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.4 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 comprises an arylamine compound represented by the following general formula (1) and an electron acceptor: ##STR00360## (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 a layer adjacent to the light emitting layer does not contain an electron acceptor.

3. The organic electroluminescent device according to claim 1, wherein the electron acceptor is an electron acceptor selected from trisbromophenylaminehexachloroantimony, 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): ##STR00361## (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 comprises only a hole transporting arylamine compound.

6. The organic electroluminescent device according to claim 5, wherein the hole transport layer comprises an arylamine compound represented by the general formula (1).

7. The organic electroluminescent device according to claim 1, wherein the electron transport layer comprises a compound having an anthracene ring structure represented by the following general formula (3): ##STR00362## (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 a substituted or unsubstituted condensed polycyclic aromatic, or a single bond; B.sub.1 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, a cyano group, a trifluoromethyl group, a linear or branched alkyl group 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 while p and q maintain a relationship that the sum of p and q is 9, p represents 7 or 8, and q represents 1 or 2).

8. The organic electroluminescent device according to claim 1, wherein the electron transport layer comprises a compound having a pyrimidine ring structure represented by the following general formula (4): ##STR00363## (wherein Ar.sub.8 represents a substituted or unsubstituted aromatic hydrocarbon 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, or a substituted or unsubstituted condensed polycyclic aromatic group; and E represents a monovalent group represented by the following structural formula (5), provided that Ar.sub.9 and Ar.sub.10 are not simultaneously a hydrogen atom: ##STR00364## (wherein Ar.sub.11 represents a substituted or unsubstituted aromatic heterocyclic group; R.sub.1 to R.sub.4 may be the same or different, and represent a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group 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).

9. The organic electroluminescent device according to claim 1, wherein the electron transport layer comprises a compound having a benzotriazole ring structure represented by the following general formula (6): ##STR00365## (wherein Ar.sub.12 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.13 represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; L.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 a substituted or unsubstituted condensed polycyclic aromatic, or a single bond; L.sub.2 represents a divalent group of a substituted or unsubstituted condensed polycyclic aromatic or a single bond; and B.sub.2 represents a substituted or unsubstituted aromatic heterocyclic group).

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

11. The organic electroluminescent device according to claim 10, wherein the light emitting layer comprises a blue light emitting dopant which is a pyrene derivative.

12. The organic electroluminescent device according to claim 10, wherein the blue light emitting dopant comprises a light emitting dopant which is an amine derivative having a condensed ring structure represented by the following general formula (7): ##STR00366## (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 a substituted or unsubstituted condensed polycyclic aromatic, or a single bond; Ar.sub.14 and Ar.sub.15 may be the same or different, and represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, and may bind to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring; R.sub.5 to R.sub.8 may be the same or different, and represent a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear or branched alkyl group of 1 to 6 carbon atoms that may have a substituent, a cycloalkyl group of 5 to 10 carbon atoms that may have a substituent, a linear or branched alkenyl group of 2 to 6 carbon atoms that may have a substituent, a linear or branched alkyloxy group of 1 to 6 carbon atoms that may have a substituent, a cycloalkyloxy group of 5 to 10 carbon atoms that may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group, or a disubstituted amino group substituted with a group selected from an aromatic hydrocarbon group, an aromatic heterocyclic group, or a condensed polycyclic aromatic group, where the respective groups may bind to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring, or may bind to the benzene ring to which R.sub.5 to R.sub.8 bind via a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or a monosubstituted amino group to form a ring; R.sub.9 to R.sub.11 may be the same or different, and represent a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a linear or branched alkyl group of 1 to 6 carbon atoms that may have a substituent, a cycloalkyl group of 5 to 10 carbon atoms that may have a substituent, a linear or branched alkenyl group of 2 to 6 carbon atoms that may have a substituent, a linear or branched alkyloxy group of 1 to 6 carbon atoms that may have a substituent, a cycloalkyloxy group of 5 to 10 carbon atoms that may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, where the respective groups may bind to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring, or may bind to the benzene ring to which R.sub.9 to R.sub.11 bind via a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or a monosubstituted amino group to form a ring; and R.sub.12 and R.sub.13 may be the same or different, and represent a linear or branched alkyl group of 1 to 6 carbon atoms that may have a substituent, a cycloalkyl group of 5 to 10 carbon atoms that may have a substituent, a linear or branched alkenyl group of 2 to 6 carbon atoms that may have a substituent, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted aryloxy group, where the respective groups may bind to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or a monosubstituted amino group to form a ring).

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

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

15. The organic electroluminescent device according to claim 2, wherein the electron acceptor is an electron acceptor selected from trisbromophenylaminehexachloroantimony, 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): ##STR00367## (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 comprises only a hole transporting arylamine compound.

18. The organic electroluminescent device according to claim 2, wherein the electron transport layer comprises a compound having an anthracene ring structure represented by the following general formula (3): ##STR00368## (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 a substituted or unsubstituted condensed polycyclic aromatic, or a single bond; B.sub.1 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, a cyano group, a trifluoromethyl group, a linear or branched alkyl group 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 while p and q maintain a relationship that the sum of p and q is 9, p represents 7 or 8, and q represents 1 or 2).

