a desired organic EL device can be obtained by providing a cathode. .

  Further, the order can be reversed, and the cathode, cathode buffer layer, electron transport layer, hole blocking layer, light emitting layer, hole transport layer, hole injection layer, and anode can be formed in this order.

  When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 V to 40 V with the anode as + and the cathode as-. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

  The organic EL device of the present invention is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is preferable to perform the work in a dry inert gas atmosphere.

<Sealing>
The organic EL element is used after being sealed with a sealing member. As a sealing means used for this invention, the method of adhere | attaching a sealing member, an electrode, and a support substrate with an adhesive agent can be mentioned, for example.

  As a sealing member, it should just be arrange | positioned so that the display area | region of an organic EL element may be covered, and concave plate shape or flat plate shape may be sufficient. Further, transparency and electrical insulation are not particularly limited.

  Specific examples include a glass plate, a polymer plate / film, and a metal plate / film. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.

  Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.

  In the present invention, a polymer film and a metal film can be preferably used because the element can be thinned.

Furthermore, the polymer film has an oxygen permeability of 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less measured by a method according to JIS K 7126-1987, and a method according to JIS K 7129-1992. It is preferable that the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured in (1) is 1 × 10 ⁻³ g / (m ² · 24 h) or less.

  For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.

  Specific examples of the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to. Moreover, heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.

  In addition, since an organic EL element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable. A desiccant may be dispersed in the adhesive. Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.

  In addition, it is also preferable that the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film. . In this case, the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can.

  Further, in order to improve the brittleness of the film, it is preferable to have a laminated structure of these inorganic layers and layers made of organic materials. The method for forming these films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

  In the gap between the sealing member and the display area of the organic EL element, an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase. preferable. A vacuum is also possible. Moreover, a hygroscopic compound can also be enclosed inside.

  Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate). Etc.), metal halides (eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.), perchloric acids (eg perchloric acid) Barium, magnesium perchlorate, and the like), and anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.

《Protective film, protective plate》
In order to increase the mechanical strength of the element, a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the support substrate with the organic layer interposed therebetween or on the sealing film. In particular, when the sealing is performed by the sealing film, the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate. As a material that can be used for this, the same glass plate, polymer plate / film, metal plate / film, and the like used for the sealing can be used, but the polymer film is light and thin. Is preferably used.

《Light extraction》
The organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1) and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said. This is because light incident on the interface (interface between the transparent substrate and air) at an angle θ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the element side surface.

  As a method for improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435), A method of improving efficiency by providing a light collecting property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on a side surface of an element (Japanese Patent Laid-Open No. 1-220394), and light emission from a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the bodies (Japanese Patent Laid-Open No. 62-172691), a flat having a lower refractive index between the substrate and the light emitter than the substrate A method of introducing a layer (Japanese Patent Laid-Open No. 2001-202827), a method of forming a diffraction grating between any one of a substrate, a transparent electrode layer and a light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 11-283951) Gazette).

  In the present invention, these methods can be used in combination with the organic EL device of the present invention. However, a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, transparent A method of forming a diffraction grating between any layers of the electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.

  In the present invention, by combining these means, it is possible to obtain an element having higher luminance or durability.

  When a medium having a low refractive index is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.

  Examples of the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.

  The thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate.

  The method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency. This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction. Light that cannot be emitted due to total internal reflection between layers is diffracted by introducing a diffraction grating in any layer or medium (in a transparent substrate or transparent electrode), and the light is removed. I want to take it out.

  The introduced diffraction grating desirably has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much.

  However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.

  As described above, the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or in the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.

  At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium.

  The arrangement of the diffraction grating is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.

<Condenser sheet>
The organic EL device of the present invention can be processed to provide, for example, a microlens array-like structure on the light extraction side of the substrate, or combined with a so-called condensing sheet, for example, in a specific direction, for example, the device light emitting surface. In contrast, the light can be condensed in the front direction, and the luminance in a specific direction can be increased.

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 μm to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

  As the condensing sheet, for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used. As such a sheet, for example, a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used.

  As the shape of the prism sheet, for example, a substrate may be formed by forming a triangle (triangular) stripe with a vertex angle of 90 degrees and a pitch of 50 μm, a shape with a rounded vertex, and a pitch. The shape may be changed at random, or other shapes.

