Organic electroluminescent device

Abstract

An organic electroluminescent device having high luminous efficiency, low driving voltage, and particularly a long lifetime is provided by combining various materials for an organic electroluminescent device, which have excellent hole and electron injection/transport performances, electron blocking ability, stability in a thin-film state, and durability as materials for an organic electroluminescent device having high luminous efficiency and high durability so as to allow the respective materials to effectively reveal their characteristics. In the organic electroluminescent device having at least an anode, a hole transport layer, a light emitting layer, an electron transport layer and a cathode in this order, the hole transport layer includes an arylamine compound represented by the following general formula (1), and the light emitting layer includes an amine derivative of the following general formula (2) having a condensed ring structure. ##STR00001##

Claims

1. An organic electroluminescent device comprising at least an anode, a hole transport layer, a light emitting layer, an electron transport layer and a cathode in this order, wherein the hole transport layer has a two-layer structure of a first hole transport layer and a second hole transport layer, and the second hole transport layer comprises an arylamine compound of the following general formula (1), and the light emitting layer comprises an amine derivative of the following general formula (2) having a condensed ring structure: ##STR00190## wherein Ar.sub.1 and Ar.sub.2 may be the same or different, and represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, and wherein Ar.sub.3 and Ar.sub.4 may be the same or different, and represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted benzothiazolyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted benzoimidazolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted phenanthrolinyl group, a substituted or unsubstituted acridinyl group, or a substituted or unsubstituted carbolinyl group, ##STR00191## wherein A.sub.1 represents a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a divalent group of a substituted or unsubstituted aromatic heterocyclic ring, a divalent group of substituted or unsubstituted condensed polycyclic aromatics, or a single bond; Ar.sub.5 and Ar.sub.6 may be the same or different, and represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, where Ar.sub.5 and Ar.sub.6 may bind to each other via a single bond, substituted or unsubstituted methylene, an oxygen atom, or a sulfur atom to form a ring; R.sub.1 to R.sub.4 may be the same or different, and represent a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear or branched alkyl group of 1 to 6 carbon atoms that may have a substituent, a cycloalkyl group of 5 to 10 carbon atoms that may have a substituent, a linear or branched alkenyl group of 2 to 6 carbon atoms that may have a substituent, a linear or branched alkyloxy group of 1 to 6 carbon atoms that may have a substituent, a cycloalkyloxy group of 5 to 10 carbon atoms that may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group, or a disubstituted amino group substituted with a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group, and a condensed polycyclic aromatic group, where the respective groups may bind to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring, and in the benzene ring to which R.sub.1 to R.sub.4 bind, any one group of R.sub.1 to R.sub.4 is removed, and the site where this group is removed and another group of R.sub.1 to R.sub.4 may bind to each other via a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or a monosubstituted amino group to form a ring; R.sub.5 to R.sub.7 may be the same or different, and represent a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear or branched alkyl group of 1 to 6 carbon atoms that may have a substituent, a cycloalkyl group of 5 to 10 carbon atoms that may have a substituent, a linear or branched alkenyl group of 2 to 6 carbon atoms that may have a substituent, a linear or branched alkyloxy group of 1 to 6 carbon atoms that may have a substituent, a cycloalkyloxy group of 5 to 10 carbon atoms that may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, where the respective groups may bind to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring, and in the benzene ring to which R.sub.5 to R.sub.7 bind, any one group of R.sub.5 to R.sub.7 is removed, and the site where this group is removed and another group of R.sub.5 to R.sub.7 may bind to each other via a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or a monosubstituted amino group to form a ring; and R.sub.8 and R.sub.9 may be the same or different, linear or branched alkyl of 1 to 6 carbon atoms that may have a substituent, cycloalkyl of 5 to 10 carbon atoms that may have a substituent, linear or branched alkenyl of 2 to 6 carbon atoms that may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or substituted or unsubstituted aryloxy, where R.sub.8 and R.sub.9 may bind to each other via a single bond, substituted or unsubstituted methylene, an oxygen atom, a sulfur atom, or a mono-substituted amino group to form a ring.

2. The organic electroluminescent device according to claim 1, wherein the arylamine compound represented by the general formula (1) is an arylamine compound represented by the following general formula (1a), ##STR00192## wherein Ar.sub.1 to Ar.sub.3 and Ar.sub.7 to Ar.sub.8 may be the same or different, and represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.

3. The organic electroluminescent device according to claim 2, wherein the light emitting layer comprises an anthracene derivative.

4. The organic electroluminescent device according to claim 3, wherein the light emitting layer comprises a host material that is an anthracene derivative.

5. The organic electroluminescent device according to claim 1, wherein the arylamine compound represented by the general formula (1) is an arylamine compound represented by the following general formula (1b), ##STR00193## wherein Ar.sub.1 to Ar.sub.2 and Ar.sub.7 to Ar.sub.10 may be the same or different, and represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.

6. The organic electroluminescent device according to claim 5, wherein the light emitting layer comprises an anthracene derivative.

7. The organic electroluminescent device according to claim 6, wherein the light emitting layer comprises a host material that is an anthracene derivative.

8. The organic electroluminescent device according to claim 1, wherein the electron transport layer comprises a compound of the following general formula (3) having an anthracene ring structure, ##STR00194## wherein A.sub.2 represents a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a divalent group of a substituted or unsubstituted aromatic heterocyclic ring, a divalent group of substituted or unsubstituted condensed polycyclic aromatics, or a single bond; B represents a substituted or unsubstituted aromatic heterocyclic group; C represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; D may be the same or different, and represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, cyano, trifluoromethyl, linear or branched alkyl of 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; and p represents 7 or 8, and q represents 1 or 2 while maintaining a relationship that a sum of p and q is 9.

9. The organic electroluminescent device according to claim 8, wherein the compound having an anthracene ring structure is a compound of the following general formula (3a) having an anthracene ring structure, ##STR00195## wherein A.sub.2 represents a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a divalent group of a substituted or unsubstituted aromatic heterocyclic ring, a divalent group of substituted or unsubstituted condensed polycyclic aromatics, or a single bond; Ar.sub.11, Ar.sub.12, and Ar.sub.13 may be the same or different, and represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; R.sub.10 to R.sub.16 may be the same or different, and represent a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, cyano, nitro, linear or branched alkyl of 1 to 6 carbon atoms that may have a substituent, cycloalkyl of 5 to 10 carbon atoms that may have a substituent, linear or branched alkenyl of 2 to 6 carbon atoms that may have a substituent, linear or branched alkyloxy of 1 to 6 carbon atoms that may have a substituent, cycloalkyloxy of 5 to 10 carbon atoms that may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or substituted or unsubstituted aryloxy, where R.sub.10 to R.sub.16 may bind to each other via a single bond, substituted or unsubstituted methylene, an oxygen atom, or a sulfur atom to form a ring; and X.sub.1, X.sub.2, X.sub.3, and X.sub.4represent a carbon atom or a nitrogen atom, where only one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4 is a nitrogen atom, and the nitrogen atom in this case does not have the hydrogen atom or the substituent for R.sub.10 to R.sub.13.

10. The organic electroluminescent device according to claim 9, wherein the light emitting layer comprises an anthracene derivative.

11. The organic electroluminescent device according to claim 8, wherein the compound having an anthracene ring structure is a compound of the following general formula (3b) having an anthracene ring structure, ##STR00196## wherein A.sub.2 represents a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a divalent group of a substituted or unsubstituted aromatic heterocyclic ring, a divalent group of substituted or unsubstituted condensed polycyclic aromatics, or a single bond; Ar.sub.14, Ar.sub.15, and Ar.sub.16 may be the same or different, and represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.

12. The organic electroluminescent device according to claim 11, wherein the light emitting layer comprises an anthracene derivative.

13. The organic electroluminescent device according to claim 8, wherein the compound having an anthracene ring structure is a compound of the following general formula (3c) having an anthracene ring structure, ##STR00197## wherein A.sub.2 represents a divalent group of a substituted or unsubstituted aromatic hydrocarbon, a divalent group of a substituted or unsubstituted aromatic heterocyclic ring, a divalent group of substituted or unsubstituted condensed polycyclic aromatics, or a single bond; Ar.sub.17, Ar.sub.18, and Ar.sub.19 may be the same or different, and represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; and R.sub.17 represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, cyano, nitro, linear or branched alkyl of 1 to 6 carbon atoms that may have a substituent, cycloalkyl of 5 to 10 carbon atoms that may have a substituent, linear or branched alkenyl of 2 to 6 carbon atoms that may have a substituent, linear or branched alkyloxy of 1 to 6 carbon atoms that may have a substituent, cycloalkyloxy of 5 to 10 carbon atoms that may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or substituted or unsubstituted aryloxy.

14. The organic electroluminescent device according to claim 13, wherein the light emitting layer comprises an anthracene derivative.

15. The organic electroluminescent device according to claim 8, wherein the light emitting layer comprises an anthracene derivative.

16. The organic electroluminescent device according to claim 15, wherein the light emitting layer comprises a host material that is an anthracene derivative.

17. The organic electroluminescent device according to claim 1, wherein the light emitting layer comprises an anthracene derivative.

18. The organic electroluminescent device according to claim 17, wherein the light emitting layer comprises a host material that is an anthracene derivative.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The FIGURE is a diagram illustrating the configuration of the organic EL devices of Examples 20 to 23 and Comparative Examples 1 to 4.

MODE FOR CARRYING OUT THE INVENTION

(2) The following presents specific examples of preferred compounds among the arylamine compounds of the general formula (1) preferably used in the organic EL device of the present invention. The present invention, however, is not restricted to these compounds.

(3) ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092##

(4) The following presents specific examples of preferred compounds among the amine derivatives of the general formula (2) having a condensed ring structure preferably used in the organic EL device of the present invention. The present invention, however, is not restricted to these compounds.

(5) ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099##

(6) The following presents specific examples of preferred compounds among the compounds of the general formula (3a) having an anthracene ring structure preferably used in the organic EL device of the present invention. The present invention, however, is not restricted to these compounds.

(7) ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106##

(8) The following presents specific examples of preferred compounds among the compounds of the general formula (3b) having an anthracene ring structure and preferably used in the organic EL device of the present invention. The present invention, however, is not restricted to these compounds.