19. The organic electroluminescent device according to claim 2, wherein the electron transport layer comprises a compound having a pyrimidine ring structure represented by the following general formula (4): ##STR00369## (wherein Ar.sub.8 represents a substituted or unsubstituted aromatic hydrocarbon 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, or a substituted or unsubstituted condensed polycyclic aromatic group; and E represents a monovalent group represented by the following structural formula (5), provided that Ar.sub.9 and Ar.sub.10 are not simultaneously a hydrogen atom: ##STR00370## (wherein Ar.sub.11 represents a substituted or unsubstituted aromatic heterocyclic group; R.sub.1 to R.sub.4 may be the same or different, and represent a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group 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).

20. The organic electroluminescent device according to claim 2, wherein the electron transport layer comprises a compound having a benzotriazole ring structure represented by the following general formula (6): ##STR00371## (wherein Ar.sub.12 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.13 represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; L.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 a substituted or unsubstituted condensed polycyclic aromatic, or a single bond; L.sub.2 represents a divalent group of a substituted or unsubstituted condensed polycyclic aromatic or a single bond; and B.sub.2 represents a substituted or unsubstituted aromatic heterocyclic group).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0184] FIG. 1 is a diagram illustrating the configuration of the organic EL devices of Examples 61 and 72 and Comparative Examples 1 to 8.

MODE FOR CARRYING OUT THE INVENTION

[0185] 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.

##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094##

[0186] The arylamine compounds described above can be synthesized by a known method (refer to Patent Document 7, for example).

[0187] The following presents specific examples of preferred compounds among the compounds of the general formula (3a) 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.

##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101##

[0188] The following presents specific examples of preferred compounds among the compounds of the general formula (3b) 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.

##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107##

[0189] The following presents specific examples of preferred compounds among the compounds of the general formula (3c) 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.

##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122##

[0190] The compounds having an anthracene ring structure described above can be synthesized by a known method (refer to Patent Documents 8 to 10, for example).

[0191] The following presents specific examples of preferred compounds among the compounds of the general formula (4) 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.

##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## ##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181## ##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186## ##STR00187## ##STR00188## ##STR00189## ##STR00190## ##STR00191## ##STR00192## ##STR00193## ##STR00194## ##STR00195## ##STR00196## ##STR00197## ##STR00198## ##STR00199## ##STR00200## ##STR00201## ##STR00202## ##STR00203## ##STR00204## ##STR00205## ##STR00206## ##STR00207## ##STR00208## ##STR00209## ##STR00210## ##STR00211## ##STR00212## ##STR00213## ##STR00214## ##STR00215## ##STR00216## ##STR00217## ##STR00218## ##STR00219## ##STR00220## ##STR00221## ##STR00222## ##STR00223## ##STR00224## ##STR00225## ##STR00226## ##STR00227## ##STR00228## ##STR00229## ##STR00230## ##STR00231## ##STR00232## ##STR00233## ##STR00234## ##STR00235## ##STR00236## ##STR00237##

[0192] The compounds having a pyrimidine ring structure described above can be synthesized by a known method (refer to Patent Documents 8 and 9, for example).

[0193] 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 benzotriazole ring structure. The present invention, however, is not restricted to these compounds.

##STR00238## ##STR00239## ##STR00240## ##STR00241## ##STR00242## ##STR00243## ##STR00244## ##STR00245## ##STR00246## ##STR00247## ##STR00248## ##STR00249## ##STR00250## ##STR00251## ##STR00252## ##STR00253## ##STR00254## ##STR00255## ##STR00256## ##STR00257## ##STR00258## ##STR00259## ##STR00260## ##STR00261## ##STR00262## ##STR00263## ##STR00264## ##STR00265## ##STR00266## ##STR00267## ##STR00268## ##STR00269## ##STR00270## ##STR00271## ##STR00272## ##STR00273## ##STR00274## ##STR00275## ##STR00276## ##STR00277## ##STR00278## ##STR00279## ##STR00280## ##STR00281## ##STR00282## ##STR00283## ##STR00284## ##STR00285##

[0194] The compounds having a benzotriazole ring structure described above can be synthesized by a known method (refer to Patent Document 11, for example).

[0195] The following presents specific examples of preferred compounds among the amine derivatives of the general formula (7) 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.

##STR00286## ##STR00287## ##STR00288## ##STR00289## ##STR00290## ##STR00291## ##STR00292## ##STR00293## ##STR00294##

[0196] 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.

[0197] 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.

[0198] 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.

[0199] 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.

[0200] 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.

[0201] 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.

[0202] As the hole injection layer of the organic EL device of the present invention, a material obtained by p-doping an arylamine compound represented by the above general formula (1) with an electron acceptor is preferably used.

[0203] As hole-injecting and transporting materials which can be mixed with or used simultaneously with the arylamine compound represented by the above general formula (1), materials such as starburst-type triphenylamine derivatives and various triphenylamine tetramers; porphyrin compounds as represented by copper phthalocyanine; accepting heterocyclic compounds such as hexacyano azatriphenylene and coating-type polymer materials; 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.

