ORGANIC ELECTROLUMINESCENT DEVICE

Abstract

In the organic electroluminescent device having at least an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode in this order, the hole injection layer includes an arylamine compound of the following general formula (1) and an electron acceptor.

##STR00001##

In the formula, Ar.sub.1 to Ar.sub.4 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.

Claims

1. An organic electroluminescent device comprising at least an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode, in this order, wherein the hole injection layer includes an arylamine compound represented by the following general formula (1) and an electron acceptor: ##STR00240## wherein Ar.sub.1 to Ar.sub.4 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.

2. The organic electroluminescent device according to claim 1, wherein the layers that are adjacent to the light emitting layer do not include an electron acceptor.

3. The organic electroluminescent device according to claim 1, wherein the electron acceptor is an electron acceptor selected from trisbromophenylamine hexachloroantimony, tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinodimethane (F4TCNQ), and a radialene derivative.

4. The organic electroluminescent device according to claim 1, wherein the electron acceptor is a radialene derivative represented by the following general formula (2): ##STR00241## wherein Ar.sub.5 to Ar.sub.7 may be the same or different, and represent an aromatic hydrocarbon group, an aromatic heterocyclic group, or a condensed polycyclic aromatic group, having an electron acceptor group as a substituent.

5. The organic electroluminescent device according to claim 1, wherein the hole transport layer includes an arylamine compound 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.

6. The organic electroluminescent device according to claim 5, wherein the arylamine compound 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 is an arylamine compound represented by the following general formula (3): ##STR00242## wherein R.sub.1 to R.sub.6 represent 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; r.sub.1 to r.sub.6 may be the same or different, r.sub.1, r.sub.2, r.sub.5, and r.sub.6 representing an integer of 0 to 5, and r.sub.3 and r.sub.4 representing an integer of 0 to 4, where when r.sub.1, r.sub.2, r.sub.5, and r.sub.6 are an integer of 2 to 5, or when r.sub.3 and r.sub.4 are an integer of 2 to 4, R.sub.1 to R.sub.6, a plurality of which bind to the same benzene ring, may be the same or different and 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 L.sub.1 represents a divalent linking group.

7. The organic EL device according to claim 5, wherein the arylamine compound 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 is an arylamine compound of the following general formula (4): ##STR00243## wherein R.sub.7 to R.sub.18 represent 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; r.sub.7 to r.sub.18 may be the same or different, r.sub.7, r.sub.8, r.sub.11, r.sub.14, r.sub.17, and r.sub.18 representing an integer of 0 to 5, and r.sub.9, r.sub.10, r.sub.12, r.sub.13, r.sub.15, and r.sub.16 representing an integer of 0 to 4. where when r.sub.7, r.sub.8, r.sub.11, r.sub.14, r.sub.17, and r.sub.18 are an integer of 2 to 5, or when r.sub.9, r.sub.10, r.sub.12, r.sub.13, r.sub.15, and r.sub.16 are an integer of 2 to 4, R.sub.7 to R.sub.18, a plurality of which bind to the same benzene ring, may be the same or different and 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 L.sub.2, L.sub.3, and L.sub.4 may be the same or different, and represent a divalent linking group or a single bond.

8. The organic EL device according to claim 1, wherein the electron transport layer includes a compound represented by the following general formula (5) having an anthracene ring structure: ##STR00244## 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; 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 EL device according to claim 1, wherein the electron transport layer includes a compound represented by the following general formula (6) having a pyrimidine ring structure: ##STR00245## wherein Ar.sub.8 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; Ar.sub.9 and Ar.sub.10 may be the same or different, and represent a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; and A represents a monovalent group represented by the following structural formula (7), where Ar.sub.9 and Ar.sub.10 are not simultaneously a hydrogen atom: ##STR00246## wherein Ar.sub.11 represents a substituted or unsubstituted aromatic heterocyclic group; and R.sub.19 to R.sub.22 may be the same or different, and represent a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, cyano, trifluoromethyl, linear or branched alkyl of 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, where R.sub.19 to R.sub.22 may bind to Ar.sub.11 via a single bond, substituted or unsubstituted methylene, an oxygen atom, or a sulfur atom to form a ring.

10. The organic EL device according to claim 1, wherein the light emitting layer includes a blue light emitting dopant.

11. The organic EL device according to claim 10, wherein the light emitting layer includes a pyrene derivative as the blue light emitting dopant.

12. The organic EL device according to claim 10, wherein the blue light emitting dopant includes a light emitting dopant which is an amine derivative having a condensed ring structure represented by the following general formula (8): ##STR00247## 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.12 and Ar.sub.13 may be the same or different, 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 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.23 to R.sub.26 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, substituted or unsubstituted aryloxy, or a disubstituted amino group substituted by groups selected from an aromatic hydrocarbon group, an aromatic heterocyclic group, and a condensed polycyclic aromatic group, where these groups 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 may bind to the benzene ring binding to R.sub.23 to R.sub.26 via substituted or unsubstituted methylene, an oxygen atom, a sulfur atom, or a monosubstituted amino group to form a ring; R.sub.27 to R.sub.29 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 these groups 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 may bind to the benzene ring binding to R.sub.27 to R.sub.29 via substituted or unsubstituted methylene, an oxygen atom, a sulfur atom, or a monosubstituted amino group to form a ring; and R.sub.30 and R.sub.31 may be the same or different, and represent linear or branched alkyl of 1 to 6 carbon atoms that may have a substituent, cycloalkyl of 5 to 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 a substituted or unsubstituted aryloxy, where these groups may bind to each other via a single bond, substituted or unsubstituted methylene, an oxygen atom, a sulfur atom, or a monosubstituted amino group to form a ring.

13. The organic EL device according to claim 1, wherein the light emitting layer includes an anthracene derivative.

14. The organic EL device according to claim 13, wherein the light emitting layer includes a host material which is the anthracene derivative.

15. The organic electroluminescent device according to claim 2, wherein the electron acceptor is an electron acceptor selected from trisbromophenylamine hexachloroantimony, tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinodimethane (F4TCNQ), and a radialene derivative.

16. The organic electroluminescent device according to claim 2, wherein the electron acceptor is a radialene derivative represented by the following general formula (2): ##STR00248## wherein Ar.sub.5 to Ar.sub.7 may be the same or different, and represent an aromatic hydrocarbon group, an aromatic heterocyclic group, or a condensed polycyclic aromatic group, having an electron acceptor group as a substituent.

17. The organic electroluminescent device according to claim 2, wherein the hole transport layer includes an arylamine compound 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.

18. The organic EL device according to claim 2, wherein the electron transport layer includes a compound represented by the following general formula (5) having an anthracene ring structure: ##STR00249## 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; 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.

19. The organic EL device according to claim 2, wherein the electron transport layer includes a compound represented by the following general formula (6) having a pyrimidine ring structure: ##STR00250## wherein Ar.sub.8 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; Ar.sub.9 and Ar.sub.10 may be the same or different, and represent a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; and A represents a monovalent group represented by the following structural formula (7), where Ar.sub.9 and Ar.sub.10 are not simultaneously a hydrogen atom: ##STR00251## wherein Ar.sub.11 represents a substituted or unsubstituted aromatic heterocyclic group; and R.sub.19 to R.sub.22 may be the same or different, and represent a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, cyano, trifluoromethyl, linear or branched alkyl of 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, where R.sub.19 to R.sub.22 may bind to Ar.sub.11 via a single bond, substituted or unsubstituted methylene, an oxygen atom, or a sulfur atom to form a ring.

20. The organic EL device according to claim 2, wherein the light emitting layer includes a blue light emitting dopant.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0205] FIG. 1 is a diagram illustrating the configuration of the organic EL devices of Examples 52 to 59 and Comparative Examples 1 to 8.

MODE FOR CARRYING OUT THE INVENTION

[0206] 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.

##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042##

[0207] The arylamine compounds described above can be synthesized according to the known methods (refer to Patent Document 7, for example).

[0208] The following presents specific examples of preferred compounds among the arylamine compounds of the general formula (3) preferably used in the organic EL device of the present invention. The present invention, however, is not restricted to these compounds.

##STR00043## ##STR00044## ##STR00045## ##STR00046##

[0209] The following presents specific examples of preferred compounds of the arylamine compounds having two triphenylamine structures in the molecule among the triphenylamine compounds having a structure in which two to six triphenylamine structures in the molecule bind via a single bond or a divalent group that does not contain a heteroatom preferably used in the organic EL device of the present invention, in addition to the arylamine compounds of general formula (3). The present invention, however, is not restricted to these compounds.

##STR00047##

[0210] The following presents specific examples of preferred compounds among the arylamine compounds of the general formula (4) preferably used in the organic EL device of the present invention. The present invention, however, is not restricted to these compounds.

##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054##

[0211] The arylamine compounds of the general formula (3) and the arylamine compounds of the general formula (4) can be synthesized by a known method (refer to Patent Documents 8 to 10, for example).

[0212] The following presents specific examples of preferred compounds among the compounds of the general formula (5a) preferably used in the organic EL device of the present invention and having an anthracene ring structure. The present invention, however, is not restricted to these compounds.

##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060##

[0213] The following presents specific examples of preferred compounds among the compounds of the general formula (5b) preferably used in the organic EL device of the present invention and having an anthracene ring structure. The present invention, however, is not restricted to these compounds.

##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066##

[0214] The following presents specific examples of preferred compounds among the compounds of the general formula (5c) preferably used in the organic EL device of the present invention and having an anthracene ring structure. The present invention, however, is not restricted to these compounds.

##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078##

[0215] The compounds described above having an anthracene ring structure can be synthesized by a known method (refer to Patent Documents 11 to 13, for example).

[0216] The following presents specific examples of preferred compounds among the compounds of the general formula (6) preferably used in the organic EL device of the present invention and having a pyrimidine ring structure. The present invention, however, is not restricted to these compounds.

##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175##

[0217] The compounds described above having a pyrimidine ring structure can be synthesized by a known method (refer to Patent Document 13, for example).

[0218] The following presents specific examples of preferred compounds among the amine derivatives of the general formula (8) preferably used in the organic EL device of the present invention and having a condensed ring structure. The present invention, however, is not restricted to these compounds.

##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181## ##STR00182## ##STR00183## ##STR00184##

[0219] 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 a sublimation purification method. The compounds were identified by an NMR analysis. A melting point, a glass transition point (Tg), and a work function were measured as material property values. The melting point can be used as an index of vapor deposition, the glass transition point (Tg) as an index of stability in a thin-film state, and the work function as an index of hole transportability and hole blocking performance.

[0220] 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.

[0221] The melting point and the glass transition point (Tg) were measured by a high-sensitive differential scanning calorimeter (DSC3100SA produced by Bruker AXS) using powder.

[0222] 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.

[0223] 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, an electron injection 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, and a hole blocking layer between the light emitting layer and the electron transport layer. 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 electron injection layer and the electron transport layer. Further, the organic layers having a same function may have a laminate structure of two or more layers, for example, the hole transport layers may have a laminate structure of two or more layers, the light emitting layers may have a laminate structure of two or more layers, or the electron transport layers may have a laminate structure of two or more layers.

[0224] 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.