  Moreover, in order to control the light emission angle from a light emitting element, you may use together a light diffusing plate and a film with a condensing sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

<Application>
The organic EL element of the present invention can be used as a display device, a display, and various light emission sources. For example, lighting devices (home lighting, interior lighting), clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light Examples include, but are not limited to, a sensor light source. In particular, it can be effectively used as a backlight of a liquid crystal display device and an illumination light source.

  In the organic EL element of the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned. In the fabrication of the element, a conventionally known method is used. Can do.

  The light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with a total CS-1000 (Konica Minolta Sensing Co., Ltd.) is applied to the CIE chromaticity coordinates.

When the organic EL element of the present invention is a white element, white means that the chromaticity in the CIE1931 color system at 1000 cd / m ² is X when the 2 ° viewing angle front luminance is measured by the above method. = 0.33 ± 0.07 and Y = 0.33 ± 0.1.

<Display device>
The display device of the present invention will be described. The display device of the present invention comprises the organic EL element of the present invention.

  Although the display device of the present invention may be single color or multicolor, the multicolor display device will be described here. In the case of a multicolor display device, a shadow mask is provided only at the time of forming a light emitting layer, and a film can be formed on one surface by vapor deposition, casting, spin coating, ink jet, printing, or the like.

  In the case of patterning only the light emitting layer, the method is not limited. However, the vapor deposition method, the ink jet method, the spin coating method, and the printing method are preferable.

  The configuration of the organic EL element provided in the display device is selected from the above-described configuration examples of the organic EL element as necessary.

  Moreover, the manufacturing method of an organic EL element is as having shown to the one aspect | mode of manufacture of the organic EL element of said invention.

  In the case of applying a DC voltage to the obtained multicolor display device, light emission can be observed by applying a voltage of about 2V to 40V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The alternating current waveform to be applied may be arbitrary.

  The multicolor display device can be used as a display device, a display, and various light emission sources. In a display device or display, full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.

  Examples of the display device and display include a television, a personal computer, a mobile device, an AV device, a character broadcast display, and an information display in an automobile. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.

  Light sources include home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc. The present invention is not limited to these examples.

  Hereinafter, an example of a display device having the organic EL element of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic view showing an example of a display device composed of organic EL elements, and is a schematic view of a display such as a mobile phone that displays image information by light emission of the organic EL elements.

  The display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.

  The control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of a plurality of pixels based on image information from the outside, and the pixels for each scanning line respond to the image data signal by the scanning signal. The image information is sequentially emitted to scan the image and display the image information on the display unit A.

  FIG. 2 is a schematic diagram of the display unit A.

  The display unit A includes a wiring unit including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3 and the like on a substrate. The main members of the display unit A will be described below.

  In the figure, the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).

  The scanning line 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at the orthogonal positions (details are illustrated). Not)

  When a scanning signal is applied from the scanning line 5, the pixel 3 receives an image data signal from the data line 6 and emits light according to the received image data.

  Full-color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region on the same substrate.

  Next, the light emission process of the pixel will be described.

  FIG. 3 is a schematic diagram of a pixel.

  The pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like. A full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 10 in a plurality of pixels, and juxtaposing them on the same substrate.

  In FIG. 3, an image data signal is applied from the control unit B to the drain of the switching transistor 11 through the data line 6. When a scanning signal is applied from the control unit B to the gate of the switching transistor 11 via the scanning line 5, the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is supplied to the capacitor 13 and the driving transistor 12. Is transmitted to the gate.

  By transmitting the image data signal, the capacitor 13 is charged according to the potential of the image data signal, and the drive of the drive transistor 12 is turned on. The drive transistor 12 has a drain connected to the power supply line 7 and a source connected to the electrode of the organic EL element 10, and the power supply line 7 connects to the organic EL element 10 according to the potential of the image data signal applied to the gate. Current is supplied.

  When the scanning signal is moved to the next scanning line 5 by the sequential scanning of the control unit B, the driving of the switching transistor 11 is turned off. However, even if the driving of the switching transistor 11 is turned off, the capacitor 13 maintains the potential of the charged image data signal, so that the driving of the driving transistor 12 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 10 continues. When the scanning signal is next applied by sequential scanning, the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.

  That is, the light emission of the organic EL element 10 is performed by providing the switching transistor 11 and the drive transistor 12 which are active elements with respect to the organic EL element 10 of each of the plurality of pixels. It is carried out. Such a light emitting method is called an active matrix method.