[0204] As the hole transport layer of the organic EL device of the present invention, in addition to the arylamine compounds represented by the above general formula (1), benzidine derivatives such as N,N′-diphenyl-N,N′-di(m-tolyl)benzidine (TPD), N,N′-diphenyl-N,N′-di(α-naphthyl)benzidine (NPD), and N,N,N′,N′-tetrabiphenylylbenzidine, arylamine compounds having a structure in which two triphenylamine structures are joined within a molecule via a single bond or a divalent group that does not contain a heteroatom, such as 1,1-bis[4-(di-4-tolylamino)phenyl]cyclohexane (TAPC), arylamine compounds having a structure in which four triphenylamine structures are joined within a molecule via a single bond or a divalent group that does not contain a heteroatom, various triphenylamine trimers, and the like can be used. Further, as the hole injection and transport layers, coating-type polymer materials such as poly(3,4-ethylenedioxythiophene) (PEDOT)/poly(styrene sulfonate) (PSS) can be used.

[0205] As the hole transport layer of the organic EL device of the present invention, hole-transporting arylamine compounds are preferably used, and particularly, the arylamine compounds represented by the above general formula (1) are preferably used. Then, the compounds which are not p-doped are preferably used.

[0206] These may be individually deposited for film forming, but 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 an individually deposited layer and a mixedly deposited layer. These materials may be formed into a thin film by a vapor deposition method or other known methods such as a spin coating method and an inkjet method.

[0207] As the electron blocking layer of the organic EL device of the present invention, the arylamine compounds represented by the above general formula (1) are preferably used, however, in addition thereto, arylamine compounds having a structure in which four triphenylamine structures are joined within a molecule via a single bond or a divalent group that does not contain a heteroatom, arylamine compounds having a structure in which two triphenylamine structures are joined within a molecule via a single bond or a divalent group that does not contain a heteroatom, compounds having an electron blocking effect, including, for example, carbazole derivatives such as 4,4′,4″-tri(N-carbazolyl)triphenylamine (TCTA), 9,9-bis[4-(carbazol-9-yl)phenyl]fluorene, 1,3-bis(carbazol-9-yl)benzene (mCP), and 2,2-bis(4-carbazol-9-ylphenyl)adamantane (Ad-Cz), and compounds having a triphenylsilyl group and a triarylamine structure, as represented by 9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylsilyl)phenyl]-9H-fluorene can be used. These may be individually deposited for film forming, but 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 an individually deposited layer and a 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.

[0208] In the organic EL device of the present invention, it is preferable that layers (for example, the hole transport layer, the electron blocking layer, etc.) adjacent to the light emitting layer are not p-doped with an electron acceptor.

[0209] In these layers, arylamine compounds having high electron blocking performance are preferably used, and the arylamine compounds represented by the above general formula (1) and the like are preferably used.

[0210] Further, the film thickness of these layers is not particularly limited as long as it is a commonly used film thickness, however, as the hole transport layer, a layer having a film thickness of 20 to 100 nm is used, and as the electron blocking layer, a layer having a film thickness of 5 to 30 nm is used.

[0211] 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 (7) having a condensed ring. 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.

[0212] 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.

[0213] 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.

[0214] 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).

[0215] 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.

[0216] 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 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.

[0217] 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 (3) having an anthracene ring structure, and the compounds of the general formula (4) 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.

[0218] 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.

[0219] 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.

[0220] 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 N,N-bis(biphenyl-4-yl)-N-(6-phenylbiphenyl-3-yl)amine (Compound 1-2)

[0221] N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine (11.8 g), toluene (94 mL), phenylboronic acid (2.7 g), and an aqueous solution obtained by previously dissolving potassium carbonate (5.9 g) in water (36 mL) were added into a nitrogen-substituted reaction vessel and aerated with nitrogen gas under ultrasonic irradiation for 30 minutes. Tetrakistriphenylphosphine palladium (0.74 g) was added thereto, and the resulting mixture was heated and stirred at 72° C. for 18 hours. After the mixture was cooled to a room temperature, an organic layer was collected by liquid separation. The organic layer was washed with water, and washed with a saturated salt solution sequentially, and then dried over anhydrous magnesium sulfate and concentrated to obtain a crude product. Subsequently, the crude product was purified using column chromatography, whereby a white powder of N,N-bis(biphenyl-4-yl)-N-(6-phenylbiphenyl-3-yl)amine (Compound 1-2, 8.4 g, yield: 72%) was obtained.

[0222] The structure of the obtained white powder was identified by NMR.

[0223] .sup.1H-NMR (CDCl.sub.3) detected 31 hydrogen signals, as follows.

[0224] δ (ppm)=7.56-7.68 (7H), 7.45-7.52 (4H) 7.14-7.41 (20H)

##STR00295##

Example 2

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

[0225] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 1-naphthylboronic acid, whereby a white powder of N,N-bis(biphenyl-4-yl)-N-{6-(naphthyl-1-yl)biphenyl-3-yl}amine (Compound 1-3, 9.2 g, yield: 61%) was obtained.

[0226] The structure of the obtained white powder was identified by NMR.

[0227] .sup.1H-NMR (CDCl.sub.3) detected 33 hydrogen signals, as follows.