[0225] As the hole injection layer of the organic EL device of the present invention, the arylamine compound of the general formula (1) subjected to p-type doping with an electron acceptor is preferably used.

[0226] As a hole injection/transport material that can be mixed with or can be used simultaneously with the arylamine compound of the general formula (1), material such as starburst-type triphenylamine derivatives and various triphenylamine tetramers; porphyrin compounds as represented by copper phthalocyanine; accepting heterocyclic compounds such as hexacyanoazatriphenylene; coating-type polymer materials, and the like can be used. 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.

[0227] As the hole transport layer of the organic EL device of the present invention, the arylamine compound of the general formula (3) and the arylamine compound of the general formula (4) are preferably used.

[0228] The compounds that are not subjected to p-type doping are preferably used.

[0229] These may be individually formed into a film, may be used as a single layer formed with another hole transport material mixed, or may be formed as a laminated structure of the individually deposited layers, a laminated structure of the mixed layers, or a laminated structure of the individually deposited layer and the mixed 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.

[0230] As the electron blocking layer of the organic EL device of the present invention, the arylamine compound of the general formula (1) is preferably used, and in addition, compounds having an electron blocking effect can be used, for example, an arylamine compound having a structure in which four triphenylamine structures in the molecule are joined within a molecule via a single bond or a divalent group that does not contain a heteroatom, an arylamine compound having a structure in which two triphenylamine structures in the molecule are joined within a molecule via a single bond or a divalent group that does not contain a heteroatom, 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. These may be individually formed into a film, may be used as a single layer formed with another hole transport material mixed, or may be formed as a laminated structure of the individually deposited layers, a laminated structure of the mixed layers, or a laminated structure of the individually deposited layer and the mixed 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.

[0231] In the organic EL device of the present invention, it is preferable that the electron acceptor in the layer adjacent to the light emitting layer (for example, the hole transport layer and the electron blocking layer) is not subjected to p-type doping.

[0232] In these layers, the arylamine compound of the general formula (3) and the arylamine compound of the general formula (4) are preferably used, and the arylamine compound of the general formula (1) is particularly preferably used.

[0233] The thicknesses of these layers are not particularly limited, as far as the thicknesses are ordinarily used, and may be, for example, 20 to 100 nm for the hole transport layer and 5 to 30 nm for the electron blocking layer.

[0234] Examples of material used for the light emitting layer of the organic EL device of the present invention can be various metal complexes, anthracene derivatives, bis(styryl)benzene derivatives, pyrene derivatives, oxazole derivatives, and polyparaphenylene vinylene derivatives, in addition to quinolinol derivative metal complexes such as Alq.sub.3. Further, the light emitting layer may be made of a host material and a dopant material. Examples of the host material can be preferably anthracene derivatives. Other 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 preferably pyrene derivatives, amine derivatives of the general formula (8) having a condensed ring structure. Other examples of the dopant material can be quinacridone, coumarin, rubrene, perylene, derivatives thereof, benzopyran derivatives, indenophenanthrene derivatives, rhodamine derivatives, and aminostyryl derivatives. 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.

[0235] 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 FIrpic 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. 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.

[0236] 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.

[0237] 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).

[0238] 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.

[0239] 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.

[0240] Material used for the electron transport layer of the organic EL device of the present invention can be preferably the compounds of the general formula (5) having an anthracene ring structure, and the compounds of the general formula (6) having a pyrimidine ring structure. Other examples of material can be metal complexes of quinolinol derivatives such as Alq.sub.3 and BAlq, various metal complexes, triazole derivatives, triazine derivatives, oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline derivatives, phenanthroline derivatives, and silole derivatives. 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.

[0241] 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.

[0242] 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.

[0243] 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 4,4″-bis{(biphenyl-4-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-1)

[0244] (Biphenyl-4-yl)-phenylamine (39.5 g), 4,4″-diiodo-1,1′:4′,1″-terphenyl (32.4 g), a copper powder (0.42 g), potassium carbonate (27.8 g), 3,5-di-tert-butylsalicylic acid (1.69 g), sodium bisulfite (2.09 g), dodecylbenzene (32 ml), and toluene (50 ml) were added into a reaction vessel and heated up to 210° C. while removing the toluene by distillation. After the obtained product was stirred for 30 hours, the product was cooled, and toluene (50 ml) and methanol (100 ml) were added. A precipitated solid was collected by filtration and washed with a methanol/water (5/1, v/v) mixed solution (500 ml). The solid was heated after adding 1,2-dichlorobenzene (350 ml), and insoluble matter was removed by filtration. After the filtrate was left to cool, methanol (400 ml) was added, and a precipitated crude product was collected by filtration. The crude product was washed under reflux with methanol (500 ml) to obtain a gray powder of 4,4″-bis{(biphenyl-4-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-1; 45.8 g; yield 91%).

[0245] The structure of the obtained gray powder was identified by NMR.

[0246] .sup.1H-NMR (CDCl.sub.3) detected 40 hydrogen signals, as follows.

[0247] δ (ppm)=7.68-7.63 (4H), 7.62-7.48 (12H), 7.45 (4H), 7.38-7.10 (20H).

##STR00185##

Example 2

Synthesis of 4,4″-bis{(biphenyl-4-yl)-4-tolylamino}-1,1′:4′,1″-terphenyl (Compound 1-10)

[0248] (Biphenyl-4-yl)-4-tolylamine (16.7 g), 4,4″-diiodo-1,1′:4′,1″-terphenyl (12.9 g), a copper powder (0.17 g), potassium carbonate (11.2 g), 3,5-di-tert-butylsalicylic acid (0.71 g), sodium bisulfite (0.89 g), dodecylbenzene (20 ml), and toluene (20 ml) were added into a reaction vessel and heated up to 210° C. while removing the toluene by distillation. The obtained product was stirred for 28 hours, and after the product was cooled, toluene (150 ml) was added, and insoluble matter was removed by filtration. Methanol (100 ml) was added, and a precipitated crude product was collected by filtration. Recrystallization of the crude product using a toluene/methanol mixed solvent was repeated three times to obtain a yellowish white powder of 4,4″-bis{(biphenyl-4-yl)-4-tolylamino}-1,1′:4′,1″-terphenyl (Compound 1-10; 12.3 g; yield 61%).

[0249] The structure of the obtained yellowish white powder was identified by NMR.

[0250] .sup.1H-NMR (CDCl.sub.3) detected 44 hydrogen signals, as follows.

[0251] δ (ppm)=7.68-7.62 (4H), 7.61-7.41 (16H), 7.38-7.08 (18H), 2.38 (6H).

##STR00186##

Example 3

Synthesis of 4,4″-bis{(biphenyl-4-yl)-(phenyl-d.SUB.5.)amino}-1,1′:4′,1″-terphenyl (Compound 1-14)

[0252] (Biphenyl-4-yl)-(phenyl-d.sub.5)amine (25.3 g), 4,4″-diiodo-1,1′:4′,1″-terphenyl (20.3 g), a copper powder (0.30 g), potassium carbonate (17.5 g), 3,5-di-tert-butylsalicylic acid (1.05 g), sodium bisulfite (1.31 g), dodecylbenzene (20 ml), and toluene (30 ml) were added into a reaction vessel and heated up to 210° C. while removing the toluene by distillation. After the obtained product was stirred for 23 hours, the product was cooled, and toluene (30 ml) and methanol (60 ml) were added. A precipitated solid was collected by filtration and washed with a methanol/water (1/5, v/v) mixed solution (180 ml) followed by washing with methanol (90 ml). An obtained gray powder was heated after adding 1,2-dichlorobenzene (210 ml), and insoluble matter was removed by filtration. After the filtrate was left to cool, methanol (210 ml) was added, and a precipitated crude product was collected by filtration. The crude product was washed under reflux with methanol (210 ml) to obtain a gray powder of 4,4″-bis{(biphenyl-4-yl)-(phenyl-d.sub.5)amino}-1,1′:4′,1″-terphenyl (Compound 1-14; 29.3 g; yield 96%).

[0253] The structure of the obtained gray powder was identified by NMR.

[0254] .sup.1H-NMR (THF-d.sub.8) detected 30 hydrogen signals, as follows.

[0255] δ (ppm)=7.69 (4H), 7.65-7.52 (12H), 7.39 (4H), 7.28 (2H), 7.20-7.14 (8H).

##STR00187##

Example 4

Synthesis of 4,4″-bis{(naphthalen-1-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-2)

[0256] (Naphthalen-1-yl)-phenylamine (40.0 g), 4,4″-diiodo-1,1′:4′,1″-terphenyl (43.7 g), a copper powder (0.53 g), potassium carbonate (34.4 g), 3,5-di-tert-butylsalicylic acid (2.08 g), sodium bisulfite (2.60 g), dodecylbenzene (40 ml), and xylene (40 ml) were added into a reaction vessel and heated up to 210° C. while removing the xylene by distillation. After the obtained product was stirred for 35 hours, the product was cooled. Toluene (100 ml) was added, and a precipitated solid was collected by filtration. 1,2-dichlorobenzene (210 ml) was added to the obtained solid, and the solid was dissolved under heat, and after silica gel (30 g) was added, insoluble matter was removed by filtration. After the filtrate was left to cool, a precipitated crude product was collected by filtration. The crude product was washed under reflux with methanol to obtain a pale yellow powder of 4,4″-bis{(naphthalen-1-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-2; 21.9 g; yield 40%).

[0257] The structure of the obtained pale yellow powder was identified by NMR.

[0258] .sup.1H-NMR (THF-d.sub.8) detected 36 hydrogen signals, as follows.

[0259] δ (ppm)=7.98-7.88 (4H), 7.80 (2H), 7.60 (4H), 7.52-7.40 (8H), 7.36 (4H), 7.18 (4H), 7.08-7.01 (8H), 6.93 (2H).

##STR00188##

Example 5

Synthesis of 4,4″-bis{(naphthalen-2-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-6)

[0260] (Naphthalen-2-yl)-phenylamine (50.0 g), 4,4″-diiodo-1,1′:4′,1″-terphenyl (50.0 g), tert-butoxy sodium (23.9 g), and xylene (500 ml) were added into a reaction vessel and aerated with nitrogen gas for 1 hour under ultrasonic irradiation. Palladium acetate (0.47 g) and a toluene solution (2.96 ml) containing 50% (w/v) tri-tert-butylphosphine were added, and the mixture was heated up to 120° C. and stirred for 15 hours. After the mixture was left to cool, the mixture was concentrated under reduced pressure, and methanol (300 ml) was added. A precipitated solid was collected by filtration and dissolved under heat after adding 1,2-dichlorobenzene (300 ml). After silica gel (140 g) was added, insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure, and after the product was purified by recrystallization with 1,2-dichlorobenzene (250 ml), the purified product was washed under reflux with methanol to obtain a white powder of 4,4″-bis{(naphthalen-2-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-6; 51.0 g; yield 74%).

[0261] The structure of the obtained white powder was identified by NMR.

[0262] .sup.1H-NMR (THF-d.sub.8) detected 36 hydrogen signals, as follows.

[0263] δ (ppm)=7.77 (4H), 7.70 (4H), 7.64-7.58 (6H), 7.48 (2H), 7.40-7.21 (10H), 7.21-7.12 (8H), 7.04 (2H).