  Here, the light emission of the organic EL element 10 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or by turning on / off a predetermined light emission amount by a binary image data signal. Good. The potential of the capacitor 13 may be held continuously until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.

  In the present invention, not only the active matrix method described above, but also a passive matrix light emission drive in which the organic EL element emits light according to the data signal only when the scanning signal is scanned.

  FIG. 4 is a schematic diagram of a passive matrix display device. In FIG. 4, a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.

  When the scanning signal of the scanning line 5 is applied by sequential scanning, the pixels 3 connected to the applied scanning line 5 emit light according to the image data signal.

  In the passive matrix system, the pixel 3 has no active element, and the manufacturing cost can be reduced.

《Lighting device》
The lighting device of the present invention will be described. The illuminating device of this invention has the said organic EL element.

  The organic EL element of the present invention may be used as an organic EL element having a resonator structure. The purpose of use of the organic EL element having such a resonator structure is as follows. The light source of a machine, the light source of an optical communication processing machine, the light source of a photosensor, etc. are mentioned, However, It is not limited to these. Moreover, you may use for the said use by making a laser oscillation.

  Further, the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a display for directly viewing a still image or a moving image. It may be used as a device (display).

  The driving method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, a full-color display device can be manufactured by using two or more organic EL elements of the present invention having different emission colors.

  The organic EL material represented by the general formula (1) of the present invention can be applied to an organic EL element that emits substantially white light as a lighting device. A plurality of light emitting colors are simultaneously emitted by a plurality of light emitting materials to obtain white light emission by color mixing. The combination of a plurality of emission colors may include three emission maximum wavelengths of three primary colors of blue, green, and red, or two using the complementary colors such as blue and yellow, blue green and orange, etc. The thing containing the light emission maximum wavelength may be used.

  In addition, a combination of light emitting materials for obtaining a plurality of emission colors is a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescence or phosphorescence, and light from the light emitting material as excitation light. Any of those combined with a dye material that emits light may be used, but in the white organic EL device according to the present invention, only a combination of a plurality of light-emitting dopants may be mixed.

  It is only necessary to provide a mask only when forming a light emitting layer, a hole transport layer, an electron transport layer, etc., and simply arrange them separately by coating with the mask. In addition, for example, an electrode film can be formed by a vapor deposition method, a cast method, a spin coating method, an ink jet method, a printing method, or the like, and productivity is also improved.

  According to this method, unlike a white organic EL device in which light emitting elements of a plurality of colors are arranged in parallel in an array, the elements themselves are luminescent white.

  There is no restriction | limiting in particular as a luminescent material used for a light emitting layer, For example, if it is a backlight in a liquid crystal display element, the metal complex which concerns on this invention so that it may suit the wavelength range corresponding to CF (color filter) characteristic, Any one of known luminescent materials may be selected and combined to whiten.

<< One Embodiment of Lighting Device of the Present Invention >>
One aspect of the lighting device of the present invention that includes the organic EL element of the present invention will be described.

  The non-light-emitting surface of the organic EL element of the present invention is covered with a glass cover as a sealing member, a glass substrate having a thickness of 300 μm is used as a sealing substrate, and an epoxy-based photocurable adhesive (Toago) Synthetic Lux Track LC0629B) is applied, and this is overlaid on the cathode and brought into close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured, and sealed, as shown in FIGS. A lighting device as shown can be formed.

  FIG. 5 shows a schematic view of the lighting device. The organic EL element 101 of the present invention is fixed on a sealing substrate 103 and covered with a glass cover 102. The sealing operation with the glass cover is preferably performed in a glove box under a nitrogen atmosphere (in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more) without bringing the organic EL element 101 into contact with the atmosphere.

  6 shows a cross-sectional view of the lighting device shown in FIG. 5. In FIG. 6, reference numeral 104 denotes a sealing material, 105 denotes a cathode, 106 denotes an organic EL layer including a light emitting layer, and 107 denotes a glass substrate with a transparent electrode. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

<< Production of organic EL full-color display device >>
FIG. 7 shows a schematic configuration diagram of an organic EL full-color display device. Such an organic EL full-color display device can be manufactured as follows.
First, after patterning at a pitch of 100 μm on a substrate (NA techno glass NA45) having a 100 nm ITO transparent electrode (202) film formed on a glass substrate 201 as an anode, between the ITO transparent electrodes on this glass substrate A non-photosensitive polyimide partition wall 203 (width 20 μm, thickness 2.0 μm) is formed by photolithography.