(9) ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111##

(10) The following presents specific examples of preferred compounds among the compounds of the general formula (3c) having an anthracene ring structure and preferably used in the organic EL device of the present invention. The present invention, however, is not restricted to these compounds.

(11) ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123##

(12) The compounds described above having an anthracene ring structure can be synthesized by a known method (refer to Patent Documents 6 to 8, for example).

(13) In the organic EL device of the present invention, the following presents specific examples of preferred compounds among the arylamine compounds of the general formula (4) having two triphenylamine structures within a molecule and preferably used in the first hole transport layer in the case where the hole transport layer has a two-layer structure of the first hole transport layer and the second hole transport layer. The present invention, however, is not restricted to these compounds.

(14) ##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131##

(15) In the organic EL device of the present invention, the following presents specific examples of preferred compounds in the arylamine compounds preferably used in the first hole transport layer and having two triphenylamine structures within a molecule in the arylamine compounds having a structure in which two to six triphenylamine structures are joined within a molecule via a single bond or a divalent group that does not contain a heteroatom in the case where the hole transport layer has a two-layer structure of the first hole transport layer and the second hole transport layer, besides the arylamine compounds of the general formula (4) having two triphenylamine structures within a molecule. The present invention, however, is not restricted to these compounds.

(16) ##STR00132##

(17) In the organic EL device of the present invention, the following presents specific examples of preferred compounds among the arylamine compounds of the general formula (5) having four triphenylamine structures within a molecule and preferably used in the first hole transport layer in the case where the hole transport layer has a two-layer structure of the first hole transport layer and the second hole transport layer. The present invention, however, is not restricted to these compounds.

(18) ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138##

(19) The arylamine compounds of the general formula (4) having two triphenylamine structures within a molecule, and the arylamine compounds of the general formula (5) having four triphenylamine structures within a molecule can be synthesized by a known method (refer to Patent Documents 1, 9, and 10, for example).

(20) The arylamine compounds of the general formula (1) were purified by methods such as column chromatography; adsorption using, for example, a silica gel, activated carbon, or activated clay; recrystallization or crystallization using a solvent; and sublimation. The compounds were identified by an NMR analysis. A glass transition point (Tg) and a work function were measured as material property values. The glass transition point (Tg) can be used as an index of stability in a thin-film state, and the work function can be used as an index of hole transportability.

(21) Other compounds used for the organic EL device of the present invention were purified by methods such as column chromatography; adsorption using, for example, a silica gel, activated carbon, or activated clay; and recrystallization or crystallization using a solvent; and finally purified by sublimation.

(22) The glass transition point (Tg) was measured by a high-sensitive differential scanning calorimeter (DSC3100S produced by Bruker AXS) using powder.

(23) For the measurement of the work function, a 100 nm-thick thin film was fabricated on an ITO substrate, and an ionization potential measuring device (PYS-202 produced by Sumitomo Heavy Industries, Ltd.) was used.

(24) The organic EL device of the present invention may have a structure including an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode successively formed on a substrate, optionally with an electron blocking layer between the hole transport layer and the light emitting layer, a hole blocking layer between the light emitting layer and the electron transport layer, and an electron injection layer between the electron transport layer and the cathode. Some of the organic layers in the multilayer structure may be omitted, or may serve more than one function. For example, a single organic layer may serve as the hole injection layer and the hole transport layer, or as the electron injection layer and the electron transport layer, and so on. Further, any of the layers may be configured to laminate two or more organic layers having the same function, and the hole transport layer may have a two-layer laminated structure, the light emitting layer may have a two-layer laminated structure, the electron transport layer may have a two-layer laminated structure, and so on. The organic EL device of the present invention is preferably configured such that the hole transport layer has a two-layer laminated structure of a first hole transport layer and a second hole transport layer.

(25) Electrode materials with high work functions such as ITO and gold are used as the anode of the organic EL device of the present invention. The hole injection layer of the organic EL device of the present invention may be made of, for example, material such as starburst-type triphenylamine derivatives and various triphenylamine tetramers; porphyrin compounds as represented by copper phthalocyanine; accepting heterocyclic compounds such as hexacyano azatriphenylene; and coating-type polymer materials, in addition to the arylamine compounds of the general formula (1). These materials may be formed into a thin film by a vapor deposition method or other known methods such as a spin coating method and an inkjet method.

(26) The arylamine compounds of the general formula (1) are used as the hole transport layer of the organic EL device of the present invention. These may be individually deposited for film forming, may be used as a single layer deposited mixed with other hole transporting materials, or may be formed as a laminate of individually deposited layers, a laminate of mixedly deposited layers, or a laminate of the individually deposited layer and the mixedly deposited layer. These materials may be formed into a thin-film by a vapor deposition method or other known methods such as a spin coating method and an inkjet method.

(27) Examples of a hole transporting material that can be mixed or can be used at the same time with the arylamine compounds of the general formula (1) can be benzidine derivatives such as N,N-diphenyl-N,N-di(m-tolyl)benzidine (TPD), N,N-diphenyl-N,N-di(-naphthyl)benzidine (NPD), and N,N,N,N-tetrabiphenylylbenzidine; 1,1-bis[4-(di-4-tolylamino)phenyl]cyclohexane (TAPC); arylamine compounds having a structure in which two triphenylamine structures are joined within a molecule via a single bond or a divalent group that does not contain a heteroatom such as the arylamine compounds of the general formula (4); arylamine compounds having a structure in which four triphenylamine structures are joined within a molecule via a single bond or a divalent group that does not contain a heteroatom such as the arylamine compounds of the general formula (5); and various triphenylamine trimers.

(28) The material used for the hole injection layer or the hole transport layer may be obtained by p-doping materials such as trisbromophenylamine hexachloroantimony, and radialene derivatives (refer to WO2014/009310, for example) into a material commonly used for these layers, or may be, for example, polymer compounds each having, as a part of the compound structure, a structure of a benzidine derivative such as TPD.

(29) In the case where the hole transport layer of the organic EL device of the present invention has a two-layer structure, the above hole transporting materials are used as the first hole transport layer, in addition to the arylamine compounds of the general formula (4) having two triphenylamine structures within a molecule, and the arylamine compounds of the general formula (5) having four triphenylamine structures within a molecule.

(30) The above hole transporting materials are used as the second hole transport layer in addition to the arylamine compounds of the general formula (1).

(31) Examples of material used for the electron blocking layer of the organic EL device of the present invention can be compounds having an electron blocking effect, including, for example, carbazole derivatives such as 4,4,4-tri(N-carbazolyl)triphenylamine (TCTA), 9,9-bis[4-(carbazol-9-yl)phenyl]fluorene, 1,3-bis(carbazol-9-yl)benzene (mCP), and 2,2-bis(4-carbazol-9-ylphenyl)adamantane (Ad-Cz); and compounds having a triphenylsilyl group and a triarylamine structure, as represented by 9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylsilyl)phenyl]-9H-fluorene, in addition to the arylamine compounds of the general formula (1). These may be individually deposited for film forming, may be used as a single layer deposited mixed with other materials, or may be formed as a laminate of individually deposited layers, a laminate of mixedly deposited layers, or a laminate of the individually deposited layer and the mixedly deposited layer. These materials may be formed into a thin-film by using a vapor deposition method or other known methods such as a spin coating method and an inkjet method.

(32) Examples of material used for the light emitting layer of the organic EL device of the present invention can be various metal complexes including, for example, quinolinol derivative metal complexes such as Alq.sub.3; anthracene derivatives; bis(styryl)benzene derivatives; pyrene derivatives; oxazole derivatives; and polyparaphenylene vinylene derivatives; in addition to the amine derivatives of the general formula (2) having a condensed ring structure. Further, the light emitting layer may be made of a host material and a dopant material. Examples of the host material can be thiazole derivatives, benzimidazole derivatives, and polydialkyl fluorene derivatives, in addition to the above light-emitting materials. Examples of the dopant material can be quinacridone, coumarin, rubrene, perylene, pyrene, derivatives thereof, benzopyran derivatives, indenophenanthrene derivatives, rhodamine derivatives, and aminostyryl derivatives in addition to the amine derivatives of the general formula (2) having a condensed ring structure. These may be individually deposited for film forming, may be used as a single layer deposited mixed with other materials, or may be formed as a laminate of individually deposited layers, a laminate of mixedly deposited layers, or a laminate of the individually deposited layer and the mixedly deposited layer.

(33) The dopant material in the light emitting layer of the organic EL device of the present invention is preferably the amine derivatives of the general formula (2) having a condensed ring structure.

(34) Further, the light-emitting material may be a phosphorescent material. Phosphorescent materials as metal complexes of metals such as iridium and platinum may be used. Examples of the phosphorescent materials include green phosphorescent materials such as Ir(ppy).sub.3, blue phosphorescent materials such as Flrpic and FIr6, and red phosphorescent materials such as Btp.sub.2Ir(acac). Here, carbazole derivatives such as 4,4-di(N-carbazolyl)biphenyl (CBP), TCTA, and mCP may be used as the hole injecting and transporting host material other than heterocyclic compounds having an indole ring as a partial structure of a condensed ring. Compounds such as p-bis(triphenylsilyl)benzene (UGH2) and 2,2,2-(1,3,5-phenylene)-tris(1-phenyl-1H-benzimidazole) (TPBI) may be used as the electron transporting host material. In this way, a high-performance organic EL device can be produced.

(35) In order to avoid concentration quenching, the doping of the host material with the phosphorescent light-emitting material should preferably be made by co-evaporation in a range of 1 to 30 weight percent with respect to the whole light emitting layer.

(36) Further, Examples of the light-emitting material may be delayed fluorescent-emitting material such as a CDCB derivative of PIC-TRZ, CC2TA, PXZ-TRZ, 4CzIPN or the like (refer to Non-Patent Document 3, for example).

(37) These materials may be formed into a thin-film by using a vapor deposition method or other known methods such as a spin coating method and an inkjet method.

(38) The hole blocking layer of the organic EL device of the present invention may be formed by using hole blocking compounds such as various rare earth complexes, triazole derivatives, triazine derivatives, and oxadiazole derivatives, in addition to the metal complexes of phenanthroline derivatives such as bathocuproin (BCP), and the metal complexes of quinolinol derivatives such as aluminum(III) bis(2-methyl-8-quinolinate)-4-phenylphenolate (BAlq). These materials may also serve as the material of the electron transport layer. These may be individually deposited for film forming, may be used as a single layer deposited mixed with other materials, or may be formed as a laminate of individually deposited layers, a laminate of mixedly deposited layers, or a laminate of the individually deposited layer and the mixedly deposited layer. These materials may be formed into a thin-film by using a vapor deposition method or other known methods such as a spin coating method and an inkjet method.