##STR00189##

Example 6

<Synthesis of 4,4″-bis[{(biphenyl-2′,3′,4′,5′,6′-d.SUB.5.)-4-yl}-phenylamino]-1,1′:4′,1″-terphenyl (Compound 1-21)

[0264] {(Biphenyl-2′,3′,4′,5′,6′-d.sub.5)-4-yl}-phenylamine (24.8 g), 4,4″-diiodo-1,1′:4′,1″-terphenyl (19.9 g), a copper powder (0.26 g), potassium carbonate (17.2 g), 3,5-di-tert-butylsalicylic acid (2.06 g), sodium bisulfite (1.30 g), and dodecylbenzene (20 ml) were added into a reaction vessel and heated up to 215° C. After the obtained product was stirred for 21 hours, the product was cooled, and toluene (30 ml) and methanol (60 ml) were added. A precipitated solid was collected by filtration and washed with a methanol/water (1/5, v/v) mixed solution. After adding 1,2-dichlorobenzene (300 ml) to the obtained solid, the solid was heated, and insoluble matter was removed by filtration. After the filtrate was left to cool, methanol (300 ml) was added, and a precipitate was collected by filtration to obtain a yellow powder of 4,4″-bis[{(biphenyl-2′,3′,4′,5′,6′-d.sub.5)-4-yl}-phenylamino]-1,1′:4′,1″-terphenyl (Compound 1-21; 25.5 g; yield 85%).

[0265] The structure of the obtained yellow powder was identified by NMR.

[0266] .sup.1H-NMR (THF-d.sub.8) detected 30 hydrogen signals, as follows.

[0267] δ (ppm)=7.69 (4H), 7.65-7.52 (8H), 7.28 (4H), 7.20-7.12 (10H), 7.03 (4H).

##STR00190##

Example 7

Synthesis of 4,4″-bis{(biphenyl-3-yl)-(biphenyl-4-yl)amino}-1,1′:4′,1″-terphenyl (Compound 1-22)

[0268] (Biphenyl-3-yl)-(biphenyl-4-yl)amine (16.1 g), 4,4″-diiodo-1,1′:4′,1″-terphenyl (11.0 g), a copper powder (0.29 g), potassium carbonate (9.46 g), 3,5-di-tert-butylsalicylic acid (1.14 g), sodium bisulfite (0.71 g), and dodecylbenzene (22 ml) were added into a reaction vessel and heated up to 220° C. After the obtained product was stirred for 34 hours, the product was cooled, and toluene and heptane were added. A precipitated solid was collected by filtration and dissolved under heat after adding 1,2-dichlorobenzene (200 ml). After silica gel (50 g) was added, insoluble matter was removed by filtration. After the filtrate was concentrated under reduced pressure, toluene and acetone were added. A precipitated solid was collected by filtration, and the precipitated solid was crystallized with 1,2-dichloromethane followed by crystallization with acetone, and further crystallized with 1,2-dichloromethane followed by crystallization with methanol to obtain a pale yellow powder of 4,4″-bis{(biphenyl-3-yl)-(biphenyl-4-yl)amino}-1,1′:4′,1″-terphenyl (Compound 1-22; 25.5 g; yield 77%).

[0269] The structure of the obtained pale yellow powder was identified by NMR.

[0270] .sup.1H-NMR (THF-d.sub.8) detected 48 hydrogen signals, as follows.

[0271] δ (ppm)=7.71 (4H), 7.67-7.50 (16H), 7.47 (4H), 7.43-7.20 (20H), 7.12 (4H).

##STR00191##

Example 8

<Synthesis of 4,4″-bis{(phenanthren-9-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-3)

[0272] (Phenanthren-9-yl)-phenylamine (16.9 g), 4,4″-diiodo-1,1′:4′,1″-terphenyl (12.6 g), a copper powder (0.16 g), potassium carbonate (10.9 g), 3,5-di-tert-butylsalicylic acid (0.65 g), sodium bisulfite (0.83 g), and dodecylbenzene (13 ml) were added into a reaction vessel and heated up to 210° C. After the obtained product was stirred for 23 hours, the product was cooled, and toluene (26 ml) and methanol (26 ml) were added. A precipitated solid was collected by filtration and washed with a methanol/water (1/5, v/v) mixed solution (120 ml). The precipitated solid was crystallized with 1,2-dichlorobenzene followed by crystallization with methanol to obtain a white powder of 4,4″-bis{(phenanthren-9-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-3; 9.38 g; yield 47%).

[0273] The structure of the obtained yellow powder was identified by NMR.

[0274] .sup.1H-NMR (THF-d.sub.8) detected 40 hydrogen signals, as follows.

[0275] δ (ppm)=8.88-8.73 (4H), 8.09 (2H), 7.71 (2H), 7.68-7.41 (18H), 7.21-7.10 (12H), 6.92 (2H).

##STR00192##

Example 9

<Synthesis of 4,4″-bis{(biphenyl-3-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-5)

[0276] (Biphenyl-3-yl)-phenylamine (12.7 g), 4,4″-diiodo-1,1′:4′,1″-terphenyl (11.3 g), a copper powder (0.30 g), potassium carbonate (9.72 g), 3,5-di-tert-butylsalicylic acid (1.17 g), sodium bisulfite (0.73 g), and dodecylbenzene (23 ml) were added into a reaction vessel and heated up to 220° C. After the obtained product was stirred for 21 hours, the product was cooled, and after 1,2-dichlorobenzene (250 ml) and silica (30 g) were added, insoluble matter was removed by filtration. After the filtrate was concentrated under reduced pressure, heptane was added. A precipitated solid was collected by filtration, and the precipitated solid was crystallized with a 1,2-dichlorobenzene/heptane mixed solvent and further crystallized with a 1,2-dichlorobenzene/methanol mixed solvent to obtain a pale brown powder of 4,4″-bis{(biphenyl-3-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-5; 10.8 g; yield 64%).

[0277] The structure of the obtained pale brown powder was identified by NMR.

[0278] .sup.1H-NMR (THF-d.sub.8) detected 40 hydrogen signals, as follows.

[0279] δ (ppm)=7.69 (4H), 7.60 (4H), 7.52 (4H), 7.42-7.21 (16H), 7.20-7.13 (8H), 7.10-7.00 (4H).

##STR00193##

Example 10

Synthesis of 4,4″-bis{(triphenylen-2-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-23)

[0280] (Triphenylen-2-yl)-phenylamine (11.9 g), 4,4″-diiodo-1,1′:4′,1″-terphenyl (8.55 g), tert-butoxy sodium (4.09 g), and xylene (86 ml) were added into a reaction vessel and aerated with nitrogen gas for 40 minutes under ultrasonic irradiation. Palladium acetate (0.08 g) and a toluene solution (0.55 ml) containing 50% (w/v) tri-tert-butylphosphine were added, and the mixture was heated up to 100° C. After the mixture was stirred for 7 hours, the mixture was cooled. Methanol (80 ml) was added, and a precipitated solid was collected by filtration. 1,2-dichlorobenzene (300 ml) was added to the obtained solid, and the solid was heated, and after silica gel (45 g) was added, insoluble matter was removed by filtration. The filtrate was concentrated under reduced pressure, and after purified by recrystallization with 1,2-dichlorobenzene, the purified product was washed under reflux with methanol to obtain a pale yellowish green powder of 4,4″-bis{(triphenylen-2-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-23; 11.4 g; yield 74%).

[0281] The structure of the obtained pale yellowish green powder was identified by NMR.

[0282] .sup.1H-NMR (THF-d.sub.8) detected 44 hydrogen signals, as follows.

[0283] δ (ppm)=8.72-8.62 (8H), 8.45 (2H), 8.36 (2H), 7.75 (4H), 7.70-7.21 (26H), 7.09 (2H).

##STR00194##

Example 11

Synthesis of 4,4″-bis{di(naphthalen-2-yl)amino}-1,1′:4′,1″-terphenyl (Compound 1-24)

[0284] Di(naphthalen-2-yl)amine (12.2 g), 4,4″-diiodo-1,1′:4′,1″-terphenyl (9.49 g), a copper powder (0.14 g), potassium carbonate (8.2 g), 3,5-di-tert-butylsalicylic acid (0.51 g), sodium bisulfite (0.69 g), dodecylbenzene (15 ml), and toluene (20 ml) were added into a reaction vessel and heated up to 210° C. while removing the toluene by distillation. After the obtained product was stirred for 28 hours, the product was cooled, and 1,2-dichlorobenzene (20 ml) and methanol (20 ml) were added. A precipitated solid was collected by filtration and washed with a methanol/water (1/4, v/v) mixed solution (200 ml). Then, the solid was dissolved under heat after adding 1,2-dichlorobenzene (100 ml), and after silica gel was added, insoluble matter was removed by filtration. After the filtrate was left to cool, methanol (250 ml) was added, and a precipitated solid was collected by filtration. The precipitated solid was crystallized with a 1,2-dichlorobenzene/methanol mixed solvent followed by washing under reflux with methanol to obtain a yellowish white powder of 4,4″-bis{di(naphthalen-2-yl)amino}-1,1′:4′,1″-terphenyl (Compound 1-24; 10.5 g; yield 70%).

[0285] The structure of the obtained yellowish white powder was identified by NMR.

[0286] .sup.1H-NMR (THF-d.sub.8) detected 40 hydrogen signals, as follows.

[0287] δ (ppm)=7.82-7.75 (6H), 7.72 (4H), 7.68-7.60 (8H), 7.56 (4H), 7.40-7.30 (14H), 7.24 (4H).

##STR00195##

Example 12

<Synthesis of 4,4″-bis[{4-(naphthalen-2-yl)phenyl}-phenylamino]-1,1′:4′,1″-terphenyl (Compound 1-25)

[0288] {4-(Naphthalen-2-yl)phenyl}-phenylamine (16.6 g), 4,4″-diiodo-1,1′:4′,1″-terphenyl (11.8 g), a copper powder (0.18 g), potassium carbonate (10.5 g), 3,5-di-tert-butylsalicylic acid (0.61 g), sodium bisulfite (0.83 g), dodecylbenzene (15 ml), and toluene (20 ml) were added into a reaction vessel and heated up to 210° C. while removing the toluene by distillation. After the obtained product was stirred for 19 hours, the product was cooled, and toluene (20 ml) and methanol (20 ml) were added. A precipitated solid was collected by filtration, washed with a methanol/water (1/4, v/v) mixed solution (180 ml), and further washed with methanol (100 ml). An obtained brownish yellow powder was heated after adding 1,2-dichlorobenzene (175 ml), and insoluble matter was removed by filtration. After the filtrate was left to cool, methanol (200 ml) was added, and a precipitated solid was collected by filtration. The precipitated solid was crystallized with a 1,2-dichlorobenzene/methanol mixed solvent followed by washing under reflux with methanol to obtain a brownish white powder of 4,4″-bis[{4-(naphthalen-2-yl)phenyl}-phenylamino]-1,1′:4′,1″-terphenyl (Compound 1-25; 11.9 g; yield 53%).

[0289] The structure of the obtained brownish white powder was identified by NMR.

[0290] .sup.1H-NMR (THF-d.sub.8) detected 44 hydrogen signals, as follows.