  Next, a hole injection layer composition having the following composition is ejected and injected between polyimide partition walls on the ITO electrode using an inkjet head (for example, manufactured by Epson Corporation; MJ800C), irradiated with ultraviolet light for 200 seconds, 60 ° C., A hole injection layer 204 having a thickness of 40 nm is formed by a drying process for 10 minutes.

  Next, the following blue light-emitting layer composition, green light-emitting layer composition, and red light-emitting layer composition are similarly discharged and injected onto the hole injection layer using an inkjet head, and dried at 60 ° C. for 10 minutes. It processes and forms each light emitting layer (205B, 205G, 205R).

  Then, lithium fluoride is vacuum-deposited by 0.6 nm so as to cover the light-emitting layer, and Al (206) is vacuum-deposited by 130 nm as a cathode to produce an organic EL element.

  The organic EL device produced in this manner can emit blue, green, and red light by applying a voltage to each electrode. That is, it can be used as an organic EL full-color display device.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. The structures of the compounds used in the examples are shown below.

  The compound described as comp-1 is I-46 described in International Publication No. 2011/004639, and the compound described as comp-2 is 1-64 described in JP-A-2009-267255. It is.

[Example 1]
<< Production of Organic EL Element 1-1 >>
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
This transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, 200 mg of copper phthalocyanine (CuPc) is put in one molybdenum resistance heating boat, and 200 mg of α-NPD is put in another molybdenum resistance heating boat, Put 200 mg of CBP in a resistance heating boat made of molybdenum, put 200 mg of D-9 in another resistance heating boat made of molybdenum, put 200 mg of BAlq in another resistance heating boat made of molybdenum, and add Alq ₃ to another resistance heating boat made of molybdenum. 200 mg was added and attached to a vacuum deposition apparatus.
Next, the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, heated by energizing the heating boat containing CuPc, and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second to form a 10 nm hole injection layer. Was provided.
Further, the heating boat containing α-NPD was energized and heated, and was deposited on the hole injection layer at a deposition rate of 0.1 nm / second to provide a 30 nm hole transport layer.
Furthermore, the heating boat containing CBP and the heating boat containing D-9 were energized and heated, and co-deposited on the hole transport layer at deposition rates of 0.1 nm / second and 0.010 nm / second, respectively. A 40 nm light emitting layer was provided.
Further, the heating boat containing BAlq was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm hole blocking layer.
Further, the heating boat containing Alq ₃ was heated by energization, and deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to provide an electron transport layer of 30 nm.
Then, 0.5 nm of lithium fluoride was vapor-deposited as a cathode buffer layer, and also aluminum 110nm was vapor-deposited, the cathode was formed, and the organic EL element 1-1 was produced.

<< Production of Organic EL Elements 1-2 to 1-183 >>
In the production of the organic EL element 1-1, organic EL elements 1-2 to 1-183 were produced in the same manner except that CBP was changed to the compounds described in Tables 1 to 3.

<< Evaluation of Organic EL Elements 1-1 to 1-183 >>
When evaluating the obtained organic EL element, the non-light-emitting surface of each organic EL element after production is covered with a glass cover, and the glass cover side periphery where the glass cover and the glass substrate on which the organic EL element is produced contacts An epoxy photo-curing adhesive (Luxtrac LC0629B manufactured by Toagosei Co., Ltd.) was applied as a sealant to the cathode side, and this was adhered to the transparent support substrate to remove the organic EL element from the glass substrate side. The portion was irradiated with UV light, cured, and sealed to produce an illumination device as shown in FIGS. Using the manufactured lighting device, power efficiency, light emission lifetime, stability over time, and light emission color were evaluated. These evaluations were performed as follows.

(Power efficiency)
Using a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing Co., Ltd.), the front luminance and luminance angle dependency of each organic EL element were measured, and the power efficiency at a front luminance of 1000 cd / m ² was obtained.
In addition, the power efficiency was represented by the relative value which sets the power efficiency of the organic EL element 1-1 to 100.

(Luminescent life)
The organic EL device continuously emitted light at room temperature under a constant current condition of ^2.5 mA / cm ² , and the time (τ _1/2 ) required to reach half the initial luminance was measured. In addition, the light emission lifetime was represented by the relative value which sets the organic EL element 1-1 to 100.