[0228] δ (ppm)=7.84-7.87 (3H), 7.67-83 (6H), 7.26-7.64 (18H) 7.02-7.04 (6H)

##STR00296##

Example 3

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

[0229] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with (9,9-dimethylfluoren-2-yl)boronic acid, whereby a white powder of N,N-bis(biphenyl-4-yl)-N-{6-(9,9-dimethylfluoren-2-yl)biphenyl-3-yl}amine (Compound 1-1, 9.0 g, yield: 57%) was obtained.

[0230] The structure of the obtained white powder was identified by NMR.

[0231] .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

[0232] δ (ppm)=7.56-7.64 (10H), 7.26-50 (18H), 7.02-7.16 (5H), 1.26 (6H)

##STR00297##

Example 4

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

[0233] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-biphenylboronic acid, whereby a white powder of N,N-bis(biphenyl-4-yl)-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-4, 8.6 g, yield: 64%) was obtained.

[0234] The structure of the obtained white powder was identified by NMR.

[0235] .sup.1H-NMR (CDCl.sub.3) detected 35 hydrogen signals, as follows.

[0236] δ (ppm)=7.66-7.53 (8H), 7.51-7.15 (27H)

##STR00298##

Example 5

Synthesis of N,N-bis(biphenyl-4-yl)-N-{6-(1,1′; 4′,1″-terphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-9)

[0237] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-bromo-1,1′; 4′,1″-terphenyl, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N,N-bis(biphenyl-4-yl)-N-{3-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl}amine, whereby a white powder of N,N-bis(biphenyl-4-yl)-N-{6-(1,1′; 4′,1″-terphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-9, 4.5 g, yield: 40%) was obtained.

[0238] The structure of the obtained white powder was identified by NMR.

[0239] .sup.1H-NMR (THF-d.sub.8) detected 39 hydrogen signals, as follows.

[0240] δ (ppm)=7.73-7.58 (15H), 7.46-7.12 (24H)

##STR00299##

Example 6

Synthesis of N,N-bis(biphenyl-4-yl)-N-[6-{4-(naphthalen-1-yl)phenyl)}biphenyl-3-yl]amine (Compound 1-16)

[0241] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-(naphthalen-1-yl)phenylboronic acid, whereby a white powder of N,N-bis(biphenyl-4-yl)-N-[6-{4-(naphthalen-1-yl)phenyl)}biphenyl-3-yl]amine (Compound 1-16, 11.6 g, yield: 77%) was obtained.

[0242] The structure of the obtained white powder was identified by NMR.

[0243] .sup.1H-NMR (CDCl.sub.3) detected 37 hydrogen signals, as follows.

[0244] δ (ppm)=7.95-7.84 (3H), 7.67-7.18 (34H)

##STR00300##

Example 7

Synthesis of N,N-bis(biphenyl-4-yl)-N-[6-(9,9-dimethylfluoren-2-yl)phenyl)}biphenyl-3-yl]amine (Compound 1-20)

[0245] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-(9,9-dimethylfluoren-2-yl)phenylboronic acid, whereby a white powder of N,N-bis(biphenyl-4-yl)-N-[6-(9,9-dimethylfluoren-2-yl)phenyl)}biphenyl-3-yl]amine (Compound 1-20, 13.1 g, yield: 81%) was obtained.

[0246] The structure of the obtained white powder was identified by NMR.

[0247] .sup.1H-NMR (CDCl.sub.3) detected 43 hydrogen signals, as follows.

[0248] δ (ppm)=7.78 (2H), 7.68-7.15 (35H), 1.55 (6H)

##STR00301##

Example 8

Synthesis of N-(biphenyl-4-yl)-N-{6-(biphenyl-4-yl)biphenyl-3-yl}-N-(9,9-dimethylfluoren-2-yl)amine (Compound 1-56)

[0249] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-biphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-(9,9-dimethylfluoren-2-yl)-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(biphenyl-4-yl)-N-{6-(biphenyl-4-yl)biphenyl-3-yl}-N-(9,9-dimethylfluoren-2-yl)amine (Compound 1-56, 17.8 g, yield: 89%) was obtained.

[0250] The structure of the obtained white powder was identified by NMR.

[0251] .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

[0252] δ (ppm)=7.72-7.57 (7H), 7.52-7.33 (9H), 7.32-7.19 (17H), 1.45 (6H)

##STR00302##

Example 9

Synthesis of N,N-bis(9,9-dimethylfluoren-2-yl)-N-(6-phenylbiphenyl-3-yl)-amine (Compound 1-62)

[0253] The reaction was carried out under the same conditions as those of Example 1, except that N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl) amine was replaced with N,N-bis(9,9-dimethylfluoren-2-yl)-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N,N-bis(9,9-dimethylfluoren-2-yl)-N-(6-phenylbiphenyl-3-yl)amine (Compound 1-62, 11.5 g, yield: 57%) was obtained.

[0254] The structure of the obtained white powder was identified by NMR.

[0255] .sup.1H-NMR (THF-d.sub.8) detected 39 hydrogen signals, as follows.