(39) Material used for the electron transport layer of the organic EL device of the present invention can be the compounds of the general formula (3) having an anthracene ring structure, far preferably, the compounds of the general formulas (3a), (3b), or (3c) having an anthracene ring structure. These may be individually deposited for film forming, may be used as a single layer deposited mixed with other electron transporting materials, or may be formed as a laminate of individually deposited layers, a laminate of mixedly deposited layers, or a laminate of the individually deposited layer and the mixedly deposited layer. These materials may be formed into a thin film by a vapor deposition method or other known methods such as a spin coating method and an inkjet method.

(40) Examples of the electron transporting material that can be mixed or can be used at the same time with the compound represented by the general formula (3) having an anthracene ring structure can be various metal complexes, including, for example, metal complexes of quinolinol derivatives such as Alq.sub.3 and BAlq, triazole derivatives, triazine derivatives, oxadiazole derivatives, pyridine derivatives, pyrimidine derivatives, benzimidazole derivatives, thiadiazole derivatives, benzotriazole derivatives, carbodiimide derivatives, quinoxaline derivatives, pyridoindole derivatives, phenanthroline derivatives, and silole derivatives.

(41) Examples of material used for the electron injection layer of the organic EL device of the present invention can be alkali metal salts such as lithium fluoride and cesium fluoride; alkaline earth metal salts such as magnesium fluoride; and metal oxides such as aluminum oxide. However, the electron injection layer may be omitted in the preferred selection of the electron transport layer and the cathode.

(42) Further, in the electron injection layer or the electron transport layer, a material obtained by further N-doping a material which is commonly used for the layer with a metal such as cecium, a triarylphosphine oxide derivative (refer to WO2014/195482, for example), or the like can be used.

(43) The cathode of the organic EL device of the present invention may be made of an electrode material with a low work function such as aluminum, or an alloy of an electrode material with an even lower work function such as a magnesium-silver alloy, a magnesium-indium alloy, or an aluminum-magnesium alloy.

(44) The following describes an embodiment of the present invention in more detail based on Examples. The present invention, however, is not restricted to the following Examples.

EXAMPLE 1

Synthesis of bis(biphenyl-4-yl)-(1,1:2,1-terphenyl-4-yl)amine (Compound 1-1)

(45) Bis(biphenyl-4-yl)amine (40.5 g), 3-bromobiphenyl (28.0 g), t-butoxy sodium (13.7 g), and toluene (400 mL) were added into a nitrogen-substituted reaction vessel, and the mixture was aerated with nitrogen gas under ultrasonic irradiation for 30 minutes. Palladium acetate (0.54 g) and a toluene solution (1.46 g) containing 50% (w/v) tert-butylphosphine were added thereto, and the mixture was heated and stirred at 95 C. for 4 hours. After the insoluble matter was removed by filtration, the filtrate was heated and purified by adsorption with a silica gel at 100 C., and hot filtration was performed. The filtrate was cooled to room temperature while stirring, and a precipitated solid was collected by filtration, whereby a greenish white solid of bis(biphenyl-4-yl)-(biphenyl-3-yl)amine (50.2 g, yield: 88%) was obtained.

(46) The obtained bis(biphenyl-4-yl)-(biphenyl-3-yl)amine (50.0 g) and dimethylformamide (500 mL) were added into a nitrogen-substituted reaction vessel, and the mixture was cooled in an ice bath. N-bromosuccinimide (22.1 g) was added slowly thereto, and the mixture was stirred for 4 hours. A crude product precipitated by adding methanol was collected by filtration. Subsequently, the product was washed under reflux with ethyl acetate, whereby a pink powder of bis(biphenyl-4-yl)-(6-bromobiphenyl-3-yl)amine (40.2 g, yield: 69%) was obtained.

(47) The obtained bis(biphenyl-4-yl)-(6-bromobiphenyl-3-yl)amine (11.8 g), toluene (94 mL), phenylboronic acid (2.7 g), and an aqueous solution obtained by previously dissolving potassium carbonate (5.9 g) in water (36 mL) were added into a nitrogen-substituted reaction vessel, and the mixture was aerated with nitrogen gas under ultrasonic irradiation for 30 minutes. Tetrakis(triphenylphosphine)palladium (0.74 g) was added thereto, and the mixture was heated and stirred at 72 C. for 18 hours. The mixture was cooled to room temperature, and an organic layer was collected by liquid separation. The organic layer was washed with water, and washed with a saturated sodium chloride solution sequentially, and then dried over anhydrous magnesium sulfate and concentrated to obtain a crude product. Subsequently, the crude product was purified using column chromatography, whereby a white powder of bis(biphenyl-4-yl)-(1,1:2,1-terphenyl-4-yl)amine (Compound 1-1, 8.4 g, yield: 72%) was obtained.

(48) ##STR00139##

(49) The structure of the obtained white powder was identified by NMR.

(50) .sup.1H-NMR (CDCl.sub.3) detected 31 hydrogen signals, as follows.

(51) (ppm)=7.56-7.68 (7H), 7.45-7.52 (4H), 7.14-7.41 (20H).

EXAMPLE 2

Synthesis of bis(biphenyl-4-yl)-{6-(naphthyl-1-yl)biphenyl-3-yl}amine (Compound 1-2)

(52) The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 1-naphthylboronic acid, whereby a white powder of bis(biphenyl-4-yl)-{6-(naphthyl-1-yl)biphenyl-3-yl}amine (Compound 1-2, 9.2 g, yield: 61%) was obtained.

(53) ##STR00140##

(54) The structure of the obtained white powder was identified by NMR.

(55) .sup.1H-NMR (CDCl.sub.3) detected 33 hydrogen signals, as follows.

(56) (ppm)=7.84-7.87 (3H), 7.67-83(6H), 7.26-7.64 (18H), 7.02-7.04 (6H).

EXAMPLE 3

Synthesis of bis(biphenyl-4-yl)-{6-(9,9-dimethylfluoren-2-yl)biphenyl-3-yl}amine (Compound 1-3)

(57) The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with (9,9-dimethylfluoren-2-yl)boronic acid, whereby a white powder of bis(biphenyl-4-yl)-{6-(9,9-dimethylfluoren-2-yl)biphenyl-3-yl}amine (Compound 1-3, 9.0 g, yield: 57%) was obtained.

(58) ##STR00141##

(59) The structure of the obtained white powder was identified by NMR.

(60) .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

(61) (ppm)=7.56-7.64 (10H), 7.26-50(18H), 7.02-7.16 (5H), 1.26 (6H).

EXAMPLE 4

Synthesis of bis(biphenyl-4-yl)-(1,1:2,1:4,1-quaterphenyl-5-yl)amine (Compound 1-4)

(62) The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-biphenylboronic acid, whereby a white powder of bis(biphenyl-4-yl)-(1,1:2,1:4,1-quaterphenyl-5-yl)amine (Compound 1-4, 8.6 g, yield: 64%) was obtained.

(63) ##STR00142##

(64) The structure of the obtained white powder was identified by NMR.

(65) .sup.1H-NMR (CDCl3) detected 35 hydrogen signals, as follows.

(66) (ppm)=7.66-7.53 (8H), 7.51-7.15 (27H).

EXAMPLE 5

Synthesis of bis(6-phenylbiphenyl-3-yl)-(biphenyl-4-yl)amine (Compound 1-94)

(67) Benzamide (13.0 g), 3-bromobiphenyl (52.5 g), potassium carbonate (44.5 g), sodium hydrogen sulfite (3.4 g), phenanthroline monohydrate (2.2 g), copper powder (0.68 g), dodecylbenzene (13 mL), and toluene (30 mL) were added into a nitrogen-substituted reaction vessel, and the mixture was heated while stirring, and was refluxed for 19 hours while removing toluene. After cooling, toluene was added thereto, and the insoluble matter was removed by filtration. The filtrate was washed with water, and washed with a saturated sodium chloride solution sequentially, and then dried over anhydrous magnesium sulfate and concentrated to obtain a crude product. Subsequently, the crude product was purified using column chromatography, whereby a yellow viscous substance of N,N-bis(biphenyl-3-yl)benzamide (41.7 g, yield: 91%) was obtained.

(68) The obtained N,N-bis(biphenyl-3-yl)benzamide (41.7 g), isoamyl alcohol (36 mL), water (12 mL), and potassium hydroxide (7.6 g) were added into a reaction vessel, and the mixture was heated and refluxed for 48 hours while stirring. After the mixture was cooled to room temperature, water and toluene were added thereto, and an organic layer was collected by liquid separation. The organic layer was washed with water, and washed with a saturated sodium chloride solution sequentially, and then dried over anhydrous magnesium sulfate and concentrated to obtain a crude product. Subsequently, the crude product was purified using column chromatography, whereby a brown viscous substance of bis(biphenyl-3-yl)amine (25.3 g, yield: 80%) was obtained.

(69) The obtained bis(biphenyl-3-yl)amine (25.2 g), toluene (250 mL), 4-bromobiphenyl (20.5 g), and tert-butoxy sodium (9.0 g) were added into a nitrogen-substituted reaction vessel, and the mixture was aerated with nitrogen gas under ultrasonic irradiation for 30 minutes. Palladium acetate (0.35 g) and a toluene solution (0.95 g) containing 50% (w/v) tert-butylphosphine were added thereto, and the mixture was heated and stirred at 95 C. for 14 hours. After the insoluble matter was removed by filtration, the filtrate was washed with water, and washed with a saturated sodium chloride solution sequentially, and then dried over anhydrous magnesium sulfate and concentrated to obtain a crude product. Subsequently, the crude product was purified using column chromatography, whereby a yellowish white powder of bis(biphenyl-3-yl)-(biphenyl-4-yl)amine (31.6 g, yield: 85%) was obtained.