[0291] δ (ppm)=8.10 (2H), 7.93-7.78 (8H), 7.76-7.70 (8H), 7.62 (4H), 7.44 (4H), 7.30 (4H), 7.25-7.16 (12H), 7.05 (2H).

##STR00196##

Example 13

Synthesis of 4-{(biphenyl-4-yl)-phenylamino}-4″-[{4-(1-phenyl-indol-4-yl)phenyl}-phenylamino]-1,1′:4′,1″-terphenyl (Compound 1-26)

[0292] (4′-Bromo-1,1′-biphenyl-4-yl)-{4-(1-phenyl-indol-4-yl)phenyl}-phenylamine (7.25 g), {4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl}-(1,1′-biphenyl-4-yl)-phenylamine (5.76 g), a 2 M potassium carbonate aqueous solution (12.3 ml), toluene (80 ml), and ethanol (20 ml) were added into a reaction vessel and aerated with nitrogen gas for 40 minutes under ultrasonic irradiation. After adding tetrakistriphenylphosphinepalladium (0.43 g), the mixture was heated and refluxed for 7 hours while being stirred. After the mixture was left to cool, water (50 ml) and toluene (100 ml) were added, and insoluble matter was removed by filtration. An organic layer was collected by liquid separation, then dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a crude product. After the crude product was purified by column chromatography (support: silica gel, eluent: toluene/heptane), the purified product was crystallized with THF followed by crystallization with methanol to obtain a pale yellow powder of 4-{(biphenyl-4-yl)-phenylamino}-4″-[{4-(1-phenyl-indol-4-yl)phenyl}-phenylamino]-1,1′:4′,1″-terphenyl (Compound 1-26; 6.80 g; yield 67%).

[0293] The structure of the obtained pale yellow powder was identified by NMR.

[0294] .sup.1H-NMR (THF-d.sub.8) detected 45 hydrogen signals, as follows.

[0295] δ (ppm)=7.70 (4H), 7.68-7.50 (16H), 7.42-7.11 (23H), 7.05 (1H), 6.88 (1H).

##STR00197##

Example 14

Synthesis of 4,4″-bis{(biphenyl-4-yl)-phenylamino}-1,1′:3′,1″-terphenyl (Compound 1-27)

[0296] 3-Bromoiodobenzene (8.83 g), (biphenyl-4-yl)-{4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}-phenylamine (30.5 g), potassium carbonate (13.0 g), water (30 ml), toluene (300 ml), and ethanol (75 ml) were added into a nitrogen-substituted reaction vessel and aerated with nitrogen gas under ultrasonic irradiation for 30 minutes. The mixture was heated after adding tetrakis(triphenylphosphine)palladium (1.1 g), and stirred at 80° C. for 16 hours. The mixture was cooled to a room temperature, and methanol (300 ml) was added. A precipitated solid was collected by filtration, and the solid was dissolved under heat after adding 1,2-dichlorobenzene (270 ml). Silica gel (16 g) was added, and the mixture was stirred for 30 minutes. After insoluble matter was removed by filtration, a crude product precipitated by adding methanol (300 ml) was collected by filtration. The crude product was washed under reflux with methanol (200 ml) to obtain a white powder of 4,4″-bis{(biphenyl-4-yl)-phenylamino}-1,1′:3′,1″-terphenyl (Compound 1-27; 14.3 g; yield 71%).

[0297] The structure of the obtained white powder was identified by NMR.

[0298] .sup.1H-NMR (CDCl.sub.3) detected 40 hydrogen signals, as follows.

[0299] δ (ppm)=7.87 (1H), 7.64-7.50 (12H), 7.48-7.32 (6H), 7.31-6.98 (21H).

##STR00198##

Example 15

Synthesis of 4,4″-bis{(biphenyl-4-yl)-(phenyl-d.SUB.5.)amino}-1,1′:3′,1″-terphenyl (Compound 1-28)

[0300] 1,3-dibromobenzene (6.51 g), (biphenyl-4-yl)-{4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}-(phenyl-d.sub.5)amine (26.9 g), potassium carbonate (11.4 g), water (50 ml), toluene (200 ml), and ethanol (50 ml) were added into a nitrogen-substituted reaction vessel and aerated with nitrogen gas under ultrasonic irradiation for minutes. The mixture was heated after adding tetrakis(triphenylphosphine)palladium (0.95 g), and stirred at 70° C. for 12 hours. The mixture was cooled to a room temperature, and methanol (200 ml) was added. A precipitated solid was collected by filtration, and the solid was dissolved under heat after adding 1,2-dichlorobenzene (400 ml). Silica gel (20 g) was added, and the mixture was stirred for 30 minutes. After insoluble matter was removed by filtration, a precipitate formed by adding methanol (500 ml) was collected by filtration. The precipitate was dissolved by adding 1,2-dichlorobenzene (100 ml), and a crude product precipitated by adding toluene (100 ml) and methanol (100 ml) was collected by filtration. The crude product was washed under reflux with methanol (250 ml) to obtain a white powder of 4,4″-bis{(biphenyl-4-yl)-(phenyl-d.sub.5)amino}-1,1′:3′,1″-terphenyl (Compound 1-28; 18.3 g; yield 91%).

[0301] The structure of the obtained white powder was identified by NMR.

[0302] .sup.1H-NMR (CDCl.sub.3) detected 30 hydrogen signals, as follows.

[0303] δ (ppm)=7.87 (1H), 7.64-7.32 (18H), 7.31-6.98 (11H).

##STR00199##

Example 16

Synthesis of 4,4″-bis{(naphthalen-1-yl)-phenylamino}-1,1′:3′,1″-terphenyl (Compound 1-29)

[0304] The reaction was carried out under the same conditions as those of Example 15, except that (biphenyl-4-yl)-{4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}-(phenyl-d.sub.5)amine was replaced with (naphthalen-1-yl)-{4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}-phenylamine. As a result, a white powder of 4,4″-bis{(naphthalen-1-yl)-phenylamino}-1,1′:3′,1″-terphenyl (Compound 1-29; 8.8 g; yield 59%) was obtained.

[0305] The structure of the obtained white powder was identified by NMR.

[0306] .sup.1H-NMR (CDCl.sub.3) detected 36 hydrogen signals, as follows.

[0307] δ (ppm)=7.99 (2H), 7.92 (2H), 7.81 (2H), 7.72 (1H), 7.57-6.92 (29H).

##STR00200##

Example 17

Synthesis of 4,4″-bis[{4-(dibenzofuran-4-yl)phenyl}-phenylamino]-1,1′:3′,1″-terphenyl (Compound 1-32)

[0308] The reaction was carried out under the same conditions as those of Example 15, except that (biphenyl-4-yl)-{4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}-(phenyl-d.sub.5)amine was replaced with {4-(dibenzofuran-4-yl)phenyl}-{4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}-phenylamine. As a result, a white powder of 4,4″-bis[{4-(dibenzofuran-4-yl)phenyl}-phenylamino]-1,1′:3′,1″-terphenyl (Compound 1-32; 6.8 g; yield 86%) was obtained.

[0309] The structure of the obtained white powder was identified by NMR.

[0310] .sup.1H-NMR (CDCl.sub.3) detected 44 hydrogen signals, as follows.

[0311] δ (ppm)=8.01 (2H), 7.97-7.82 (8H), 7.67-7.24 (34H).

##STR00201##

Example 18

<Synthesis of 2,4″-bis{(biphenyl-4-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-50)

[0312] 4-Bromo-4′-{(biphenyl-4-yl)-phenylamino}-biphenyl (16.8 g), (biphenyl-4-yl)-{2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}-phenylamine (19.0 g), potassium carbonate (7.4 g), water (26 ml), toluene (200 ml), and ethanol (50 ml) were added into a nitrogen-substituted reaction vessel and aerated with nitrogen gas under ultrasonic irradiation for 30 minutes. After adding tetrakis(triphenylphosphine)palladium (0.87 g), the mixture was heated and refluxed for 20 hours while being stirred. After the mixture was cooled to a room temperature, an organic layer was collected by liquid separation, then dried over anhydrous magnesium sulfate and concentrated to obtain a crude product. After the crude product was purified by column chromatography (support: silica gel, eluent: heptane/toluene), the purified product was crystallized with an ethyl acetate/methanol mixed solvent to obtain a white powder of 2,4″-bis{(biphenyl-4-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-50; 20.8 g; yield 82%).

[0313] The structure of the obtained white powder was identified by NMR.

[0314] .sup.1H-NMR (CDCl.sub.3) detected 40 hydrogen signals, as follows.

[0315] δ (ppm)=7.61 (2H), 7.56-6.83 (38H).

##STR00202##

Example 19

Synthesis of 4,4″-bis{(triphenylen-2-yl)-phenylamino}-1,1′:3′,1″-terphenyl (Compound 1-51)

[0316] 4,4″-Dibromo-1,1′:3′,1″-terphenyl (8.2 g), (triphenylen-2-yl)-phenylamine (15.4 g), tert-butoxy sodium (5.1 g), and toluene (180 ml) were added into a nitrogen-substituted reaction vessel and aerated with nitrogen gas under ultrasonic irradiation for 30 minutes. Palladium acetate (0.11 g) and a toluene solution (0.31 ml) containing 50% (w/v) tri-tert-butylphosphine were added, and the mixture was heated and refluxed for 5 hours while being stirred.

[0317] The mixture was cooled to a room temperature and subjected to an extraction procedure using 1,2-dichlorobenzene and then to purification by adsorption with a silica gel, followed by crystallization with a 1,2-dichlorobenzene/methanol mixed solvent to obtain a yellowish white powder of 4,4″-bis{(triphenylen-2-yl)-phenylamino}-1,1′:3′,1″-terphenyl (Compound 1-51; 11.67 g; yield 64%).

[0318] The structure of the obtained yellowish white powder was identified by NMR.

[0319] .sup.1H-NMR (CDCl.sub.3) detected 44 hydrogen signals, as follows.

[0320] δ (ppm)=8.67 (4H), 8.57 (4H), 8.41 (2H), 8.36 (2H), 7.88 (1H), 7.70-7.10 (31H).

##STR00203##

Example 20

Synthesis of 4,4″-bis{(phenanthren-9-yl)-phenylamino}-1,1′:3′,1″-terphenyl (Compound 1-52)

[0321] The reaction was carried out under the same conditions as those of Example 19, except that (triphenylen-2-yl)-phenylamine was replaced with (phenanthren-9-yl)-phenylamine. As a result, a yellowish white powder of 4,4″-bis{(phenanthren-9-yl)-phenylamino}-1,1′:3′,1″-terphenyl (Compound 1-52; 8.0 g; yield 50%) was obtained.

[0322] The structure of the obtained yellowish white powder was identified by NMR.

[0323] .sup.1H-NMR (CDCl.sub.3) detected 40 hydrogen signals, as follows.

[0324] δ (ppm)=8.81-8.71 (4H), 8.10 (2H), 7.83-7.39 (20H), 7.29-6.97 (14H).