[0256] δ (ppm)=7.70-7.63 (3H), 7.44-7.02 (24H), 1.46 (12H)

##STR00303##

Example 10

Synthesis of N,N-bis(6-phenylbiphenyl-3-yl)-N-(biphenyl-4-yl)amine (Compound 1-108)

[0257] The reaction was carried out under the same conditions as those of Example 1, except that N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N,N-bis(6-bromobiphenyl-3-yl)-N-(biphenyl-4-yl)amine, whereby a white powder of N,N-bis(6-phenylbiphenyl-3-yl)-N-(biphenyl-4-yl)amine (Compound 1-108, 10.2 g, yield: 73%) was obtained.

[0258] The structure of the obtained white powder was identified by NMR.

[0259] .sup.1H-NMR (CDCl.sub.3) detected 35 hydrogen signals, as follows.

[0260] δ (ppm)=7.57-7.66 (4H), 7.10-7.49 (31H)

##STR00304##

Example 11

Synthesis of N,N,N-tris(6-phenylbiphenyl-3-yl)amine (Compound 1-143)

[0261] The reaction was carried out under the same conditions as those of Example 1, except that N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N,N,N-tris(6-bromobiphenyl-3-yl)amine, whereby a white powder of N,N,N-tris(6-phenylbiphenyl-3-yl)amine (Compound 1-143, 11.1 g, yield: 75%) was obtained.

[0262] The structure of the obtained white powder was identified by NMR.

[0263] .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

[0264] δ (ppm)=7.35-7.42 (6H), 7.15-7.35 (33H)

##STR00305##

Example 12

Synthesis of N-(biphenyl-4-yl)-N-(6-phenylbiphenyl-3-yl)-N-(9,9-dimethylfluoren-2-yl)amine (Compound 1-50)

[0265] The reaction was carried out under the same conditions as those of Example 1, except that N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-(9,9-dimethylfluoren-2-yl)-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(biphenyl-4-yl)-N-(6-phenylbiphenyl-3-yl)-N-(9,9-dimethylfluoren-2-yl)amine (Compound 1-50, 13.6 g, yield: 76%) was obtained.

[0266] The structure of the obtained white powder was identified by NMR.

[0267] .sup.1H-NMR (CDCl.sub.3) detected 35 hydrogen signals, as follows.

[0268] δ (ppm)=7.72-7.61 (4H), 7.58 (2H), 7.50-7.09 (29H)

##STR00306##

Example 13

Synthesis of N-(9,9-dimethylfluoren-2-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-(6-phenylbiphenyl-3-yl)amine (Compound 1-63)

[0269] The reaction was carried out under the same conditions as those of Example 1, except that N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(6-bromobiphenyl-3-yl)-N-(9,9-dimethylfluoren-2-yl)-N-{4-(naphthalen-1-yl)phenyl}amine, whereby a light yellowish white powder of N-(9,9-dimethylfluoren-2-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-(6-phenylbiphenyl-3-yl)amine (Compound 1-63, 12.2, g, yield: 56%) was obtained.

[0270] The structure of the obtained light yellowish white powder was identified by NMR.

[0271] .sup.1H-NMR (CDCl.sub.3) detected 37 hydrogen signals, as follows.

[0272] δ (ppm)=8.10 (1H), 7.95 (1H), 7.88 (1H), 7.72-7.65 (2H), 7.60-7.10 (26H), 1.50 (6H)

##STR00307##

Example 14

Synthesis of N-(9,9-dimethylfluoren-2-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-{6-phenylbiphenyl-3-yl}amine (Compound 1-64)

[0273] The reaction was carried out under the same conditions as those of Example 1, except that N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(6-bromobiphenyl-3-yl)-N-(9,9-dimethylfluoren-2-yl)-N-{4-(naphthalen-2-yl)phenyl}amine, whereby a light yellowish white powder of N-(9,9-dimethylfluoren-2-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-(6-phenylbiphenyl-3-yl)amine (Compound 1-64, 8.8 g, yield: 63%) was obtained.

[0274] The structure of the obtained light yellowish white powder was identified by NMR.

[0275] .sup.1H-NMR (CDCl.sub.3) detected 37 hydrogen signals, as follows.

[0276] δ (ppm)=8.08 (1H), 7.76-7.94 (4H), 7.60-7.71 (4H), 7.13-7.54 (22H), 1.52 (6H)

##STR00308##

Example 15

Synthesis of N-(biphenyl-4-yl)-N-(9,9-dimethylfluoren-2-yl)-N-{6-(4-naphthalen-1-yl-phenyl)biphenyl-3-yl}amine (Compound 1-65)

[0277] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-(naphthalen-1-yl)phenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-(9,9-dimethylfluoren-2-yl)-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(biphenyl-4-yl)-N-(9,9-dimethylfluoren-2-yl)-N-{6-(4-naphthalen-1-yl-phenyl)biphenyl-3-yl}amine (Compound 1-143, 49.8 g, yield: 84%) was obtained.

[0278] The structure of the obtained white powder was identified by NMR.

[0279] .sup.1H-NMR (CDCl.sub.3) detected 41 hydrogen signals, as follows.

[0280] δ (ppm)=7.92 (2H), 7.88 (1H), 7.72-7.18 (38H)

##STR00309##

Example 16

Synthesis of N-(biphenyl-4-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-{6-(biphenyl-4-yl)biphenyl-3-yl)}amine (Compound 1-147)

[0281] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-biphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)-N-{4-(naphthalen-1-yl)phenyl}amine, whereby a white powder of N-(biphenyl-4-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-{6-(biphenyl-4-yl)biphenyl-3-yl)}amine (Compound 1-147, 7.5 g, yield: 48%) was obtained.