(70) The obtained bis(biphenyl-3-yl)-(biphenyl-4-yl)amine (31.5 g) and dimethylformamide (320 mL) were added into a nitrogen-substituted reaction vessel, and the mixture was cooled in an ice bath. N-bromosuccinimide (26.0 g) was added slowly thereto, and the mixture was stirred for 5 hours. A crude product precipitated by adding water was collected by filtration. The crude product was washed with methanol, and then purified using column chromatography, whereby a white powder of bis(6-bromobiphenyl-3-yl)-(biphenyl-4-yl)amine (36.9 g, yield: 88%) was obtained.

(71) The reaction was carried out under the same conditions as those of Example 1, except that bis(biphenyl-4-yl)-(6-bromobiphenyl-3-yl)amine was replaced with bis(6-bromobiphenyl-3-yl)-(biphenyl-4-yl)amine obtained above, whereby a white powder of bis(6-phenylbiphenyl-3-yl)-(biphenyl-4-yl)amine (Compound 1-94, 10.2 g, yield: 73%) was obtained.

(72) ##STR00143##

(73) The structure of the obtained white powder was identified by NMR.

(74) .sup.1H-NMR (CDCl.sub.3) detected 35 hydrogen signals, as follows.

(75) (ppm)=7.57-7.66 (4H), 7.10-7.49 (31H).

EXAMPLE 6

Synthesis of tris(6-phenylbiphenyl-3-yl)amine (Compound 1-129)

(76) 3-Aminobiphenyl (10.4 g), toluene (250 mL), 3-bromobiphenyl (30.0 g), and tert-butoxy sodium (13.1 g) were added into a nitrogen-substituted reaction vessel, and the mixture was aerated with nitrogen gas under ultrasonic irradiation for 30 minutes. Tris(dibenzylideneacetone)palladium (2.25 g) and a toluene solution (1.50 g) containing 50% (w/v) tert-butylphosphine were added thereto, and the mixture was heated and stirred at 95 C. for 3 hours. After the insoluble matter was removed by filtration, the filtrate was washed with water, and washed with a saturated sodium chloride solution sequentially, and then dried over anhydrous magnesium sulfate and concentrated to obtain a crude product. Further, the crude product was purified using column chromatography, whereby a white powder of tris(biphenyl-3-yl)amine (24.6 g, yield: 85%) was obtained.

(77) The obtained tris(biphenyl-3-yl)amine (24.5 g) and dimethylformamide (245 mL) were added into a nitrogen-substituted reaction vessel, and the mixture was cooled in an ice bath. N-bromosuccinimide (30.4 g) was added slowly thereto, and the mixture was stirred for 7 hours. Toluene was added thereto, and subsequently, washing with water and washing with a saturated sodium chloride solution were performed sequentially, followed by drying over anhydrous magnesium sulfate and concentration to obtain a crude product. Then, the crude product was purified using column chromatography, whereby a white powder of tris(6-bromobiphenyl-3-yl)amine (33.6 g, yield: 92%) was obtained.

(78) The reaction was carried out under the same conditions as those of Example 1, except that bis(biphenyl-4-yl)-(6-bromobiphenyl-3-yl)amine was replaced with tris(6-bromobiphenyl-3-yl)amine obtained above, whereby a white powder of tris(6-phenylbiphenyl-3-yl)amine (Compound 1-129, 11.1 g, yield: 75%) was obtained.

(79) ##STR00144##

(80) The structure of the obtained white powder was identified by NMR.

(81) .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

(82) (ppm)=7.35-7.42 (6H), 7.15-7.35 (33H).

EXAMPLE 7

Synthesis of (biphenyl-4-yl)-{4-(naphthalen-2-yl)phenyl}-(6-phenyl-1,1:4,1-terphenyl-3-yl)amine (Compound 1-143)

(83) The reaction was carried out under the same conditions as those of Example 1, except that bis(biphenyl-4-yl)-(6-bromobiphenyl-3-yl)amine was replaced with (biphenyl-4-yl)-{4-(naphthalen-2-yl)phenyl}-(6-bromo-1,1:4,1-terphenyl-3-yl)amine, whereby a white powder of (biphenyl-4-yl)-{4-(naphthalen-2-yl)phenyl}-(6-phenyl-1,1:4,1-terphenyl-3-yl)amine (Compound 1-143, 5.8 g, yield: 56%) was obtained.

(84) ##STR00145##

(85) The structure of the obtained white powder was identified by NMR.

(86) .sup.1H-NMR (CDCl.sub.3) detected 37 hydrogen signals, as follows.

(87) (ppm)=8.08 (1H), 7.81-7.96 (3H), 7.79-7.81 (1H), 7.21-7.73 (32H).

EXAMPLE 8

Synthesis of (biphenyl-4-yl)-{4-(naphthalen-2-yl)phenyl}-(1,1:2,1:2,1:4,1-quinquephenyl-4-yl)amine (Compound 1-146)

(88) The reaction was carried out under the same conditions as those of Example 1, except that bis(biphenyl-4-yl)-(6-bromobiphenyl-3-yl)amine was replaced with (biphenyl-4-yl)-{4-(naphthalen-2-yl)phenyl}-(6-bromo-1,1:4,1-terphenyl-3-yl)amine, and phenylboronic acid was replaced with 2-biphenylboronic acid, whereby a white powder of (biphenyl-4-yl)-{4-(naphthalen-2-yl)phenyl}-(1,1:2,1:2,1:4,1-quinquephenyl-4-yl)amine (Compound 1-146, 8.5 g, yield: 49%) was obtained.

(89) ##STR00146##

(90) The structure of the obtained white powder was identified by NMR.

(91) .sup.1H-NMR (CDCl.sub.3) detected 41 hydrogen signals, as follows.

(92) (ppm)=8.1 (1H), 7.86-7.98 (4H), 7.10-7.72 (32H), 6.65-6.76 (4H).

EXAMPLE 9

Synthesis of bis{4-(naphthalen-1-yl)phenyl}-(1,1:2,1:4,1-quaterphenyl-5-yl)amine (Compound 1-148)

(93) The reaction was carried out under the same conditions as those of Example 1, except that bis(biphenyl-4-yl)-(6-bromobiphenyl-3-yl)amine was replaced with bis{4-(naphthalen-1-yl)phenyl}-(6-bromobiphenyl-3-yl)amine, and phenylboronic acid was replaced with 4-biphenylboronic acid, whereby a white powder of bis{4-(naphthalen-1-yl)phenyl}-(1,1:2,1:4,1-quaterphenyl-5-yl)amine (Compound 1-148, 10.6 g, yield: 79%) was obtained.

(94) ##STR00147##

(95) The structure of the obtained white powder was identified by NMR.

(96) .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

(97) (ppm)=8.08-8.14 (2H), 7.88-7.96 (4H), 7.24-7.64 (33H).

EXAMPLE 10

Synthesis of bis{4-(naphthalen-1-yl)phenyl}-(1,1:2,1:2,1:4,1-quinquephenyl-4-yl)amine (Compound 1-153)

(98) The reaction was carried out under the same conditions as those of Example 1, except that bis(biphenyl-4-yl)-(6-bromobiphenyl-3-yl)amine was replaced with bis{4-(naphthalen-1-yl)phenyl}-(6-bromoterphenyl-3-yl)amine, and phenylboronic acid was replaced with 2-biphenylboronic acid, whereby a white powder of bis{4-(naphthalen-1-yl)phenyl}-(1,1: 2,1: 2,1: 4, 1-quinquephenyl-4-yl)amine (Compound 1-153, 7.5 g, yield: 55%) was obtained.

(99) ##STR00148##

(100) The structure of the obtained white powder was identified by NMR.

(101) .sup.1H-NMR (CDCl.sub.3) detected 43 hydrogen signals, as follows.

(102) (ppm)=8.09-8.12 (2H), 7.88-7.97 (4H), 7.10-1.60 (33H), 6.67-6.75 (4H).

EXAMPLE 11

Synthesis of bis{4-(naphthalen-2-yl)phenyl}-(1,1:2,1:4,1-quaterphenyl-5-yl)amine (Compound 1-155)

(103) The reaction was carried out under the same conditions as those of Example 1, except that bis(biphenyl-4-yl)-(6-bromobiphenyl-3-yl)amine was replaced with bis{4-(naphthalen-2-yl)phenyl}-(6-bromobiphenyl-3-yl)amine, and phenylboronic acid was replaced with 4-biphenylboronic acid, whereby a white powder of bis{4-(naphthalen-2-yl)phenyl}-(1,1:2,1:4,1-quaterphenyl-5-yl)amine (Compound 1-155, 6.6 g, yield: 80%) was obtained.

(104) ##STR00149##

(105) The structure of the obtained white powder was identified by NMR.

(106) .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

(107) (ppm)=8.12 (2H), 7.91-7.98 (6H), 7.64-7.84 (8H), 7.28-7.59 (23H).

EXAMPLE 12

Synthesis of bis{4-(naphthalen-2-yl)phenyl}-{4-(naphthalen-1-yl)-1,1:2,1-terphenyl-4-yl}amine (Compound 1-158)

(108) The reaction was carried out under the same conditions as those of Example 11, except that 4-biphenylboronic acid was replaced with 4-(naphthalen-1-yl)phenylboronic acid, whereby a white powder of bis{4-(naphthalen-2-yl)phenyl}-{4-(naphthalen-1-yl)-1,1:2,1-terphenyl-4-yl}amine (Compound 1-158, 6.5 g, yield: 73%) was obtained.

(109) ##STR00150##

(110) The structure of the obtained white powder was identified by NMR.

(111) .sup.1H-NMR (CDCl.sub.3) detected 41 hydrogen signals, as follows.

(112) (ppm)=8.11 (2H), 7.68-7.98 (18H), 7.23-7.59 (21H).

EXAMPLE 13

Synthesis of bis{4-(naphthalen-2-yl)phenyl}-{4-(naphthalen-2-yl)-1,1:2,1-terphenyl-4-yl}amine (Compound 1-159)

(113) The reaction was carried out under the same conditions as those of Example 11, except that 4-biphenylboronic acid was replaced with 4-(naphthalen-2-yl)phenylboronic acid, whereby a white powder of bis{4-(naphthalen-2-yl)phenyl}-{4-(naphthalen-2-yl)-1,1: 2,1-terphenyl-4-yl}amine (Compound 1-159, 7.4 g, yield: 83%) was obtained.

(114) ##STR00151##

(115) The structure of the obtained white powder was identified by NMR.

(116) .sup.1H-NMR (CDCl.sub.3) detected 41 hydrogen signals, as follows.