##STR00204##

Example 21

Synthesis of 4-{bis(biphenyl-4-yl)amino}-2″-{(biphenyl-4-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-53)

[0325] 2-{(biphenyl-4-yl)-phenylamino}-4″-bromo-1,1′:4′,1″-terphenyl (12.1 g), bis(biphenyl-4-yl)amine (8.0 g), tris(dibenzylideneacetone)palladium (0.6 g), tri-tert-butylphosphine (0.22 g), and tert-butoxy sodium (6.3 g) were added into a nitrogen-substituted reaction vessel, heated and refluxed for 3 hours while being stirred. After the mixture was cooled to a room temperature, methanol (600 ml) was added, and a precipitated crude product was collected by filtration. The crude product was dissolved in toluene, and after insoluble matter was removed by filtration, purification by crystallization with methanol was carried out. Then, recrystallization with a THF/methanol mixed solvent was carried out to obtain a white powder of 4-{bis(biphenyl-4-yl)amino}-2″-{(biphenyl-4-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-53; 15 g; yield 87%).

[0326] The structure of the obtained white powder was identified by NMR.

[0327] .sup.1H-NMR (CDCl.sub.3) detected 44 hydrogen signals, as follows.

[0328] δ (ppm)=7.62 (4H), 7.58-6.91 (38H), 6.87 (2H).

##STR00205##

Example 22

Synthesis of 4,4″-bis{(naphthalen-1-yl)-(phenyl-d.SUB.5.)amino}-1,1′:3′,1″-terphenyl (Compound 1-54)

[0329] The reaction was carried out under the same conditions as those of Example 15, except that (biphenyl-4-yl)-{4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}-(phenyl-d.sub.5)amine was replaced with (naphthalen-1-yl)-{4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}-(phenyl-d.sub.5)amine. As a result, a white powder of 4,4″-bis{(naphthalen-1-yl)-(phenyl-d.sub.5)amino}-1,1′:3′,1″-terphenyl (Compound 1-54; 5.2 g; yield 30%) was obtained.

[0330] The structure of the obtained white powder was identified by NMR.

[0331] .sup.1H-NMR (CDCl.sub.3) detected 26 hydrogen signals, as follows.

[0332] δ (ppm)=7.99 (2H), 7.92 (2H), 7.81 (2H), 7.72 (1H), 7.55-7.36 (15H), 7.13-7.07 (4H).

##STR00206##

Example 23

Synthesis of 2-{bis(biphenyl-4-yl)amino}-4″-{(biphenyl-4-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-56)

[0333] The reaction was carried out under the same conditions as those of Example 18, except that (biphenyl-4-yl)-{2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}-phenylamine was replaced with bis(biphenyl-4-yl)-{2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}amine. As a result, a white powder of 2-{bis(biphenyl-4-yl)amino}-4″-{(biphenyl-4-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-56; 15.7 g; yield 94%) was obtained.

[0334] The structure of the obtained white powder was identified by NMR.

[0335] .sup.1H-NMR (CDCl.sub.3) detected 44 hydrogen signals, as follows.

[0336] δ (ppm)=7.60 (2H), 7.56-6.97 (42H).

##STR00207##

Example 24

Synthesis of 2,4″-bis{bis(biphenyl-4-yl)amino}-1,1′:4′,1″-terphenyl (Compound 1-57)

[0337] The reaction was carried out under the same conditions as those of Example 18, except that 4-bromo-4′-{(biphenyl-4-yl)-phenylamino}-biphenyl was replaced with 4-bromo-4′-{bis(biphenyl-4-yl)amino}-biphenyl, and (biphenyl-4-yl)-{2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}-phenylamine was replaced with 2-{bis(biphenyl-4-yl)amino}phenylboronic acid. As a result, a white powder of 2,4″-bis{bis(biphenyl-4-yl)amino}-1,1′:4′,1″-terphenyl (Compound 1-57; 12 g; yield 76%) was obtained.

[0338] The structure of the obtained white powder was identified by NMR.

[0339] .sup.1H-NMR (CDCl.sub.3) detected 48 hydrogen signals, as follows.

[0340] δ (ppm)=7.65-6.98 (48H).

##STR00208##

Example 25

Synthesis of 4,4″-bis{(biphenyl-4-yl)-(naphthalen-1-yl)amino}-1,1′:3′,1″-terphenyl (Compound 1-59)

[0341] The reaction was carried out under the same conditions as those of Example 19, except that (triphenylen-2-yl)-phenylamine was replaced with (biphenyl-4-yl)-(naphthalen-1-yl)amine. As a result, a white powder of 4,4″-bis{(biphenyl-4-yl)-(naphthalen-1-yl)amino}-1,1′:3′,1″-terphenyl (Compound 1-59; 6.4 g; yield 36%) was obtained.

[0342] The structure of the obtained white powder was identified by NMR.

[0343] .sup.1H-NMR (CDCl.sub.3) detected 44 hydrogen signals, as follows.

[0344] δ (ppm)=8.02 (2H), 7.94 (2H), 7.84 (2H), 7.76 (1H), 7.62-7.38 (27H), 7.33 (2H), 7.19-7.13 (8H).

##STR00209##

Example 26

Synthesis of 4,4″-bis{(9,9-dimethyl-9H-fluoren-2-yl)-phenylamino}-1,1′:3′,1″-terphenyl (Compound 1-60)

[0345] The reaction was carried out under the same conditions as those of Example 19, except that (triphenylen-2-yl)-phenylamine was replaced with (9,9-dimethyl-9H-fluoren-2-yl)-phenylamine. As a result, a white powder of 4,4″-bis{(9,9-dimethyl-9H-fluoren-2-yl)-phenylamino}-1,1′:3′,1″-terphenyl (Compound 1-60; 14.6 g; yield 80%) was obtained.

[0346] The structure of the obtained white powder was identified by NMR.

[0347] .sup.1H-NMR (CDCl.sub.3) detected 48 hydrogen signals, as follows.

[0348] δ (ppm)=7.84 (1H), 7.70-7.03 (35H), 1.48 (12H).

##STR00210##

Example 27

Synthesis of 2-{bis(biphenyl-4-yl)amino}-4″-{(naphthalen-1-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-62)

[0349] The reaction was carried out under the same conditions as those of Example 18, except that 4-bromo-4′-{(biphenyl-4-yl)-phenylamino}-biphenyl was replaced with 4-bromo-4′-{(naphthalen-1-yl)-phenylamino}-biphenyl, and (biphenyl-4-yl)-{2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}-phenylamine was replaced with 2-{bis(biphenyl-4-yl)amino}phenylboronic acid. As a result, a white powder of 2-{bis(biphenyl-4-yl)amino}-4″-{(naphthalen-1-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-62; 12.8 g; yield 75%) was obtained.

[0350] The structure of the obtained white powder was identified by NMR.

[0351] .sup.1H-NMR (CDCl.sub.3) detected 42 hydrogen signals, as follows.

[0352] δ (ppm)=7.99 (2H), 7.93 (2H), 7.81 (2H), 7.57-6.96 (36H).

##STR00211##

Example 28

Synthesis of 2-{(biphenyl-4-yl)-phenylamino}-4″-{(9,9-dimethyl-9H-fluoren-2-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-63)

[0353] The reaction was carried out under the same conditions as those of Example 18, except that 4-bromo-4′-{(biphenyl-4-yl)-phenylamino}-biphenyl was replaced with 4-bromo-4′-{(9,9-dimethyl-9H-fluoren-2-yl)-phenylamino}-biphenyl. As a result, a white powder of 2-{(biphenyl-4-yl)-phenylamino}-4″-{(9,9-dimethyl-9H-fluoren-2-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-63; 11.7 g; yield 73%) was obtained.

[0354] The structure of the obtained white powder was identified by NMR.

[0355] .sup.1H-NMR (CDCl.sub.3) detected 44 hydrogen signals, as follows.

[0356] δ (ppm)=7.68 (1H), 7.64-6.84 (37H), 1.48 (6H).

##STR00212##

Example 29

Synthesis of 4,4″-bis{(biphenyl-4-yl)-(naphthalen-1-yl)amino}-1,1′:2′,1″-terphenyl (Compound 1-67)

[0357] The reaction was carried out under the same conditions as those of Example 19, except that 4,4″-dibromo-1,1′:3′,1″-terphenyl was replaced with 4,4″-dibromo-1,1′:2′,1″-terphenyl, and (triphenylen-2-yl)-phenylamine was replaced with (biphenyl-4-yl)-(naphthalen-1-yl)amine. As a result, a white powder of 4,4″-bis{(biphenyl-4-yl)-(naphthalen-1-yl)amino}-1,1′:2′,1″-terphenyl (Compound 1-67; 5.0 g; yield 30%) was obtained.

[0358] The structure of the obtained white powder was identified by NMR.

[0359] .sup.1H-NMR (CDCl.sub.3) detected 44 hydrogen signals, as follows.

[0360] δ (ppm)=7.93-7.84 (4H), 7.79 (2H), 7.60-7.26 (24H), 7.25-6.92 (14H).

##STR00213##

Example 30

Synthesis of 4,4″-bis[{4-(naphthalen-1-yl)phenyl}-phenylamino]-1,1′:2′,1″-terphenyl (Compound 1-68)

[0361] The reaction was carried out under the same conditions as those of Example 19, except that 4,4″-dibromo-1,1′:3′,1″-terphenyl was replaced with 4,4″-dibromo-1,1′:2′,1″-terphenyl, and (triphenylen-2-yl)-phenylamine was replaced with {4-(naphthalen-1-yl)phenyl}-phenylamine. As a result, a white powder of 4,4″-bis[{4-(naphthalen-1-yl)phenyl}-phenylamino]-1,1′:2′,1″-terphenyl (Compound 1-68; 7.3 g; yield 43%) was obtained.

[0362] The structure of the obtained white powder was identified by NMR.

[0363] .sup.1H-NMR (CDCl.sub.3) detected 44 hydrogen signals, as follows.

[0364] δ (ppm)=8.01 (2H), 7.91 (2H), 7.84 (2H), 7.53-6.98 (38H).

##STR00214##

Example 31

Synthesis of 2,2″-bis[{4-(naphthalen-1-yl)phenyl}-phenylamino]-1,1′:3′,1″-terphenyl (Compound 1-69)

[0365] The reaction was carried out under the same conditions as those of Example 14, except that 3-bromoiodobenzene was replaced with 1,3-diiodobenzene, and (biphenyl-4-yl)-{4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}-phenylamine was replaced with 2-[{4-(naphthalen-1-yl)phenyl}-phenylamino]-phenylboronic acid. As a result, a white powder of 2,2″-bis[{4-(naphthalen-1-yl)phenyl}-phenylamino]-1,1′:3′,1″-terphenyl (Compound 1-69; 7.3 g; yield 43%) was obtained.

[0366] The structure of the obtained white powder was identified by NMR.

[0367] .sup.1H-NMR (CDCl.sub.3) detected 44 hydrogen signals, as follows.

[0368] δ (ppm)=7.94-6.85 (44H).

##STR00215##

Example 32

Synthesis of 4,4″-bis[{4-(naphthalen-1-yl)phenyl}-phenylamino]-1,1′:3′,1″-terphenyl (Compound 1-71)

[0369] The reaction was carried out under the same conditions as those of Example 19, except that (triphenylen-2-yl)-phenylamine was replaced with {4-(naphthalen-1-yl)phenyl}-phenylamine. As a result, a white powder of 4,4″-bis[{4-(naphthalen-1-yl)phenyl}-phenylamino]-1,1′:3′,1″-terphenyl (Compound 1-71; 16.7 g; yield 79%) was obtained.