(Stability over time)
After storing the organic EL element at 60 ° C. for 24 hours, each power efficiency before and after storage was determined, and each power efficiency ratio was determined according to the following formula, which was used as a measure of stability over time.
Stability over time (%) = power efficiency after storage / power efficiency before storage x 100
For power efficiency, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing Co., Ltd.) was used to measure the front luminance and luminance angle dependency of each organic EL element, and the power efficiency at a front luminance of 1000 cd / m ² was measured. Asked.

(Luminescent color)
The color of light emitted when continuous light emission was performed under a constant current condition of ^2.5 mA / cm ² was visually evaluated.

  As shown in Tables 1 to 3, the organic EL element (illumination device) according to the example using the host compound of the present invention (the compound represented by the general formula (1)) is an organic EL element according to a comparative example ( It is clear that the power efficiency, the light emission lifetime and the stability over time are superior to those of the lighting device.

[Example 2]
<< Production of organic EL element 2-1 >>
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
On this transparent support substrate, using a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water, 3000 rpm, A thin film was formed by spin coating under a condition of 30 seconds, and then dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 20 nm.
The substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of ADS254BE (American Dye Source, Inc.) dissolved in 10 ml of monochlorobenzene was used on the first hole transport layer at 2500 rpm for 30 seconds. A thin film was formed by spin coating. Furthermore, it vacuum-dried at 130 degreeC for 1 hour, and the 2nd positive hole transport layer was formed.
A thin film was formed on this second hole transport layer by spin coating using a solution of 100 mg CBP and 13 mg D-9 dissolved in 10 ml butyl acetate at 1000 rpm for 30 seconds. Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and was set as the light emitting layer with a film thickness of about 45 nm.
Next, a thin film was formed on this light emitting layer by spin coating under a condition of 1000 rpm and 30 seconds using a solution of 50 mg of BCP dissolved in 10 ml of hexafluoroisopropanol (HFIP). Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and was set as the electron carrying layer with a film thickness of about 25 nm.
Subsequently, this substrate is fixed to a substrate holder of a vacuum deposition apparatus, and after the vacuum chamber is depressurized to 4 × 10 ⁻⁴ Pa, 0.4 nm of potassium fluoride is deposited as a cathode buffer layer, and further, 110 nm of aluminum is deposited. Thus, a cathode was formed, and an organic EL element 2-1 was produced.

<< Production of organic EL elements 2-2 to 2-183 >>
Organic EL elements 2-2 to 2-183 were prepared in the same manner except that CBP was changed to the compounds shown in Tables 4 to 6 in preparation of the organic EL element 2-1.

<< Evaluation of Organic EL Elements 2-1 to 2-183 >>
When evaluating the obtained organic EL element, it was sealed in the same manner as the organic EL elements 1-1 to 1-183 in [Example 1], and a lighting device as shown in FIGS. evaluated. The external illumination quantum efficiency (EQE), the light emission lifetime, the voltage increase rate, and the light emission color were evaluated using the manufactured illumination device. These evaluations were performed as follows.

(External quantum efficiency (EQE))
By causing the organic EL device to emit light at room temperature (about 23 ° C. to 25 ° C.) and a constant current of ^2.5 mA / cm ² , and measuring the light emission luminance (L) [cd / m ² ] immediately after the start of light emission, The external extraction quantum efficiency (η) was calculated.
Here, CS-1000 (manufactured by Konica Minolta Sensing) was used for measurement of light emission luminance.
The external extraction quantum efficiency (EQE) was expressed as a relative value with the organic EL element 2-1 being 100.

(Luminescent life)
The organic EL device continuously emitted light at a constant current of 6 mA / cm ² at room temperature, and the time (τ _1/2 ) required to reach half the initial luminance was measured. In addition, the light emission lifetime was represented by the relative value which sets the organic EL element 2-1 to 100.

(Voltage increase rate)
The initial voltage and the voltage after 50 hours were measured when driven under a constant current condition of 6 mA / cm ² . The relative value of the voltage after 50 hours with respect to the initial voltage was defined as the voltage increase rate.

(Luminescent color)
The luminescent color was evaluated by the same method as in [Example 1].

  As shown in Tables 4-6, the organic EL element (illumination device) which concerns on the Example using the host compound (compound represented by General formula (1)) of this invention is the organic EL element which concerns on a comparative example ( It is clear that the EQE, the voltage increase rate, and the light emission life are superior to those of the lighting device.