(117) (ppm)=8.10-8.12 (3H), 7.89-7.98 (9H), 7.65-7.84 (9H), 7.32-7.58 (20H).

EXAMPLE 14

Synthesis of (biphenyl-4-yl)-(1,1: 2,1: 4,1-quaterphenyl-5-yl)-(9,9-dimethylfluoren-2-yl)amine (Compound 1-56)

(118) The reaction was carried out under the same conditions as those of Example 1, except that bis(biphenyl-4-yl)-(6-bromobiphenyl-3-yl)amine was replaced with (6-bromobiphenyl-3-yl)-(biphenyl-4-yl)-(9,9-dimethylfluoren-2-yl)amine, and phenylboronic acid was replaced with 4-biphenylboronic acid, whereby a white powder of (biphenyl-4-yl)-(1,1: 2,1: 4,1-quaterphenyl-5-yl)-(9,9-dimethylfluoren-2-yl-)amine (Compound 1-56, 17.8 g, yield: 89%) was obtained.

(119) ##STR00152##

(120) The structure of the obtained white powder was identified by NMR.

(121) .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

(122) (ppm)=7.57-7.70 (7H), 7.18-7.52 (26H), 1.52 (6H).

EXAMPLE 15

Synthesis of (biphenyl-4-yl)-{4-(naphthalen-1-yl)-(1,1: 2,1-terphenyl)-4-yl}-(9,9-dimethylfluoren-2-yl)amine (Compound 1-163)

(123) The reaction was carried out under the same conditions as those of Example 14, except that 4-biphenylboronic acid was replaced with 4-(naphthalen-1-yl)phenylboronic acid, whereby a white powder of (biphenyl-4-yl)-{4-(naphthalen-1-yl)-(1,1: 2,1-terphenyl)-4-yl}-(9,9-dimethylfluoren-2-yl)amine (Compound 1-163, 17.8 g, yield: 89%) was obtained.

(124) ##STR00153##

(125) The structure of the obtained white powder was identified by NMR.

(126) .sup.1H-NMR (CDCl.sub.3) detected 41 hydrogen signals, as follows.

(127) (ppm)=7.85-7.96 (3H), 7.18-74 (32H), 1.53 (6H).

EXAMPLE 16

Synthesis of (biphenyl-4-yl)-(1,1: 2,1-terphenyl-4-yl)-(9,9-diphenylfluoren-2-yl)amine (Compound 1-165)

(128) The reaction was carried out under the same conditions as those of Example 1, except that bis(biphenyl-4-yl)-(6-bromobiphenyl-3-yl)amine was replaced with (6-bromobiphenyl-3-yl)-(biphenyl-4-yl)-(9,9-diphenylfluoren-2-yl)amine, whereby a white powder of (biphenyl-4-yl)-(1,1: 2,1-terphenyl-4-yl)-(9,9-diphenylfluoren-2-yl)amine (Compound 1-165, 11.0 g, yield: 61%) was obtained.

(129) ##STR00154##

(130) The structure of the obtained white powder was identified by NMR.

(131) .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

(132) (ppm)=7.60-7.74 (4H), 7.14-7.52 (33H), 7.00-7.03 (2H).

EXAMPLE 17

Synthesis of (biphenyl-4-yl)-(1,1: 2,1: 4,1-quaterphenyl-5-yl)-(9,9-diphenylfluoren-2-yl)amine (Compound 1-166)

(133) The reaction was carried out under the same conditions as those of Example 16, except that phenylboronic acid was replaced with 4-biphenylboronic acid, whereby a white powder of (biphenyl-4-yl)-(1,1: 2,1: 4,1-quaterphenyl-5-yl)-(9,9-diphenylfluoren-2-yl)amine (Compound 1-166, 6.5 g, yield: 71%) was obtained.

(134) ##STR00155##

(135) The structure of the obtained white powder was identified by NMR.

(136) .sup.1H-NMR (CDCl.sub.3) detected 43 hydrogen signals, as follows.

(137) (ppm)=7.61-7.77 (6H), 7.20-7.51 (34H), 7.06-7.11 (3H).

EXAMPLE 18

Synthesis of (biphenyl-4-yl)-(1,1: 2,1: 3,1-quaterphenyl-5-yl)-(9,9-diphenylfluoren-2-yl)amine (Compound 1-167)

(138) The reaction was carried out under the same conditions as those of Example 16, except that phenylboronic acid was replaced with 3-biphenylboronic acid, whereby a white powder of (biphenyl-4-yl)-(1,1: 2,1: 3,1-quaterphenyl-5-yl)-(9,9-diphenylfluoren-2-yl)amine (Compound 1-167, 8.0 g, yield: 87%) was obtained.

(139) ##STR00156##

(140) The structure of the obtained white powder was identified by NMR.

(141) .sup.1H-NMR (CDCl.sub.3) detected 43 hydrogen signals, as follows.

(142) (ppm)=7.70-7.76 (2H), 7.63-7.65 (2H), 7.18-7.54 (36H), 7.08-7.12 (3H).

EXAMPLE 19

Synthesis of (biphenyl-4-yl)-(1,1: 2,1: 2,1-quaterphenyl-5-yl)-(9,9-diphenylfluoren-2-yl)amine (Compound 1-168)

(143) The reaction was carried out under the same conditions as those of Example 16, except that phenylboronic acid was replaced with 2-biphenylboronic acid, whereby a white powder of (biphenyl-4-yl)-(1,1: 2,1: 2,1-quaterphenyl-5-yl)-(9,9-diphenylfluoren-2-yl)amine (Compound 1-168, 5.2 g, yield: 57%) was obtained.

(144) ##STR00157##

(145) The structure of the obtained white powder was identified by NMR.

(146) .sup.1H-NMR (CDCl.sub.3) detected 43 hydrogen signals, as follows.

(147) (ppm)=7.60-7.74 (4H), 6.95-7.49 (35H), 6.68-6.71 (2H), 6.54-6.57 (2H).

EXAMPLE 20

Synthesis of phenyl-(1,1: 2,1-terphenyl-4-yl)-(9,9-diphenylfluoren-2-yl)amine (Compound 1-169)

(148) The reaction was carried out under the same conditions as those of Example 1, except that bis(biphenyl-4-yl)-(6-bromobiphenyl-3-yl)amine was replaced with (6-bromobiphenyl-3-yl)-phenyl-(9,9-diphenylfluoren-2-yl)amine, and phenylboronic acid was replaced with 4-biphenylboronic acid, whereby a white powder of phenyl-(1,1: 2,1-terphenyl-4-yl)-(9,9-diphenylfluoren-2-yl)amine (Compound 1-169, 4.2 g, yield: 37%) was obtained.

(149) ##STR00158##

(150) The structure of the obtained white powder was identified by NMR.

(151) .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

(152) (ppm)=7.55-7.79 (4H), 7.06-7.52 (35H).

EXAMPLE 21

Synthesis of (biphenyl-4-yl)-(1,1: 2,1-terphenyl-4-yl)-(9,9-spirobi[fluoren]-2-yl)amine (Compound 1-172)

(153) The reaction was carried out under the same conditions as those of Example 1, except that bis(biphenyl-4-yl)-(6-bromobiphenyl-3-yl)amine was replaced with (biphenyl-4-yl)-(6-bromobiphenyl3-yl)-(9,9-spirobi[fluoren]-2-yl)amine, whereby a white powder of (biphenyl-4-yl)-(1,1: 2,1-terphenyl-4-yl)-(9,9-spirobi[fluoren]-2-yl)amine (Compound 1-172, 6.0 g, yield: 52%) was obtained.

(154) ##STR00159##

(155) The structure of the obtained white powder was identified by NMR.

(156) .sup.1H-NMR (CDCl.sub.3) detected 37 hydrogen signals, as follows.

(157) (ppm)=7.81-7.88 (4H), 7.59-7.62 (2H), 7.34-7.50 (8H), 7.03-7.28 (15H), 6.73-6.92 (8H).

EXAMPLE 22

Synthesis of (biphenyl-4-yl)-(1,1: 2,1: 2,1-quaterphenyl-5-yl)-(9,9-spirobi[fluoren]-2-yl)amine (Compound 1-175)

(158) The reaction was carried out under the same conditions as those of Example 21, except that phenylboronic acid was replaced with 2-biphenylboronic acid, whereby a white powder of (biphenyl-4-yl)-(1,1: 2,1: 2,1-quaterphenyl-5-yl)-(9,9-spirobi[fluoren]-2-yl)amine (Compound 1-175, 6.1 g, yield: 42%) was obtained.

(159) ##STR00160##

(160) The structure of the obtained white powder was identified by NMR.

(161) .sup.1H-NMR (CDCl.sub.3) detected 41 hydrogen signals, as follows.

(162) (ppm)=7.75-7.86 (4H), 7.34-7.58 (14H), 6.85-20 (17H), 6.70-6.72 (2H), 6.59-6.62 (2H), 6.40-6.42 (2H).

EXAMPLE 23

Synthesis of {4-(naphthalen-2-yl)phenyl}-(1,1: 2,1: 4,1-quaterphenyl-5-yl)-(9,9-spirobi[fluoren]-2-yl)amine (Compound 1-184)

(163) The reaction was carried out under the same conditions as those of Example 1, except that bis(biphenyl-4-yl)-(6-bromobiphenyl-3-yl)amine was replaced with {4-(naphthalen-2-yl)phenyl}-(6-bromobiphenyl-3-yl)-(9,9-spirobi[fluoren]-2-yl)amine, and phenylboronic acid was replaced with 4-biphenylboronic acid, whereby a white powder of {4-(naphthalen-2-yl)phenyl}-(1,1: 2,1: 4,1-quaterphenyl-5-yl)-(9,9-spirobi[fluoren]-2-yl)-amine (Compound 1-184, 12.8 g, yield: 80%) was obtained.

(164) ##STR00161##

(165) The structure of the obtained white powder was identified by NMR.

(166) .sup.1H-NMR (CDCl.sub.3) detected 43 hydrogen signals, as follows.

(167) (ppm)=8.00 (1H), 7.74-7.93 (8H), 7.33-7.56 (10H), 6.85-7.19 (18H), 6.58-6.72 (5H), 6.39-6.42 (1H).