[0370] The structure of the obtained white powder was identified by NMR.

[0371] .sup.1H-NMR (CDCl.sub.3) detected 44 hydrogen signals, as follows.

[0372] δ (ppm)=8.08 (2H), 7.94 (2H), 7.90-7.80 (3H), 7.65-7.00 (37H).

##STR00216##

Example 33

Synthesis of 2,2″-bis{(9,9-dimethyl-9H-fluoren-2-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-75)

[0373] The reaction was carried out under the same conditions as those of Example 15, except that 1,3-dibromobenzene was replaced with 1,4-dibromobenzene, and (biphenyl-4-yl)-{4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}-(phenyl-d.sub.5)amine was replaced with 2-{(9,9-dimethyl-9H-fluoren-2-yl)-phenylamino}-phenylboron is acid. As a result, a white powder of 2,2″-bis{(9,9-dimethyl-9H-fluoren-2-yl)-phenylamino}-1,1′:4′,1″-terphenyl (Compound 1-75; 13.7 g; yield 76%) was obtained.

[0374] The structure of the obtained white powder was identified by NMR.

[0375] .sup.1H-NMR (THF-d.sub.8) detected 48 hydrogen signals, as follows.

[0376] δ (ppm)=7.53 (2H), 7.35-6.81 (30H), 6.76 (2H), 6.67 (2H), 1.29 (12H).

##STR00217##

Example 34

Synthesis of 2,2″-bis{bis(biphenyl-4-yl)amino}-1,1′:4′,1″-terphenyl (Compound 1-76)

[0377] The reaction was carried out under the same conditions as those of Example 15, except that 1,3-dibromobenzene was replaced with 1,4-dibromobenzene, and (biphenyl-4-yl)-{4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}-(phenyl-d.sub.5)amine was replaced with 2-{bis(biphenyl-4-yl)amino}-phenylboronic acid. As a result, a white powder of 2,2″-bis{bis(biphenyl-4-yl)amino}-1,1′:4′,1″-terphenyl (Compound 1-76; 15.7 g; yield 78%) was obtained.

[0378] The structure of the obtained white powder was identified by NMR.

[0379] .sup.1H-NMR (THF-d.sub.8) detected 48 hydrogen signals, as follows.

[0380] δ (ppm)=7.51-7.45 (8H), 7.33-7.18 (28H), 7.00 (4H), 6.90-6.82 (8H).

##STR00218##

Example 35

Synthesis of 2-{(9,9-dimethyl-9H-fluoren-2-yl)-phenylamino}-2″-[{4-(naphthalen-1-yl)phenyl}-phenylamino]-1,1′:4′,1″-terphenyl (Compound 1-81)

[0381] The reaction was carried out under the same conditions as those of Example 18, except that 4-bromo-4′-{(biphenyl-4-yl)-phenylamino}-biphenyl was replaced with 4-bromo-2′-{4-(naphthalen-1-yl)phenyl}-phenylamino}-biphenyl, and (biphenyl-4-yl)-{2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl}-phenylamine was replaced with 2-{(9,9-dimethyl-9H-fluoren-2-yl)-phenylamino}-phenylboron is acid. As a result, a white powder of 2-{(9,9-dimethyl-9H-fluoren-2-yl)-phenylamino}-2″-[{4-(naphthalen-1-yl)phenyl}-phenylamino]-1,1′:4′,1″-terphenyl (Compound 1-81; 7.3 g; yield 48%) was obtained.

[0382] The structure of the obtained white powder was identified by NMR.

[0383] .sup.1H-NMR (THF-d.sub.8) detected 46 hydrogen signals, as follows.

[0384] δ (ppm)=7.89-7.76 (3H), 7.55-6.69 (37H), 1.29 (6H).

##STR00219##

Example 36

Synthesis of 4,4″-bis{N-phenyl-N-(2-phenyl-biphenyl-4-yl)amino}-1,1′;4′,1″-terphenyl (Compound 1-103)

[0385] 4,4″-diiodo-1,1′;4′,1″-terphenyl (13.0 g), N-phenyl-N-(2-phenyl-biphenyl-4-yl)amine (20.0 g), copper powder (0.18 g), potassium carbonate (11.3 g), 3,5-di-tert-butylsalicylic acid (0.7 g), sodium bisulfite (0.86 g), and dodecylbenzene (30 mL) were added into a nitrogen-substituted reaction vessel, and heated and stirred for 24 hours at 210° C. After cooling, xylene (30 mL) and methanol (60 mL) were added, and then a solid matter was collected by filtration. Toluene (250 mL) and silica gel (20 g) were added to the solid matter, and after stirring while heating to 90° C., insoluble matters were removed by hot filtration. After concentration, a crude product deposited by adding ethyl acetate and methanol was collected, and subjected to recrystallization from chlorobenzene and reflux washing with methanol, so as to obtain 16.9 g of white powder of 4,4″-bis{N-phenyl-N-(2-phenyl-biphenyl-4-yl)amino}-1,1′;4′,1″-terphenyl (Compound 1-103) (yield: 72%).

##STR00220##

[0386] The structure of the obtained white powder was identified by NMR.

[0387] .sup.1H-NMR (CDCl.sub.3) detected 48 hydrogen signals, as follows.

[0388] δ (ppm)=7.68 (4H), 7.62-7.55 (4H), 7.39-7.06 (40H).

Example 37

Synthesis of 4,4″-bis{N-phenyl-N-(2-phenyl-biphenyl-4-yl)amino}-1,1′;2′,1″-terphenyl (Compound 1-104)

[0389] The reaction was carried out under the same conditions as those of Example 19, except that 4,4″-dibromo-1,1′:3′,1″-terphenyl was replaced with 4,4″-dibromo-1,1′:2′,1″-terphenyl, and (triphenylen-2-yl)phenylamine was replaced with N-phenyl-N-(2-phenyl-biphenyl-4-yl)amine. As a result, 4.3 g of white powder of 4,4″-bis{N-phenyl-N-(2-phenyl-biphenyl-4-yl)amino}-1,1′;2′,1″-terphenyl (Compound 1-104) (yield: 42%) was obtained.

##STR00221##

[0390] The structure of the obtained pale yellow powder was identified by NMR.

[0391] .sup.1H-NMR (CDCl.sub.3) detected 48 hydrogen signals, as follows.

[0392] δ (ppm)=7.50-7.39 (4H), 7.31-6.97 (44H).

Example 38

Synthesis of 4,4″-bis{N-phenyl-N-(2-phenyl-biphenyl-4-yl)amino}-1,1′;3′,1″-terphenyl (Compound 1-105)

[0393] The reaction was carried out under the same conditions as those of Example 19, except that (triphenylen-2-yl)phenylamine was replaced with N-phenyl-N-(2-phenyl-biphenyl-4-yl)amine. As a result, 7.7 g of white powder of 4,4″-bis{N-phenyl-N-(2-phenyl-biphenyl-4-yl)amino}-1,1′;3′,1″-terphenyl (Compound 1-105) (yield: 53%) was obtained.

##STR00222##

[0394] The structure of the obtained pale yellow powder was identified by NMR.

[0395] .sup.1H-NMR (CDCl.sub.3) detected 48 hydrogen signals, as follows.

[0396] δ (ppm)=7.81 (2H), 7.61-7.48 (14H), 7.39-7.06 (32H).

Example 39

[0397] The melting points and the glass transition points of the arylamine compounds of the general formula (1) were measured using a high-sensitive differential scanning calorimeter (DSC3100SA produced by Bruker AXS).

TABLE-US-00001 Glass transition Melting point point Compound of Example 1 263° C. 111° C. Compound of Example 2 210° C. 113° C. Compound of Example 3 265° C. 111° C. Compound of Example 4 279° C. 107° C. Compound of Example 5 266° C. 104° C. Compound of Example 6 263° C. 111° C. Compound of Example 7 262° C. 117° C. Compound of Example 8 303° C. 149° C. Compound of Example 10 365° C. 163° C. Compound of Example 11 289° C. 138° C. Compound of Example 13 No melting point 125° C. observed Compound of Example 14 252° C. 108° C. Compound of Example 15 252° C. 108° C. Compound of Example 16 No melting point 106° C. observed Compound of Example 17 No melting point 135° C. observed Compound of Example 18 No melting point 107° C. observed Compound of Example 19 323° C. 159° C. Compound of Example 20 290° C. 146° C. Compound of Example 21 No melting point 119° C. observed Compound of Example 22 No melting point 106° C. observed Compound of Example 23 No melting point 118° C. observed Compound of Example 24 No melting point 133° C. observed Compound of Example 25 No melting point 136° C. observed Compound of Example 26 286° C. 124° C. Compound of Example 27 No melting point 117° C. observed Compound of Example 28 218° C. 114° C. Compound of Example 29 No melting point 127° C. observed Compound of Example 31 No melting point 110° C. observed Compound of Example 32 No melting point 122° C. observed Compound of Example 33 269° C. 117° C. Compound of Example 34 277° C. 122° C. Compound of Example 35 No melting point 117° C. observed Compound of Example 36 249° C. 124° C. Compound of Example 37 No melting point 115° C. observed Compound of Example 38 No melting point 122° C. observed

[0398] 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 40

[0399] 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.).

TABLE-US-00002 Work function Compound of Example 1 5.65 eV Compound of Example 3 5.65 eV Compound of Example 4 5.67 eV Compound of Example 5 5.66 eV Compound of Example 6 5.69 eV Compound of Example 7 5.63 eV Compound of Example 8 5.70 eV Compound of Example 9 5.72 eV Compound of Example 10 5.62 eV Compound of Example 11 5.61 eV Compound of Example 12 5.62 eV Compound of Example 13 5.67 eV Compound of Example 14 5.75 eV Compound of Example 15 5.75 eV Compound of Example 16 5.79 eV Compound of Example 17 5.68 eV Compound of Example 18 5.76 eV Compound of Example 19 5.70 eV Compound of Example 20 5.79 eV Compound of Example 21 5.71 eV Compound of Example 22 5.79 eV Compound of Example 23 5.72 eV Compound of Example 24 5.70 eV Compound of Example 25 5.71 eV Compound of Example 26 5.65 eV Compound of Example 27 5.70 eV Compound of Example 28 5.67 eV Compound of Example 29 5.69 eV Compound of Example 30 5.75 eV Compound of Example 31 5.84 eV Compound of Example 32 5.76 eV Compound of Example 33 5.72 eV Compound of Example 34 5.67 eV Compound of Example 35 5.76 eV Compound of Example 36 5.67 eV Compound of Example 37 5.75 eV Compound of Example 38 5.76 eV

[0400] 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 41

Synthesis of N5′,N5′,N9′,N9′-tetrakis{4-(tert-butyl)phenyl}spiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran)-5′,9′-diamine (Compound 8-1)

[0401] 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 heated and refluxed for 2 hours while being stirred. After the mixture was cooled to a room temperature, dichloromethane and water were added, and an organic layer was collected by liquid separation. The organic layer was concentrated and then purified by column chromatography to obtain 3.1 g of powder of N5′,N5′,N9′,N9′-tetrakis{4-(tert-butyl)phenyl}spiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran)-5′,9′-diamine (Compound 8-1) (yield: 36%).