[0282] The structure of the obtained white powder was identified by NMR.

[0283] .sup.1H-NMR (CDCl.sub.3) detected 37 hydrogen signals, as follows.

[0284] δ (ppm)=8.08 (1H), 7.95 (1H), 7.88 (1H), 7.68-7.18 (34H)

##STR00310##

Example 17

Synthesis of N-(biphenyl-4-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-[6-{4-(naphthalen-1-yl)phenyl}biphenyl-3-yl]amine (Compound 1-148)

[0285] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-(naphthalen-1-yl)phenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-(6-bromobiphenyl-3-yl)amine, whereby a light yellowish white powder of N-(biphenyl-4-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-[6-{4-(naphthalen-1-yl)phenyl}biphenyl-3-yl]amine (Compound 1-148, 8.4 g, yield: 60%) was obtained.

[0286] The structure of the obtained light yellowish white powder was identified by NMR.

[0287] .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

[0288] δ (ppm)=8.09 (1H), 7.98-7.84 (5H), 7.69-7.20 (33H)

##STR00311##

Example 18

Synthesis of N-(biphenyl-4-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-{6-(p-terphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-150)

[0289] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-(p-terphenyl)boronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-(6-bromobiphenyl-3-yl)amine, whereby a light yellowish white powder of N-(biphenyl-4-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-{6-(p-terphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-150, 6.3 g, yield: 47%) was obtained.

[0290] The structure of the obtained light yellowish white powder was identified by NMR.

[0291] .sup.1H-NMR (CDCl.sub.3) detected 41 hydrogen signals, as follows.

[0292] δ (ppm)=8.12 (1H), 7.98-7.83 (2H), 7.72-7.15 (38H)

##STR00312##

Example 19

Synthesis of N,N-bis(biphenyl-4-yl)-N-[4-phenyl-3-{4-(naphthalen-1-yl)phenyl}phenyl]amine (Compound 1-152)

[0293] 4-Bromobiphenyl (13.5 g), 2-{4-(naphthalen-1-yl)phenyl)}-4-aminobiphenyl (9.0 g), palladium acetate (0.11 g), a toluene solution (50%) containing tri-tert-butylphosphine (0.15 g), and toluene (90 mL) were added into a nitrogen-substituted reaction vessel, and the mixture was heated and stirred at 100° C. for 24 hours. After insoluble matter was removed by filtration, concentration was carried out to obtain a crude product. Subsequently, the crude product was purified using column chromatography, whereby a yellowish white powder of N,N-bis(biphenyl-4-yl)-N-[4-phenyl-3-{4-(naphthalen-1-yl)phenyl}phenyl]amine (Compound 1-152, 5.4 g, yield: 33%) was obtained.

[0294] The structure of the obtained yellowish white powder was identified by NMR.

[0295] .sup.1H-NMR (CDCl.sub.3) detected 37 hydrogen signals, as follows.

[0296] δ (ppm)=7.94-7.76 (3H), 7.68-7.15 (34H)

##STR00313##

Example 20

Synthesis of N,N-bis(9,9-dimethylfluoren-2-yl)-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-153)

[0297] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-biphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N,N-bis(9,9-dimethylfluoren-2-yl)-N-(6-bromobiphenyl-3-yl)amine, whereby a light yellowish white powder of N,N-bis(9,9-dimethylfluoren-2-yl)-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-153, 16.7 g, yield: 92%) was obtained.

[0298] The structure of the obtained light yellowish white powder was identified by NMR.

[0299] .sup.1H-NMR (CDCl.sub.3) detected 43 hydrogen signals, as follows.

[0300] δ (ppm)=7.80-7.59 (6H), 7.51-7.12 (25H), 1.51 (12H)

##STR00314##

Example 21

Synthesis of N,N-bis{4-(naphthalen-1-yl)phenyl}-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-155)

[0301] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-biphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N,N-bis{4-(naphthalen-1-yl)phenyl}-N-(6-bromobiphenyl-3-yl)amine, whereby a light yellowish white powder of N,N-bis{4-(naphthalen-1-yl)phenyl}-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-155, 10.6 g, yield: 79%) was obtained.

[0302] The structure of the obtained light yellowish white powder was identified by NMR.

[0303] .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

[0304] δ (ppm)=8.08-8.14 (2H), 7.88-7.96 (4H), 7.24-7.64 (33H)

##STR00315##

Example 22

Synthesis of N,N-bis{4-(naphthalen-1-yl)phenyl}-N-[6-{4-(naphthalen-1-yl)phenyl}biphenyl-3-yl]amine (Compound 1-156)

[0305] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-(naphthalen-1-yl)phenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N,N-bis{4-(naphthalen-1-yl)phenyl}-N-(6-bromobiphenyl-3-yl)amine, whereby a light yellowish white powder of N,N-bis{4-(naphthalen-1-yl)phenyl}-N-[6-{4-(naphthalen-1-yl)phenyl}biphenyl-3-yl]amine (Compound 1-156, 10.6 g, yield: 79%) was obtained.