EXAMPLE 24

Synthesis of {4-(naphthalen-2-yl)phenyl}-(1,1: 2,1: 2,1-quaterphenyl-5-yl)-(9,9-spirobi[fluoren]-2-yl)amine (Compound 1-186)

(168) The reaction was carried out under the same conditions as those of Example 23, except that 4-biphenylboronic acid was replaced with 2-biphenylboronic acid, whereby a white powder of {4-(naphthalen-2-yl)phenyl}-(1,1: 2,1: 2,1-quaterphenyl-5-yl)-(9,9-spirobi[fluoren]-2-yl)amine (Compound 1-186, 14.5 g, yield: 91%) was obtained.

(169) ##STR00162##

(170) The structure of the obtained white powder was identified by NMR.

(171) .sup.1H-NMR (CDCl.sub.3) detected 43 hydrogen signals, as follows.

(172) (ppm)=8.03 (1H), 7.76-7.94 (8H), 7.07-7.62 (28H), 6.84-6.96 (5H), 6.72-6.74 (1H).

EXAMPLE 25

Synthesis of (biphenyl-4-yl)-{(1,1: 2,1-terphenyl-4-yl}-(phenanthren-9-yl)amine (Compound 1-187)

(173) The reaction was carried out under the same conditions as those of Example 1, except that bis(biphenyl-4-yl)-(6-bromobiphenyl-3-yl)amine was replaced with (6-bromobiphenyl-3-yl)-(biphenyl-4-yl)-(phenanthren-9-yl)amine, whereby a white powder of (biphenyl-4-yl)-{(1,1:2,1-terphenyl-4-yl}-(phenanthren-9-yl)amine (Compound 1-187, 3.5 g, yield: 22%) was obtained.

(174) ##STR00163##

(175) The structure of the obtained white powder was identified by NMR.

(176) .sup.1H-NMR (CDCl.sub.3) detected 31 hydrogen signals, as follows.

(177) (ppm)=8.70-8.81 (2H), 8.17 (1H), 7.83 (1H), 7.78 (1H), 7.72-7.74 (26H).

EXAMPLE 26

Synthesis of (biphenyl-4-yl)-{(1,1: 2,1: 4,1-quaterphenyl-5-yl}-(phenanthren-9-yl)amine (Compound 1-188)

(178) The reaction was carried out under the same conditions as those of Example 25, except that phenylboronic acid was replaced with 4-biphenylboronic acid, whereby a white powder of (biphenyl-4-yl)-{(1,1: 2,1: 4,1-quaterphenyl-5-yl}-(phenanthren-9-yl)amine (Compound 1-188, 13.0 g, yield: 77%) was obtained.

(179) ##STR00164##

(180) The structure of the obtained white powder was identified by NMR.

(181) .sup.1H-NMR (CDCl.sub.3) detected 35 hydrogen signals, as follows.

(182) (ppm)=8.73-8.82 (2H), 8.17 (1H), 7.85 (1H), 7.78 (1H), 7.09-7.75 (30H).

EXAMPLE 27

Synthesis of (biphenyl-4-yl)-{(1,1: 2,1: 3,1-quaterphenyl-5-yl}-(phenanthren-9-yl)amine (Compound 1-189)

(183) The reaction was carried out under the same conditions as those of Example 25, except that phenylboronic acid was replaced with 3-biphenylboronic acid, whereby a white powder of (biphenyl-4-yl)-{(1,1: 2,1: 3,1-quaterphenyl-5-yl}-(phenanthren-9-yl)amine (Compound 1-189, 5.0 g, yield: 40%) was obtained.

(184) ##STR00165##

(185) The structure of the obtained white powder was identified by NMR.

(186) .sup.1H-NMR (CDCl.sub.3) detected 35 hydrogen signals, as follows.

(187) (ppm)=8.76-8.83 (2H), 8.21-8.24 (1H), 7.12-7.87 (32H).

EXAMPLE 28

Synthesis of (biphenyl-4-yl)-{(1,1: 2,1: 2,1-quaterphenyl-5-yl}-(phenanthren-9-yl)amine (Compound 1-190)

(188) The reaction was carried out under the same conditions as those of Example 25, except that phenylboronic acid was replaced with 2-biphenylboronic acid, whereby a white powder of (biphenyl-4-yl)-{(1,1: 2,1: 2,1-quaterphenyl-5-yl}-(phenanthren-9-yl)amine (Compound 1-190, 13.0 g, yield: 77%) was obtained.

(189) ##STR00166##

(190) The structure of the obtained white powder was identified by NMR.

(191) .sup.1H-NMR (CDCl.sub.3) detected 35 hydrogen signals, as follows.

(192) (ppm)=8.75-8.83 (2H), 8.17-8.19 (1H), 6.93-7.73 (28H), 6.69-6.72 (2H), 6.54-6.56 (2H).

EXAMPLE 29

(193) The glass transition points of the arylamine compounds of the general formula (1) were determined using a high-sensitive differential scanning calorimeter (DSC3100S produced by Bruker AXS).

(194) TABLE-US-00001 Glass transition point Compound of Example 2 103 C. Compound of Example 3 115 C. Compound of Example 4 104 C. Compound of Example 5 101 C. Compound of Example 6 112 C. Compound of Example 7 112 C. Compound of Example 8 115 C. Compound of Example 9 117 C. Compound of Example 10 123 C. Compound of Example 11 114 C. Compound of Example 12 116 C. Compound of Example 13 119 C. Compound of Example 14 116 C. Compound of Example 15 119 C. Compound of Example 16 125 C. Compound of Example 17 137 C. Compound of Example 18 124 C. Compound of Example 19 126 C. Compound of Example 20 125 C. Compound of Example 21 128 C. Compound of Example 22 134 C. Compound of Example 23 137 C. Compound of Example 24 148 C. Compound of Example 25 115 C. Compound of Example 26 129 C. Compound of Example 27 116 C. Compound of Example 28 117 C.

(195) The arylamine compounds of the general formula (1) have glass transition points of 100 C. or higher, demonstrating that the compounds have a stable thin-film state.

EXAMPLE 30

(196) A 100 nm-thick vapor-deposited film was fabricated on an ITO substrate using the arylamine compounds of the general formula (1), and a work function was measured using an ionization potential measuring device (PYS-202 produced by Sumitomo Heavy Industries, Ltd.).

(197) TABLE-US-00002 Work function Compound of Example 1 5.68 eV Compound of Example 2 5.72 eV Compound of Example 3 5.66 eV Compound of Example 4 5.67 eV Compound of Example 5 5.72 eV Compound of Example 6 5.75 eV Compound of Example 7 5.70 eV Compound of Example 8 5.70 eV Compound of Example 9 5.72 eV Compound of Example 10 5.79 eV Compound of Example 11 5.67 eV Compound of Example 12 5.68 eV Compound of Example 13 5.69 eV Compound of Example 14 5.62 eV Compound of Example 15 5.63 eV Compound of Example 16 5.66 eV Compound of Example 17 5.67 eV Compound of Example 18 5.68 eV Compound of Example 19 5.64 eV Compound of Example 20 5.75 eV Compound of Example 21 5.64 eV Compound of Example 22 5.65 eV Compound of Example 23 5.63 eV Compound of Example 24 5.63 eV Compound of Example 25 5.76 eV Compound of Example 26 5.74 eV Compound of Example 27 5.75 eV Compound of Example 28 5.76 eV

(198) As the results show, the arylamine compounds of the general formula (1) have desirable energy levels compared to the work function 5.4 eV of common hole transport materials such as NPD and TPD, and thus possess desirable hole transportability.

EXAMPLE 31

Synthesis of N5,N5,N9,N9-tetrakis{4-(tert-butyl)phenyl}spiro(fluorene-9,7-fluoreno[4,3-b]benzofuran)-5,9-diamine (Compound 2-1)

(199) 5,9-dibromospiro(fluorene-9,7-fluoreno[4,3-b]benzofuran) (5.0 g), bis{4-(tert-butyl)phenyl}amine (6.0 g), palladium acetate (0.08 g), sodium tert-butoxide (3.4 g), tri-tert-butylphosphine (0.07 g), and toluene (60 ml) were added into a nitrogen-substituted reaction vessel, and the mixture was heated and stirred for 2 hours under reflux. The mixture was cooled to a room temperature, dichloromethane and water were added, and an organic layer was collected by liquid separation. After the organic layer was concentrated, purification by column chromatography was performed to obtain a powder of N5,N5,N9,N9-tetrakis{4-(tert-butyl)phenyl}spiro (fluorene-9,7-fluoreno[4,3-b]benzofuran)-5,9-diamine (Compound 2-1; 3.1 g; yield 36%).

(200) ##STR00167##

EXAMPLE 32

Synthesis of N2,N2,N7,N7-tetrakis{4-(tert-butyl)phenyl}spiro(dibenzo[5,6:7,8]fluoreno[4,3-b] benzofuran-5,9-fluorene)-2,7-diamine (Compound 2-2)

(201) The reaction was carried out under the same conditions as those of Example 31, except that 5,9-dibromospiro(fluorene-9,7-fluoreno[4,3-b]benzofuran) was replaced with 2,7-dibromospiro(dibenzo[5,6:7,8]fluoreno [4,3-b]benzofuran-5,9-fluorene). As a result, a powder of N2,N2,N7,N7-tetrakis{4-(tert-butyl)phenyl}spiro(dibenzo [5,6:7,8]fluoreno[4,3-b]benzofuran-5,9-fluorene)-2,7-diamine (Compound 2-2; 2.5 g; yield 31%) was obtained.

(202) ##STR00168##

EXAMPLE 33

Synthesis of N5,N5,N9,N9-tetrakis{4-(tert-butyl)phenyl}spiro(benzo[5,6]fluoreno[4,3-b]benzofuran-7,9-fluorene)-5,9-diamine (Compound 2-3)

(203) The reaction was carried out under the same conditions as those of Example 31, except that 5,9-dibromospiro(fluorene-9,7-fluoreno[4,3-b]benzofuran) was replaced with 5,9-dibromospiro(benzo[5,6]fluoreno[4,3-b]benzofuran-7,9-fluorene). As a result, a powder of N5,N5,N9,N9-tetrakis{4-(tert-butyl)phenyl}spiro(benzo[5,6] fluoreno[4,3-b]benzofuran-7,9-fluorene)-5,9-diamine (Compound 2-3; 3.0 g; yield 36%) was obtained.