##STR00223##

Example 42

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 8-2)

[0402] The reaction was carried out under the same conditions as those of Example 41, 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, 2.5 g of 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 8-2) (yield: 31%) was obtained.

##STR00224##

Example 43

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 8-3)

[0403] The reaction was carried out under the same conditions as those of Example 41, 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, 3.0 g of 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 8-3) (yield: 36%) was obtained.

##STR00225##

Example 44

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

[0404] The reaction was carried out under the same conditions as those of Example 41, except that 5′,9′-dibromospiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran) was replaced with 6′,10′-dibromospiro(fluorene-9,8′-fluoreno[4,3-b]benzofuran). As a result, 2.5 g of powder of N6′,N6′,N10′,N10′-tetrakis{4-(tert-butyl)phenyl}spiro(fluorene-9,8′-fluoreno[4,3-b]benzofuran)-6′,10′-diamine (Compound 8-4) (yield: 34%) was obtained.

##STR00226##

Example 45

Synthesis of N5,N5,N9,N9-tetrakis{4-(tert-butyl)phenyl}spiro(fluoreno[4,3-b]benzofuran-7,9′-xanthene)-5,9-diamine (Compound 8-5)

[0405] The reaction was carried out under the same conditions as those of Example 41, 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, 2.4 g of powder of N5,N5,N9,N9-tetrakis{4-(tert-butyl)phenyl}spiro(fluoreno[4,3-b]benzofuran-7,9′-xanthene)-5,9-diamine (Compound 8-5) (yield: 28%) was obtained.

##STR00227##

Example 46

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 8-6)

[0406] The reaction was carried out under the same conditions as those of Example 41, 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 2.4 g of 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 8-6) (yield: 28%) was obtained.

##STR00228##

Example 47

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 8-7)

[0407] The reaction was carried out under the same conditions as those of Example 41, 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, 3.0 g of 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 8-7) (yield: 35%) was obtained.

##STR00229##

Example 48

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 8-8)

[0408] The reaction was carried out under the same conditions as those of Example 41, 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, 3.2 g of powder of N5′,N9′-bis{4-(tert-butyl)phenyl}-N5′,N9′-bis{4-(trimethyl silyl)phenyl}spiro(fluorene-9,7′-fluoreno[4,3-b]benzothiophene)-5′,9′-diamine (Compound 8-8) (yield: 37%) was obtained.

##STR00230##

Example 49

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 8-9)

[0409] The reaction was carried out under the same conditions as those of Example 41, 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, 2.8 g of 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 8-9) (yield: 34%) was obtained.

##STR00231##

Example 50

Synthesis of N5′,N5′,N9′,N9′-tetrakis{4-(tert-butyl)phenyl}-12′,12′-dim ethyl-12′H-spiro(fluorene-9,7′-indeno[1,2-a]fluorene)-5′,9′-diamine (Compound 8-10)

[0410] The reaction was carried out under the same conditions as those of Example 41, except that 5′,9′-dibromospiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran) was replaced with 5′,9′-dibromo-12′,12′-dimethyl-12′H-spiro(fluorene-9,7′-indeno[1,2-a]fluorene). As a result, 1.8 g of powder of N5′,N5′,N9′,N9′-tetrakis{4-(tert-butyl)phenyl}-12′,12′-dim ethyl-12′H-spiro(fluorene-9,7′-indeno[1,2-a]fluorene)-5′,9′-diamine (Compound 8-10) (yield: 49%) was obtained.

##STR00232##

Example 51

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

[0411] The reaction was carried out under the same conditions as those of Example 41, except that 5′,9′-dibromospiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran) was replaced with 6′,10′-dibromo-5′-methyl-5′H-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, 2.3 g of powder of N6′,N10′-bis(biphenyl-4-yl)-N6′,N10′-bis{4-(tert-butyl)phenyl}-5′-methyl-5′H-spiro(fluorene-9,8′-indeno[2,1-c]carbazole)-6′,10′-diamine (Compound 8-11) (yield: 41%) was obtained.

##STR00233##

Example 52

[0412] The organic EL device, as shown in FIG. 1, was fabricated by vapor-depositing a hole injection layer 3, a hole transport layer 4, alight emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode (aluminum electrode) 8 in this order on a glass substrate 1 on which an ITO electrode was formed as a transparent anode 2 beforehand.

[0413] Specifically, the glass substrate 1 having ITO having a 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. Thereafter, after performing an 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. Subsequently, as the hole injection layer 3 covering the transparent anode 2, an electron acceptor (Acceptor-1) of the structural formula below and Compound (1-1) of Example 1 were formed in a film thickness of 30 nm by dual vapor deposition at a vapor deposition rate ratio of Acceptor-1/Compound (1-1)=3/97. As the hole transport layer 4 on the hole injection layer 3, Compound 1-1 of Example 1 was formed in a film thickness of 40 nm. As the light emitting layer 5 on the hole transport layer 4, Compound EMD-1 of the structural formula below and Compound EMH-1 of the structural formula below were formed in a film thickness of 20 nm by dual vapor deposition at a vapor deposition rate ratio of EMD-1/EMH-1=5/95. As the electron transport layer 6 on the light emitting layer 5, Compound (5b-1) having an anthracene ring structure of the structural formula below and Compound ETM-1 of the structural formula below were formed in a film thickness of 30 nm by dual vapor deposition at a vapor deposition rate ratio of Compound (5b-1)/ETM-1=50/50. As the electron injection layer 7 on the electron transport layer 6, lithium fluoride was formed in a film thickness of 1 nm. Finally, aluminum was vapor-deposited in a thickness of 100 nm to form the cathode 8. The characteristics of the thus fabricated organic EL device were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of the measurement of emission characteristics performed by applying a direct current voltage to the fabricated organic EL device.

##STR00234## ##STR00235##

Example 53

[0414] An organic EL device was fabricated under the same conditions used in Example 52, except that Compound (6-125) having a pyrimidine ring structure was used as the material of the electron transport layer 6 instead of Compound (5b-1) having an anthracene ring structure, and Compound (6-125) and Compound ETM-1 of the above structural formula were formed in a film thickness of 30 nm by dual vapor deposition at a vapor deposition rate ratio of Compound (6-125)/ETM-1=50/50. The characteristics of the thus fabricated organic EL device were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of the measurement of emission characteristics performed by applying a direct current voltage to the fabricated organic EL device.

##STR00236##

Example 54

[0415] An organic EL device was fabricated under the same conditions used in Example 52, except that the amine derivative (8-1) having a condensed ring structure was used as the material of the light emitting layer 5 instead of Compound EMD-1 of the above structural formula, and the amine derivative (8-1) having a condensed ring structure and Compound EMH-1 of the above structural formula were formed in a film thickness of 25 nm by dual vapor deposition at a vapor deposition rate ratio of amine derivative (8-1)/EMH-1=5/95. The characteristics of the thus fabricated organic EL device were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of the measurement of emission characteristics performed by applying a direct current voltage to the fabricated organic EL device.

##STR00237##

Example 55

[0416] An organic EL device was fabricated under the same conditions used in Example 53, except that the amine derivative (8-1) having a condensed ring structure was used as the material of the light emitting layer 5 instead of Compound EMD-1 of the above structural formula, and the amine derivative (8-1) having a condensed ring structure and Compound EMH-1 of the above structural formula were formed in a film thickness of 25 nm by dual vapor deposition at a vapor deposition rate ratio of amine derivative (8-1)/EMH-1=5/95. The characteristics of the thus fabricated organic EL device were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of the measurement of emission characteristics performed by applying a direct current voltage to the fabricated organic EL device.

Example 56

[0417] An organic EL device was fabricated under the same conditions used in Example 52, except that Compound (1-2) of Example 4 was used as the material of the hole injection layer 3 instead of Compound (1-1) of Example 1, and the electron acceptor (Acceptor-1) of the above structural formula and Compound (1-2) of Example 4 were formed in a film thickness of 30 nm by dual vapor deposition at a vapor deposition rate ratio of Acceptor-1/Compound (1-2)=3/97, and Compound (1-2) of Example 4 was used as the material of the hole transport layer 4 instead of Compound (1-1) of Example 1, and formed in a film thickness of 40 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 the measurement of emission characteristics performed by applying a direct current voltage to the fabricated organic EL device.

##STR00238##

Example 57

[0418] An organic EL device was fabricated under the same conditions used in Example 53, except that Compound (1-2) of Example 4 was used as the material of the hole injection layer 3 instead of Compound (1-1) of Example 1, and the electron acceptor (Acceptor-1) of the above structural formula and Compound (1-2) of Example 4 were formed in a film thickness of 30 nm by dual vapor deposition at a vapor deposition rate ratio of Acceptor-1/Compound (1-2)=3/97, and Compound (1-2) of Example 4 was used as the material of the hole transport layer 4 instead of Compound (1-1) of Example 1, and formed in a film thickness of 40 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 the measurement of emission characteristics performed by applying a direct current voltage to the fabricated organic EL device.

Example 58

[0419] An organic EL device was fabricated under the same conditions used in Example 54, except that Compound (1-2) of Example 4 was used as the material of the hole injection layer 3 instead of Compound (1-1) of Example 1, and the electron acceptor (Acceptor-1) of the above structural formula and Compound (1-2) of Example 4 were formed in a film thickness of 30 nm by dual vapor deposition at a vapor deposition rate ratio of Acceptor-1/Compound (1-2)=3/97, and Compound (1-2) of Example 4 was used as the material of the hole transport layer 4 instead of Compound (1-1) of Example 1, and formed in a film thickness of 40 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 the measurement of emission characteristics performed by applying a direct current voltage to the fabricated organic EL device.

Example 59

[0420] An organic EL device was fabricated under the same conditions used in Example 55, except that Compound (1-2) of Example 4 was used as the material of the hole injection layer 3 instead of Compound (1-1) of Example 1, and the electron acceptor (Acceptor-1) of the above structural formula and Compound (1-2) of Example 4 were formed in a film thickness of 30 nm by dual vapor deposition at a vapor deposition rate ratio of Acceptor-1/Compound (1-2)=3/97, and Compound (1-2) of Example 4 was used as the material of the hole transport layer 4 instead of Compound (1-1) of Example 1, and formed in a film thickness of 40 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 the measurement of emission characteristics performed by applying a direct current voltage to the fabricated organic EL device.

Comparative Example 1

[0421] For comparison, an organic EL device was fabricated under the same conditions used in Example 52, except that HTM-1 of the structural formula below was used as the material of the hole injection layer 3 instead of Compound (1-1) of Example 1, and the electron acceptor (Acceptor-1) of the above structural formula and HTM-1 of the structural formula below were formed in a film thickness of 30 nm by dual vapor deposition at a vapor deposition rate ratio of Acceptor-1/HTM-1=3/97, and HTM-1 of the structural formula below was used as the material of the hole transport layer 4 instead of Compound (1-1) of Example 1, and formed in a film thickness of 40 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 the measurement of emission characteristics performed by applying a direct current voltage to the fabricated organic EL device.