Example 3
<< Production of Organic EL Element 3-1 >>
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, 200 mg of TPD is put into a molybdenum resistance heating boat, 200 mg of CBP is put into another molybdenum resistance heating boat, and D- 200 mg, 9 mg D-1 in another molybdenum resistance heating boat, 200 mg D-6 in another molybdenum resistance heating boat, 200 mg BCP in another molybdenum resistance heating boat, vacuum deposition Attached to the device.
Next, after reducing the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing TPD is heated by energization, and deposited on a transparent support substrate at a deposition rate of 0.1 nm / second to form a 10 nm hole transport layer. Was provided.
Further, the heating boat containing CBP, D-9, D-1, and D-6 was energized and heated, and the deposition rates were 0.1 nm / second, 0.025 nm / second, 0.0007 nm / second, and 0.005 nm, respectively. A 60 nm light emitting layer was provided by co-evaporation on the hole transport layer at 0002 nm / second.
Further, the heating boat containing BCP was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 20 nm electron transport layer.
Then, 0.5 nm of potassium fluoride was vapor-deposited as a cathode buffer layer, and also aluminum 110nm was vapor-deposited, the cathode was formed, and the organic EL element 3-1 was produced.

<< Production of Organic EL Elements 3-2 to 3-183 >>
In the production of the organic EL element 3-1, organic EL elements 3-2 to 3-183 were similarly produced except that CBP was changed to the compounds described in Tables 7 to 9.

<< Evaluation of Organic EL Elements 3-1 to 1-383 >>
When evaluating the obtained organic EL element, it was sealed in the same manner as the organic EL elements 1-1 to 1-183 in [Example 1], and a lighting device as shown in FIGS. evaluated. Using the manufactured lighting device, the driving voltage, stability over time, and emission color were evaluated. These evaluations were performed as follows.

(Drive voltage)
Each voltage was measured when the organic EL element was driven at room temperature (about 23 ° C. to 25 ° C.) and a constant current condition of ^2.5 mA / cm ² , and the measurement results are shown below. The relative values are shown with 1 being 100.
Voltage = (drive voltage of each element / drive voltage of the organic EL element 3-1) × 100
A smaller value indicates a lower drive voltage for comparison.

(Stability over time)
After storing the organic EL element at 85 ° C. for 24 hours, each power efficiency before and after storage was determined, and each power efficiency ratio was determined according to the following formula, which was used as a measure of stability over time.
Stability over time (%) = power efficiency after storage / power efficiency before storage x 100
For power efficiency, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing Co., Ltd.) was used to measure the front luminance and luminance angle dependency of each organic EL element, and the power efficiency at a front luminance of 1000 cd / m ² was measured. Asked.

(Luminescent color)
The luminescent color was evaluated by the same method as in [Example 1].

  As shown in Tables 7 to 9, the organic EL element (illumination device) according to the example using the host compound of the present invention (the compound represented by the general formula (1)) is an organic EL element according to a comparative example ( It is clear that the driving voltage and the stability over time are excellent (that is, the durability is excellent) as compared with the lighting device).

Example 4
<< Production of Organic EL Element 4-1 >>
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
On this transparent support substrate, using a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water, 3000 rpm, A thin film was formed by spin coating under a condition of 30 seconds, and then dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 20 nm.
The substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of ADS254BE (American Dye Source, Inc.) dissolved in 10 ml of monochlorobenzene was used on the first hole transport layer at 2500 rpm for 30 seconds. A thin film was formed by spin coating. Furthermore, it vacuum-dried at 130 degreeC for 1 hour, and the 2nd positive hole transport layer was formed.
On this second hole transport layer, a solution obtained by dissolving 100 mg CBP, 20 mg D-9, 0.5 mg D-1, 0.2 mg D-6 in 10 ml butyl acetate was used at 600 rpm, 30 A thin film was formed by spin coating under the condition of seconds. Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and was set as the light emitting layer with a film thickness of about 70 nm.
Next, a thin film was formed on the light-emitting layer by spin coating under a condition of 1500 rpm and 30 seconds using a solution of 50 mg of BCP dissolved in 10 ml of hexafluoroisopropanol (HFIP). Furthermore, it vacuum-dried at 60 degreeC for 1 hour, and was set as the electron carrying layer with a film thickness of about 20 nm.
Subsequently, this substrate is fixed to a substrate holder of a vacuum deposition apparatus, and after the vacuum chamber is depressurized to 4 × 10 ⁻⁴ Pa, 0.4 nm of potassium fluoride is deposited as a cathode buffer layer, and further, 110 nm of aluminum is deposited. Thus, a cathode was formed, and an organic EL element 4-1 was produced.