[0306] The structure of the obtained light yellowish white powder was identified by NMR.

[0307] .sup.1H-NMR (CDCl.sub.3) detected 41 hydrogen signals, as follows.

[0308] δ (ppm)=8.14 (2H), 7.99-7.72 (6H), 7.61-7.10 (33H)

##STR00316##

Example 23

Synthesis of N,N-bis{4-(naphthalen-1-yl)phenyl}-N-[6-{4-(naphthalen-2-yl)phenyl}biphenyl-3-yl]amine (Compound 1-157)

[0309] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-(naphthalen-2-yl)phenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N,N-bis{4-(naphthalen-1-yl)phenyl}-N-(6-bromobiphenyl-3-yl)amine, whereby a light yellowish white powder of N,N-bis{4-(naphthalen-1-yl)phenyl}-N-[6-{4-(naphthalen-2-yl)phenyl}biphenyl-3-yl]amine (Compound 1-157, 9.7 g, yield: 74%) was obtained.

[0310] The structure of the obtained light yellowish white powder was identified by NMR.

[0311] .sup.1H-NMR (CDCl.sub.3) detected 41 hydrogen signals, as follows.

[0312] δ (ppm)=8.08-8.14 (3H), 7.66-7.97 (8H), 7.28-7.66 (30H)

##STR00317##

Example 24

Synthesis of N,N-bis{4-(naphthalen-1-yl)phenyl}-N-{6-(p-terphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-158)

[0313] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-(p-terphenyl)boronic acid pinacol ester, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N,N-bis{4-(naphthalen-1-yl)phenyl}-N-(6-bromobiphenyl-3-yl)amine, whereby a light yellowish white powder of N,N-bis{4-(naphthalen-1-yl)phenyl}-N-{6-(p-terphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-158, 6.2 g, yield: 63%) was obtained.

[0314] The structure of the obtained light yellowish white powder was identified by NMR.

[0315] .sup.1H-NMR (CDCl.sub.3) detected 43 hydrogen signals, as follows.

[0316] δ (ppm)=8.08-8.14 (3H), 7.89-7.95 (4H), 7.25-7.71 (36H)

##STR00318##

Example 25

Synthesis of N,N-bis{4-(naphthalen-1-yl)phenyl}-N-{6-(biphenyl-2-yl)biphenyl-3-yl}amine (Compound 1-159)

[0317] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 2-biphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with bis{4-(naphthalen-1-yl)phenyl}-N-(6-bromobiphenyl-3-yl)amine, whereby a light yellowish white powder of N,N-bis{4-(naphthalen-1-yl)phenyl}-N-{6-(biphenyl-2-yl)biphenyl-3-yl}amine (Compound 1-159, 4.9 g, yield: 48%) was obtained.

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

[0319] .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

[0320] δ (ppm)=8.08-8.12 (2H), 7.86-7.94 (4H), 7.00-7.57 (29H), 6.63-6.75 (4H)

##STR00319##

Example 26

Synthesis of N-(biphenyl-4-yl)-N-{4-(9,9-dimethylfluoren-2-yl)phenyl}-N-(6-phenylbiphenyl-3-yl)amine (Compound 1-160)

[0321] The reaction was carried out under the same conditions as those of Example 1, except that N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-{4-(9,9-dimethylfluoren-2-yl)phenyl}-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(biphenyl-4-yl)-N-{4-(9,9-dimethylfluoren-2-yl)phenyl}-N-(6-phenylbiphenyl-3-yl)amine (Compound 1-160, 8.3 g, yield: 48%) was obtained.

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

[0323] .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

[0324] δ (ppm)=7.79 (2H), 7.69-7.52 (7H), 7.50-7.41 (3H), 7.40-7.10 (21H), 1.57 (6H)

##STR00320##

Example 27

Synthesis of N-(biphenyl-4-yl)-N-{4-(9,9-dimethylfluoren-2-yl)phenyl}-N-{6-(biphenyl-3-yl)biphenyl-3-yl}amine (Compound 1-162)

[0325] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 3-biphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-{4-(9,9-dimethylfluoren-2-yl)phenyl}-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(biphenyl-4-yl)-N-{4-(9,9-dimethylfluoren-2-yl)phenyl}-N-{6-(biphenyl-3-yl)biphenyl-3-yl}amine (Compound 1-162, 8.7 g, yield: 49%) was obtained.

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

[0327] .sup.1H-NMR (CDCl.sub.3) detected 43 hydrogen signals, as follows.

[0328] δ (ppm)=7.78 (2H), 7.65-7.46 (6H), 7.45-7.05 (29H), 1.54 (6H)

##STR00321##

Example 28

Synthesis of N-(biphenyl-4-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-163)

[0329] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-biphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(biphenyl-4-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-163, 4.9 g, yield: 44%) was obtained.

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

[0331] .sup.1H-NMR (CDCl.sub.3) detected 37 hydrogen signals, as follows.

[0332] δ (ppm)=7.73 (1H), 7.61-7.70 (3H), 7.54-7.58 (1H), 7.19-7.52 (32H)

##STR00322##

Example 29

Synthesis of N-(biphenyl-4-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-[6-{4-(naphthalen-1-yl)phenyl}biphenyl-3-yl]amine (Compound 1-164)

[0333] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-(naphthalen-1-yl)phenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(biphenyl-4-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-[6-{4-(naphthalen-1-yl)phenyl}biphenyl-3-yl]amine (Compound 1-164, 9.2 g, yield: 74%) was obtained.