##STR00239##

Comparative Example 2

[0422] For comparison, an organic EL device was fabricated under the same conditions used in Example 53, except that HTM-1 of the above structural formula was used as the material of the hole injection layer 3 instead of Compound (1-1) of Example 1, and the electron acceptor (Acceptor-1) of the above structural formula and HTM-1 of the above structural formula were formed in a film thickness of 30 nm by dual vapor deposition at a vapor deposition rate ratio of Acceptor-1/HTM-1=3/97, and HTM-1 of the above structural formula was used as the material of the hole transport layer 4 instead of Compound (1-1) of Example 1, and formed in a film thickness of 40 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 the measurement of emission characteristics performed by applying a direct current voltage to the fabricated organic EL device.

Comparative Example 3

[0423] For comparison, an organic EL device was fabricated under the same conditions used in Example 54, except that HTM-1 of the above structural formula was used as the material of the hole injection layer 3 instead of Compound (1-1) of Example 1, and the electron acceptor (Acceptor-1) of the above structural formula and HTM-1 of the above structural formula were formed in a film thickness of 30 nm by dual vapor deposition at a vapor deposition rate ratio of Acceptor-1/HTM-1=3/97, and HTM-1 of the above structural formula was used as the material of the hole transport layer 4 instead of Compound (1-1) of Example 1, and formed in a film thickness of 40 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 the measurement of emission characteristics performed by applying a direct current voltage to the fabricated organic EL device.

Comparative Example 4

[0424] For comparison, an organic EL device was fabricated under the same conditions used in Example 55, except that HTM-1 of the above structural formula was used as the material of the hole injection layer 3 instead of Compound (1-1) of Example 1, and the electron acceptor (Acceptor-1) of the above structural formula and HTM-1 of the above structural formula were formed in a film thickness of 30 nm by dual vapor deposition at a vapor deposition rate ratio of Acceptor-1/HTM-1=3/97, and HTM-1 of the above structural formula was used as the material of the hole transport layer 4 instead of Compound (1-1) of Example 1, and formed in a film thickness of 40 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 the measurement of emission characteristics performed by applying a direct current voltage to the fabricated organic EL device.

Comparative Example 5

[0425] For comparison, an organic EL device was fabricated under the same conditions used in Example 53, except that the electron acceptor (Acceptor-1) of the above structural formula and Compound (1-1) of Example 1 were used as the material of the hole transport layer 4 instead of Compound (1-1) of Example 1, and the electron acceptor (Acceptor-1) of the above structural formula and Compound (1-1) of Example 1 were formed in a film thickness of 40 nm by dual vapor deposition at a vapor deposition rate ratio of Acceptor-1/Compound (1-1)=3/97. The characteristics of the thus fabricated organic EL device were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of the measurement of emission characteristics performed by applying a direct current voltage to the fabricated organic EL device.

Comparative Example 6

[0426] For comparison, an organic EL device was fabricated under the same conditions used in Example 55, except that the electron acceptor (Acceptor-1) of the above structural formula and Compound (1-1) of Example 1 were used as the material of the hole transport layer 4 instead of Compound (1-1) of Example 1, and the electron acceptor (Acceptor-1) of the above structural formula and Compound (1-1) of Example 1 were formed in a film thickness of 40 nm by dual vapor deposition at a vapor deposition rate ratio of Acceptor-1/Compound (1-1)=3/97. The characteristics of the thus fabricated organic EL device were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of the measurement of emission characteristics performed by applying a direct current voltage to the fabricated organic EL device.

Comparative Example 7

[0427] For comparison, an organic EL device was fabricated under the same conditions used in Example 57, except that the electron acceptor (Acceptor-1) of the above structural formula and Compound (1-2) of Example 4 were used as the material of the hole transport layer 4 instead of Compound (1-2) of Example 4, and the electron acceptor (Acceptor-1) of the above structural formula and Compound (1-2) of Example 4 were formed in a film thickness of 40 nm by dual vapor deposition at a vapor deposition rate ratio of Acceptor-1/Compound (1-2)=3/97. The characteristics of the thus fabricated organic EL device were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of the measurement of emission characteristics performed by applying a direct current voltage to the fabricated organic EL device.

Comparative Example 8

[0428] For comparison, an organic EL device was fabricated under the same conditions used in Example 59, except that the electron acceptor (Acceptor-1) of the above structural formula and Compound (1-2) of Example 4 were used as the material of the hole transport layer 4 instead of Compound (1-2) of Example 4, and the electron acceptor (Acceptor-1) of the above structural formula and Compound (1-2) of Example 4 were formed in a film thickness of 40 nm by dual vapor deposition at a vapor deposition rate ratio of Acceptor-1/Compound (1-2)=3/97. The characteristics of the thus fabricated organic EL device were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of the measurement of emission characteristics performed by applying a direct current voltage to the fabricated organic EL device.

[0429] Table 1 summarizes the results of the measurement of device lifetime performed with organic EL devices fabricated in Examples 52 to 59 and Comparative Examples 1 to 8. The 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% with respect to the initial luminance as 100%, 95% attenuation) when carrying out constant current driving.

TABLE-US-00003 TABLE 1 Current Power Device Hole Hole Light Electron Voltage Luminance efficiency efficiency lifetime injection transport emitting transport [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. Compound Compound EMD-1/ Compound 3.90 657 6.57 5.30 116 h 52 1-1/ 1-1 EMH-1 5b-1/ Acceptor-1 ETM-1 Ex. Compound Compound EMD-1/ Compound 3.87 719 7.20 5.85 137 h 53 1-1/ 1-1 EMH-1 6-125/ Acceptor-1 ETM-1 Ex. Compound Compound Compound Compound 3.82 643 6.44 5.29 117 h 54 1-1/ 1-1 8-1/ 5b-1/ Acceptor-1 EMH-1 ETM-1 Ex. Compound Compound Compound Compound 3.85 691 6.92 5.65 135 h 55 1-1/ 1-1 8-1/ 6-125/ Acceptor-1 EMH-1 ETM-1 Ex. Compound Compound EMD-1/ Compound 3.93 626 6.27 5.01 120 h 56 1-2/ 1-2 EMH-1 5b-1/ Acceptor-1 ETM-1 Ex. Compound Compound EMD-1/ Compound 3.89 676 6.77 5.48 142 h 57 1-2/ 1-2 EMH-1 6-125/ Acceptor-1 ETM-1 Ex. Compound Compound Compound Compound 3.81 606 6.06 4.99 143 h 58 1-2/ 1-2 8-1/ 5b-1/ Acceptor-1 EMH-1 ETM-1 Ex. Compound Compound Compound Compound 3.82 662 6.63 5.45 128 h 59 1-2/ 1-2 8-1/ 6-125/ Acceptor-1 EMH-1 ETM-1 Com. HTM-1/ HTM-1 EMD-1/ Compound 3.86 502 5.03 4.10  55 h Ex. 1 Acceptor-1 EMH-1 5b-1/ ETM-1 Com. HTM-1/ HTM-1 EMD-1/ Compound 3.84 543 5.44 4.45  69 h Ex. 2 Acceptor-1 EMH-1 6-125/ ETM-1 Com. HTM-1/ HTM-1 Compound Compound 3.75 483 4.84 4.07  6 h Ex. 3 Acceptor-1 8-1/ 5b-1/ EMH-1 ETM-1 Com. HTM-1/ HTM-1 Compound Compound 3.77 520 5.21 4.35  58 h Ex. 4 Acceptor-1 8-1/ 6-125/ EMH-1 ETM-1 Com. Compound Compound EMD-1/ Compound 3.84 55 0.55 0.45  1 h Ex. 5 1-1/ 1-1/ EMH-1 6-125/ Acceptor-1 Acceptor-1 ETM-1 Com. Compound Compound Compound Compound 3.86 62 0.62 0.50  1 h Ex. 6 1-1/ 1-1/ 8-1/ 6-125/ Acceptor-1 Acceptor-1 EMH-1 ETM-1 Com. Compound Compound EMD-1/ Compound 3.91 78 0.78 0.63  1 h Ex. 7 1-2/ 1-2/ EMH-1 6-125/ Acceptor-1 Acceptor-1 ETM-1 Com. Compound Compound Compound Compound 3.91 81 0.80 0.64  1 h Ex. 8 1-2/ 1-2/ 8-1/ 6-125/ Acceptor-1 Acceptor-1 EMH-1 ETM-1

[0430] As shown in Table 1, the luminous efficiency upon passing a current with a current density of 10 mA/cm.sup.2 was 0.55 to 0.80 cd/A for the organic EL devices in Comparative Examples 5 to 8 having the hole transport layer that was also doped with an electron acceptor, whereas was a high efficiency of 4.84 to 5.44 cd/A for the organic EL devices in Comparative Examples 1 to 4 having the hole transport layer that was not doped with an electron acceptor. The luminous efficiency was a further higher efficiency of 6.06 to 7.20 cd/A for the organic EL devices in Examples 52 to 59 using the arylamine derivative of the general formula (1) in the hole injection layer. The power efficiency was 0.45 to 0.64 lm/W for the organic EL devices in Comparative Examples 5 to 8 having the hole transport layer that was also doped with an electron acceptor, whereas was a high efficiency of 4.07 to 4.45 lm/W for the organic EL devices in Comparative Examples 1 to 4 having the hole transport layer that was not doped with an electron acceptor. The power efficiency was a further higher efficiency of 4.99 to 5.85 lm/W for the organic EL devices in Examples 52 to 59 using the arylamine compound of the general formula (1) in the hole injection layer. The device lifetime (95% attenuation) was 1 hour for the organic EL devices in Comparative Examples 5 to 8 having the hole transport layer that was also doped with an electron acceptor, whereas was a long lifetime of 6 to 69 hours for the organic EL devices in Comparative Examples 1 to 4 having the hole transport layer that was not doped with an electron acceptor. The device lifetime was 116 to 143 hours, which showed large increase of lifetime, for the organic EL devices in Examples 52 to 59 using the arylamine compound of the general formula (1) in the hole injection layer.

[0431] It has been found that in the organic EL devices of the present invention, holes can be efficiently injected and transported from the electrode to the hole transport layer by selecting the particular arylamine compound (having the particular structure) as the material of the hole injection layer, and subjecting to p-type doping with an electron acceptor, and the carrier balance in the organic EL device can be improved to achieve an organic EL device having a higher luminous efficiency and a longer lifetime than the conventional organic EL devices by selecting the particular arylamine compound (having the particular structure) without p-type doping as the material of the hole transport layer.

INDUSTRIAL APPLICABILITY

[0432] The organic EL devices of the present invention with the combination of the particular arylamine compound (having the particular structure) and the electron acceptor that achieves excellent carrier balance in the organic EL device has an improved luminous efficiency and an improved durability of the organic EL device, and can be applied, for example, to home electric appliances and illuminations.

DESCRIPTION OF REFERENCE NUMERAL

[0433] 1 Glass substrate [0434] 2 Transparent anode [0435] 3 Hole injection layer [0436] 4 Hole transport layer [0437] 5 Light emitting layer [0438] 6 Electron transport layer [0439] 7 Electron injection layer [0440] 8 Cathode