(204) ##STR00169##

EXAMPLE 34

Synthesis of N6,N6,N10,N10-tetrakis{4-(tert-butyl)phenyl}spiro(fluorene-9,8-fluoreno[3,4-b]benzofuran)-6,10-diamine (Compound 2-4)

(205) The reaction was carried out under the same conditions as those of Example 31, except that 5,9-dibromospiro(fluorene-9,7-fluoreno[4,3-b]benzofuran) was replaced with 6,10-dibromospiro(fluorene-9,8-fluoreno[3,4-b]benzofuran). As a result, a powder of N6,N6,N10,N10-tetrakis{4-(tert-butyl)phenyl}spiro (fluorene-9,8-fluoreno[3,4-b]benzofuran)-6,10-diamine (Compound 2-4; 2.5 g; yield 34%) was obtained.

(206) ##STR00170##

EXAMPLE 35

Synthesis of N5,N5,N9,N9-tetrakis{4-(tert-butyl)phenyl}spiro(fluoreno[4,3-b]benzofuran-7,9-xanthene)-5,9-diamine (Compound 2-5)

(207) The reaction was carried out under the same conditions as those of Example 31, except that 5,9-dibromospiro(fluorene-9,7-fluoreno[4,3-b]benzofuran) was replaced with 5,9-dibromospiro(fluoreno[4,3-b]benzofuran-7,9-xanthene). As a result, a powder of N5,N5,N9,N9-tetrakis{4-(tert-butyl)phenyl}spiro(fluoreno[4,3-b] benzofuran-7,9-xanthene)-5,9-diamine (Compound 2-5; 2.4 g; yield 28%) was obtained.

(208) ##STR00171##

EXAMPLE 36

Synthesis of N5,N9-bis(biphenyl-4-yl)-N5,N9-bis{4-(tert-butyl)phenyl}-2-fluorospiro(fluorene-9,7-fluoreno[4,3-b]benzofuran)-5,9-diamine (Compound 2-6)

(209) The reaction was carried out under the same conditions as those of Example 31, except that 5,9-dibromospiro(fluorene-9,7-fluoreno[4,3-b]benzofuran) was replaced with 5,9-dibromo-2-fluorospiro(fluorene-9,7-fluoreno[4,3-b]benzofuran), and bis{4-(tert-butyl)phenyl}amine was replaced with (biphenyl-4-yl)-{4-(tert-butyl)phenyl}amine. As a result, a powder of N5,N9-bis(biphenyl-4-yl)-N5,N9-bis{4-(tert-butyl) phenyl}-2-fluorospiro(fluorene-9,7-fluoreno[4,3-b]benzofuran)-5,9-diamine (Compound 2-6; 2.4 g; yield 28%) was obtained.

(210) ##STR00172##

EXAMPLE 37

Synthesis of N5,N9-bis{4-(tert-butyl)phenyl}-N5,N9-bis{4-(trimethylsilyl)phenyl}spiro(benzo[5,6]fluoreno[4,3-b]benzofuran-7,9-fluorene)-5,9-diamine (Compound 2-7)

(211) The reaction was carried out under the same conditions as those of Example 31, except that 5,9-dibromospiro(fluorene-9,7-fluoreno[4,3-b]benzofuran) was replaced with 5,9-dibromospiro(benzo[5,6]fluoreno[4,3-b]benzofuran-7,9-fluorene), and bis{4-(tert-butyl)phenyl}amine was replaced with {4-(tert-butyl)phenyl}-{4-(trimethylsilyl)phenyl}amine. As a result, a powder of N5,N9-bis{4-(tert-butyl)phenyl}-N5,N9-bis{4-(trimethylsilyl)phenyl}spiro(benzo[5,6]fluoreno[4,3-b]benzofuran-7,9-fluorene)-5,9-diamine (Compound 2-7; 3.0 g; yield 35%) was obtained.

(212) ##STR00173##

EXAMPLE 38

Synthesis of N5,N9-bis{4-(tert-butyl)phenyl}-N5,N9-bis{4-(trimethylsilyl)phenyl}spiro(fluorene-9,7-fluoreno[4,3-b]benzothiophene)-5,9-diamine (Compound 2-8)

(213) The reaction was carried out under the same conditions as those of Example 31, except that 5,9-dibromospiro(fluorene-9,7-fluoreno[4,3-b]benzofuran) was replaced with 5,9-dibromospiro(fluorene-9,7-fluoreno[4,3-b]benzothiophene), and bis{4-(tert-butyl)phenyl}amine was replaced with {4-(tert-butyl)phenyl}-{4-(trimethylsilyl)phenyl}amine. As a result, a powder of N5,N9-bis{4-(tert-butyl)phenyl}-N5,N9-bis{4-(trimethylsilyl)phenyl}spiro(fluorene-9,7-fluoreno[4,3-b]benzothiophene)-5,9-diamine (Compound 2-8; 3.2 g; yield 37%) was obtained.

(214) ##STR00174##

EXAMPLE 39

Synthesis of N5,N9-bis(biphenyl-4-yl)-N5,N9-bis{4-(tert-butyl)phenyl}spiro(benzo[4,5]thieno[2,3:5,6] fluoreno[4,3-b]benzofuran-7,9-fluorene)-5,9-diamine (Compound 2-9)

(215) The reaction was carried out under the same conditions as those of Example 31, except that 5,9-dibromospiro(fluorene-9,7-fluoreno[4,3-b]benzofuran) was replaced with 5,9-dibromospiro(benzo[4,5]thieno [2,3:5,6]fluoreno[4,3-b]benzofuran-7,9-fluorene), and bis{4-(tert-butyl)phenyl}amine was replaced with {4-(tert-butyl)phenyl}-(biphenyl-4-yl)amine. As a result, a powder of N5,N9-bis(biphenyl-4-yl)-N5,N9-bis{4-(tert-butyl)phenyl}spiro(benzo[4,5]thieno[2,3:5,6]fluoreno[4,3-b]benzofuran-7,9-fluorene)-5,9-diamine (Compound 2-9; 2.8 g; yield 34%) was obtained.

(216) ##STR00175##

EXAMPLE 40

Synthesis of N5,N5,N9,N9-tetrakis{4-(tert-butyl)phenyl}-12,12-dimethyl-12H-spiro(fluorene-9,7-indeno[1,2-a]fluorene)-5,9-diamine (Compound 2-10)

(217) The reaction was carried out under the same conditions as those of Example 31, except that 5,9-dibromospiro(fluorene-9,7-fluoreno[4,3-b]benzofuran) was replaced with 5,9-dibromo-12,12-dimethyl-12H-spiro(fluorene-9,7-indeno[1,2-a]fluorene). As a result, a powder of N5,N5,N9,N9-tetrakis{4-(tert-butyl)phenyl}-12,12-dimethyl-12H-spiro(fluorene-9,7-indeno[1,2-a]fluorene)-5,9-diamine (Compound 2-10; 1.8 g; yield 49%) was obtained.

(218) ##STR00176##

EXAMPLE 41

Synthesis of N6,N10-bis(biphenyl-4-yl)-N6,N10-bis{4-(tert-butyl)phenyl}-5-methyl-5H-spiro(fluorene-9,8-indeno[2,1-c]carbazole)-6,10-diamine (Compound 2-11)

(219) The reaction was carried out under the same conditions as those of Example 31, except that 5,9-dibromospiro(fluorene-9,7-fluoreno[4,3-b]benzofuran) was replaced with 6,10-dibromo-5-methyl-5H-spiro(fluorene-9,8-indeno[2,1-c]carbazole), and bis{4-(tert-butyl)phenyl}amine was replaced with {4-(tert-butyl)phenyl}-(biphenyl-4-yl)amine. As a result, a powder of N6,N10-bis(biphenyl-4-yl)-N6,N10-bis{4-(tert-butyl)phenyl}-5-methyl-5H-spiro(fluorene-9,8-indeno [2,1-c]carbazole)-6,10-diamine (Compound 2-11; 2.3 g; yield 41%) was obtained.

(220) ##STR00177##

EXAMPLE 42

(221) The organic EL device, as shown in FIG. 1, was fabricated by vapor-depositing a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a light emitting layer 6, an electron transport layer 7, an electron injection layer 8, and a cathode (aluminum electrode) 9 in this order on a glass substrate 1 on which an ITO electrode was formed as a transparent anode 2 beforehand.

(222) Specifically, the glass substrate 1 having ITO (film thickness of 150 nm) formed thereon was subjected to ultrasonic washing in isopropyl alcohol for 20 minutes and then dried for 10 minutes on a hot plate heated to 200 C. After UV ozone treatment for 15 minutes, the glass substrate with ITO was installed in a vacuum vapor deposition apparatus, and the pressure was reduced to 0.001 Pa or lower. Compound HIM-1 of the structural formula below was then formed in a film thickness of 5 nm as the hole injection layer 3 so as to cover the transparent anode 2. The first hole transport layer 4 was formed on the hole injection layer 3 by forming the arylamine compounds (4-1) of the structural formula below having two triphenylamine structures within a molecule in a film thickness of 60 nm. The second hole transport layer 5 was formed on the first hole transport layer 4 by forming the compound (1-1) of Example 1 in a film thickness of 5 nm. Then, the light emitting layer 6 was formed on the second hole transport layer 5 in a film thickness of 20 nm by dual vapor deposition of the compound (2-2) of Example 32 and Compound EMH-1 of the structural formula below at a vapor deposition rate ratio of the compound (2-4): EMH-1 =5:95. The electron transport layer 7 was formed on the light emitting layer 6 in a film thickness of 30 nm by dual vapor deposition of the compound (3a-1) of the structural formula below having an anthracene ring structure and Compound ETM-1 of the structural formula below at a vapor deposition rate ratio of the compound (3a-1): ETM-1=50:50. The electron injection layer 8 was formed on the electron transport layer 7 by forming lithium fluoride in a film thickness of 1 nm. Finally, the cathode 9 was formed by vapor-depositing aluminum in a thickness of 100 nm. The characteristics of the thus fabricated organic EL device were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of emission characteristics measurements performed by applying a DC voltage to the fabricated organic EL device.