<< Production of organic EL elements 4-2 to 4-183 >>
In the production of the organic EL element 4-1, organic EL elements 4-2 to 4-183 were similarly produced except that CBP was changed to the compounds shown in Tables 10 to 12.

<< Evaluation of Organic EL Elements 4-1 to 4-183 >>
When evaluating the obtained organic EL element, it was sealed in the same manner as the organic EL elements 1-1 to 1-183 in [Example 1], and a lighting device as shown in FIGS. evaluated. The external illumination quantum efficiency (EQE), temporal stability, and emission color were evaluated using the produced illumination device. These evaluations were performed as follows.

(External quantum efficiency (EQE))
The external extraction quantum efficiency (EQE) was evaluated in the same manner as in [Example 2].

(Stability over time)
The organic EL element was stored at 60 ° C. and 70% RH for one month, and then the respective power efficiencies before and after the storage were determined, and the respective power efficiency ratios were determined according to the following formulas, which were used as a measure of stability over time.
Stability over time (%) = power efficiency after storage / power efficiency before storage x 100
For power efficiency, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing Co., Ltd.) was used to measure the front luminance and luminance angle dependency of each organic EL element, and the power efficiency at a front luminance of 1000 cd / m ² was measured. Asked.

(Luminescent color)
The luminescent color was evaluated by the same method as in [Example 1].

  As shown in Tables 10 to 12, the organic EL element (illumination device) according to the example using the host compound of the present invention (the compound represented by the general formula (1)) is the organic EL element according to the comparative example. It is clear that the external extraction quantum efficiency (EQE) and the temporal stability are excellent (that is, the durability life is excellent) as compared with the (lighting device).

DESCRIPTION OF SYMBOLS 1 Display 3 Pixel 5 Scan line 6 Data line 7 Power supply line 10 Organic EL element 11 Switching transistor 12 Drive transistor 13 Capacitor A Display part B Control part 101 Organic EL element 102 Glass cover 103 Glass substrate 104 Sealing material 105 Cathode 106 Organic EL layer 107 Glass substrate with transparent electrode 108 Nitrogen gas 109 Water catching agent 201 Glass substrate 202 ITO transparent electrode 203 Partition 204 Hole injection layer 205B, 205G, 205R Light emitting layer 206 Cathode

Claims (11)

An organic luminescence device comprising at least one light-emitting layer, which contains a compound represented by the following general formula (1).

(In the general formula (1), Cz ¹ and Cz ² represent a substituted or unsubstituted carbazolyl group, L ¹ and L ² represent a divalent linking group or a single bond, and A represents the general formula (2). Represents.
In General Formula (2), A ¹ and A ² represent substituted or unsubstituted dibenzofuran or dibenzothiophene. ) The organic electroluminescence device according to claim ¹ , wherein at least one of the A ¹ and A ² is a substituted or unsubstituted dibenzofuran. ^2. The organic electroluminescence device according to claim ¹ , wherein both of A ¹ and A ² are substituted or unsubstituted dibenzofuran. The organic electroluminescence device according to claim 1, wherein the A is represented by the following general formula (3), (4), (5) or (6).

(However, in general formula (3), (4), (5) or (6), R ¹ and R ² each independently represents a hydrogen atom or a monovalent substituent, and n1 and n2 are 1-6. Represents an integer.) The organic electroluminescence device according to claim 4, wherein the R ¹ and R ² are hydrogen atoms.   The organic electroluminescent element according to claim 1, wherein the compound represented by the general formula (1) is contained in a light emitting layer.   The organic light-emitting device according to claim 1, wherein the light-emitting layer contains a metal complex compound having a transition metal as a central metal.   The organic electroluminescence element according to claim 1, which emits white light.   A display device comprising the organic electroluminescence element according to claim 1.   An illuminating device comprising the organic electroluminescent element according to claim 1. An organic electroluminescent material represented by the following general formula (1).

(In the general formula (1), Cz ¹ and Cz ² represent a substituted or unsubstituted carbazolyl group, L ¹ and L ² represent a divalent linking group or a single bond, and A represents the general formula (2). Represents.
In General Formula (2), A ¹ and A ² represent substituted or unsubstituted dibenzofuran or dibenzothiophene. )

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