(223) ##STR00178## ##STR00179##

EXAMPLE 43

(224) An organic EL device was fabricated under the same conditions used in Example 42, except that the compound (2-2) of Example 32 was replaced with the compound (2-4) of Example 34 as the material of the light emitting layer 6, and the layer was formed in a film thickness of 20 nm by dual vapor deposition of the compound (2-4) and the compound EMH-1 of the above structural formula at a vapor deposition rate ratio of the compound (2-4): EMH-1=5:95. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

(225) ##STR00180##

EXAMPLE 44

(226) An organic EL device was fabricated under the same conditions used in Example 42, except that the second hole transport layer 5 was formed by forming the compound (1-4) of Example 4 in a film thickness of 5 nm, instead of using the compound (1-1) of Example 1. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of emission characteristics measurements performed by applying a DC voltage to the fabricated organic EL device.

(227) ##STR00181##

EXAMPLE 45

(228) An organic EL device was fabricated under the same conditions used in Example 43, except that the second hole transport layer 5 was formed by forming the compound (1-4) of Example 4 in a film thickness of 5 nm, instead of using the compound (1-1) of Example 1. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of emission characteristics measurements performed by applying a DC voltage to the fabricated organic EL device.

EXAMPLE 46

(229) An organic EL device was fabricated under the same conditions used in Example 43, except that the second hole transport layer 5 was formed by forming the compound (1-143) of Example 7 in a film thickness of 5 nm, instead of using the compound (1-2) of Example 1. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of emission characteristics measurements performed by applying a DC voltage to the fabricated organic EL device.

(230) ##STR00182##

EXAMPLE 47

(231) An organic EL device was fabricated under the same conditions used in Example 43, except that the second hole transport layer 5 was formed by forming the compound (1-155) of Example 11 in a film thickness of 5 nm, instead of using the compound (1-1) of Example 1. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of emission characteristics measurements performed by applying a DC voltage to the fabricated organic EL device.

(232) ##STR00183##

EXAMPLE 48

(233) An organic EL device was fabricated under the same conditions used in Example 43, except that the second hole transport layer 5 was formed by forming the compound (1-158) of Example 12 in a film thickness of 5 nm, instead of using the compound (1-1) of Example 1. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of emission characteristics measurements performed by applying a DC voltage to the fabricated organic EL device.

(234) ##STR00184##

EXAMPLE 49

(235) An organic EL device was fabricated under the same conditions used in Example 43, except that the second hole transport layer 5 was formed by forming the compound (1-166) of Example 17 in a film thickness of 5 nm, instead of using the compound (1-1) of Example 1. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of emission characteristics measurements performed by applying a DC voltage to the fabricated organic EL device.

(236) ##STR00185##

EXAMPLE 50

(237) An organic EL device was fabricated under the same conditions used in Example 43, except that the second hole transport layer 5 was formed by forming the compound (1-187) of Example 25 in a film thickness of 5 nm, instead of using the compound (1-1) of Example 1. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of emission characteristics measurements performed by applying a DC voltage to the fabricated organic EL device.

(238) ##STR00186##

EXAMPLE 51

(239) An organic EL device was fabricated under the same conditions used in Example 43, except that the second hole transport layer 5 was formed by forming the compound (1-188) of Example 26 in a film thickness of 5 nm, instead of using the compound (1-1) of Example 1. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of emission characteristics measurements performed by applying a DC voltage to the fabricated organic EL device.

(240) ##STR00187##

COMPARATIVE EXAMPLE1

(241) For comparison, an organic EL device was fabricated under the same conditions used in Example 42, except that the first hole transport layer 4 was formed by forming the arylamine compound (4-2) of the structural formula below having two triphenylamine structures within a molecule in a film thickness of 60 nm, instead of using the compound (4-1) of the structural formula having two triphenylamine structures within a molecule, then the second hole transport layer 5 was formed by forming the arylamine compound (4-2) of the structural formula below having two triphenylamine structures within a molecule in a film thickness of 5 nm, instead of using the compound (1-1) of Example 1. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of emission characteristics measurements performed by applying a DC voltage to the fabricated organic EL device.

(242) ##STR00188##

COMPARATIVE EXAMPLE2

(243) For comparison, an organic EL device was fabricated under the same conditions used in Example 43, except that the first hole transport layer 4 was formed by forming the arylamine compound (4-2) of the structural formula having two triphenylamine structures within a molecule in a film thickness of 60 nm, instead of using the compound (4-1) of the structural formula having two triphenylamine structures within a molecule, then the second hole transport layer 5 was formed by forming the arylamine compound (4-2) of the structural formula having two triphenylamine structures within a molecule in a film thickness of 5 nm, instead of using the compound (1-1) of Example 1. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of emission characteristics measurements performed by applying a DC voltage to the fabricated organic EL device.

COMPARATIVE EXAMPLE3

(244) For comparison, an organic EL device was fabricated under the same conditions used in Example 42, except that the second hole transport layer 5 was formed by forming a compound HTM-1 of the structural formula below in a film thickness of 5 nm, instead of using the compound (1-1) of Example 1. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of emission characteristics measurements performed by applying a DC voltage to the fabricated organic EL device.

(245) ##STR00189##

COMPARATIVE EXAMPLE4

(246) For comparison, an organic EL device was fabricated under the same conditions used in Example 43, except that the second hole transport layer 5 was formed by forming a compound HTM-1 of the above structural formula in a film thickness of 5 nm, instead of using the compound (1-1) of Example 1. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of emission characteristics measurements performed by applying a DC voltage to the fabricated organic EL device.

(247) Table 1 summarizes the results of the device lifetime measurements performed with the organic EL devices fabricated in Examples 42 to 51 and Comparative Examples 1 to 4. A device lifetime was measured as the time elapsed until the emission luminance of 2,000 cd/m.sup.2 (initial luminance) at the start of emission was attenuated to 1,900 cd/m.sup.2 (corresponding to attenuation to 95% when taking the initial luminance as 100%) when carrying out constant current driving.

(248) TABLE-US-00003 TABLE 1 Second Current Power Device First hole hole Light Electron Luminance efficiency efficiency lifetime transport transport emitting Transport Voltage [V] [cd/m.sup.2] [cd/A] [lm/W] (Attenuation layer layer layer layer (@10 mA/cm.sup.2) (@10 mA/cm.sup.2) (@10 mA/cm.sup.2) (@10 mA/cm.sup.2) to 95%) Ex. 42 Compound Compound Compound Compound 3.92 790 7.89 6.32 135 h 4-1 1-1 2-2/ 3a-1/ETM-1 EMH-1 Ex 43 Compound Compound Compound Compound 3.84 787 7.86 6.45 181 h 4-1 1-1 2-4/ 3a-1/ETM-1 EMH-1 Ex. 44 Compound Compound Compound Compound 3.96 801 8.00 6.34 140 h 4-1 1-4 2-2/ 3a-1/ETM-1 EMH-1 Ex. 45 Compound Compound Compound Compound 3.82 793 7.93 6.53 205 h 4-1 1-4 2-4/ 3a-1/ETM-1 EMH-1 Ex. 46 Compound Compound Compound Compound 3.83 833 8.33 6.84 192 h 4-1 1-143 2-4/ 3a-1/ETM-1 EMH-1 Ex. 47 Compound Compound Compound Compound 3.83 846 8.47 6.95 188 h 4-1 1-155 2-4/ 3a-1/ETM-1 EMH-1 Ex. 48 Compound Compound Compound Compound 3.82 857 8.57 7.05 173 h 4-1 1-158 2-4/ 3a-1/ETM-1 EMH-1 Ex. 49 Compound Compound Compound Compound 3.79 822 8.22 6.82 222 h 4-1 1-166 2-4/ 3a-1/ETM-1 EMH-1 Ex. 50 Compound Compound Compound Compound 3.84 776 7.76 6.36 212 h 4-1 1-187 2-4/ 3a-1/ETM-1 EMH-1 Ex. 51 Compound Compound Compound Compound 3.86 804 8.04 6.55 187 h 4-1 1-188 2-4/ 3a-1/ETM-1 EMH-1 Com. Compound Compound Compound Compound 3.81 685 6.85 5.65 40 h Ex. 1 4-2 4-2 2-2/ 3a-1/ETM-1 EMH-1 Com. Compound Compound Compound Compound 3.72 701 7.01 5.93 52 h Ex. 2 4-2 4-2 2-4/ 3a-1/ETM-1 EMH-1 Com. Compound HTM-1 Compound Compound 3.91 747 7.46 6.00 35 h Ex. 3 4-1 2-2/ 3a-1/ETM-1 EMH-1 Com. Compound HTM-1 Compound Compound 3.86 745 7.44 6.15 46 h Ex. 4 4-1 2-4/ 3a-1/ETM-1 EMH-1

(249) As shown in Table 1, the current efficiency upon passing a current with a current density of 10 mA/cm.sup.2 was 7.76 to 8.57 cd/A for the organic EL devices in Examples 42 to 51, which was higher than 6.85 to 7.46 cd/A for the organic EL devices in Comparative Examples 1 to 4. Further, the power efficiency was 6.32 to 7.05 lm/W for the organic EL devices in Examples 42 to 51, which was higher than 5.65 to 6.15 lm/W for the organic EL devices in Comparative Examples 1 to 4. Table 1 also shows that the device lifetime (attenuation to 95%) was 135 to 222 hours for the organic EL devices in Examples 42 to 51, showing achievement of a far longer lifetime than 35 to 52 hours for the organic EL devices in Comparative Examples 1 to 4.

(250) It was found that the organic EL device of the present invention can achieve an organic EL device having high luminous efficiency and a long lifetime compared to the conventional organic EL devices by combining an arylamine compound having a specific structure and an amine derivative having a specific condensed ring structure (and a compound having a specific anthracene ring structure) so that carrier balance inside the organic EL device is improved, and further by combining the compounds so that the carrier balance matches the characteristics of the light-emitting material.

INDUSTRIAL APPLICABILITY

(251) In the organic EL device of the present invention in which an arylamine compound having a specific structure and an amine derivative having a specific condensed ring structure (and a compound having a specific anthracene ring structure) are combined, luminous efficiency can be improved, and also durability of the organic EL device can be improved to attain potential applications for, for example, home electric appliances and illuminations.

DESCRIPTION OF REFERENCE NUMERAL

(252) 1 Glass substrate 2 Transparent anode 3 Hole injection layer 4 First hole transport layer 5 Second hole transport layer 6 Light emitting layer 7 Electron transport layer 8 Electron injection layer 9 Cathode