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

[0335] .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

[0336] δ (ppm)=8.10 (1H), 7.89-7.10 (38H)

##STR00323##

Example 30

<Synthesis of N-(biphenyl-4-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-[6-{4-(naphthalen-2-yl)phenyl}biphenyl-3-yl]amine (Compound 1-165)>

[0337] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-naphthalen-2-ylphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(biphenyl-4-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-[6-{4-(naphthalen-2-yl)phenyl}biphenyl-3-yl]amine (Compound 1-165, 9.8 g, yield: 70%) was obtained.

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

[0339] .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

[0340] δ (ppm)=8.07 (2H), 7.99-7.85 (6H), 7.84-7.40 (15H), 7.39-7.12 (16H)

##STR00324##

Example 31

Synthesis of N-(biphenyl-4-yl)-N-(9,9-diphenylfluoren-2-yl)-N-(6-phenylbiphenyl-3-yl)amine (Compound 1-166)

[0341] The reaction was carried out under the same conditions as those of Example 1, except that N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-(9,9-diphenylfluoren-2-yl)-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(biphenyl-4-yl)-N-(9,9-diphenylfluoren-2-yl)-N-(6-phenylbiphenyl-3-yl)amine (Compound 1-166, 11.0 g, yield: 61%) was obtained.

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

[0343] .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

[0344] δ (ppm)=7.60-7.74 (4H), 7.14-7.52 (33H), 7.00-7.03 (2H)

##STR00325##

Example 32

Synthesis of N-(p-terphenyl-4-yl)-N-(9,9-dimethylfluoren-2-yl)-N-(6-phenylbiphenyl-3-yl)amine (Compound 1-167)

[0345] The reaction was carried out under the same conditions as those of Example 1, except that N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(p-terphenyl-4-yl)-N-(9,9-dimethylfluoren-2-yl)-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(p-terphenyl-4-yl)-N-(9,9-dimethylfluoren-2-yl)-N-(6-phenylbiphenyl-3-yl)amine (Compound 1-167, 18.3 g, yield: 74%) was obtained.

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

[0347] .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

[0348] δ (ppm)=7.72-7.57 (6H), 7.51-7.11 (27H), 1.53 (6H)

##STR00326##

Example 33

Synthesis of N-(9,9-dimethylfluoren-2-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-169)

[0349] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-biphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(9,9-dimethylfluoren-2-yl)-N-{(4-naphthalen-2-yl)phenyl}-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(9,9-dimethylfluoren-2-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-169, 10.4 g, yield: 67%) was obtained.

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

[0351] .sup.1H-NMR (CDCl.sub.3) detected 41 hydrogen signals, as follows.

[0352] δ (ppm)=8.12 (1H), 7.78-7.92 (4H), 7.60-7.71 (6H), 7.21-7.54 (24H), 1.53 (6H)

##STR00327##

Example 34

Synthesis of N-(biphenyl-4-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-{2-(biphenyl-4-yl)biphenyl-4-yl}amine (Compound 1-170)

[0353] The reaction was carried out under the same conditions as those of Example 1, except that N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-{2-(biphenyl-4-yl)-bromobenzen-4-yl}amine, whereby a white powder of N-(biphenyl-4-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-{2-(biphenyl-4-yl)biphenyl-4-yl}amine (Compound 1-170, 10.4 g, yield: 67%) was obtained.

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

[0355] .sup.1H-NMR (CDCl.sub.3) detected 37 hydrogen signals, as follows.

[0356] δ (ppm)=8.08 (1H), 7.81-7.96 (3H), 7.79-7.81 (1H), 7.21-7.73 (32H)

##STR00328##

Example 35

Synthesis of N-(biphenyl-4-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-[2-{4-(naphthalen-2-yl)phenyl}biphenyl-4-yl]amine (Compound 1-171)

[0357] The reaction was carried out under the same conditions as those of Example 1, except that N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-[2-{4-(naphthalen-2-yl)phenyl}-(bromobiphenyl-4-yl)]amine, whereby a white powder of N-(biphenyl-4-yl)-N-{4-(naphthalen-2-yl)phenyl}-N-[2-{4-(naphthalen-2-yl)phenyl}biphenyl-4-yl]amine (Compound 1-171, 10.0 g, yield: 81%) was obtained.

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

[0359] .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

[0360] δ (ppm)=8.04-8.10 (2H), 7.78-7.96 (8H), 7.24-7.65 (29H)

##STR00329##

Example 36

Synthesis of N-(biphenyl-4-yl)-N-(9,9-diphenylfluoren-2-yl)-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-174)

[0361] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-biphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-(9,9-diphenylfluoren-2-yl)-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(biphenyl-4-yl)-N-(9,9-diphenylfluoren-2-yl)-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-174, 6.5 g, yield: 71%) was obtained.

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

[0363] .sup.1H-NMR (CDCl.sub.3) detected 43 hydrogen signals, as follows.

[0364] δ (ppm)=7.61-7.77 (6H), 7.20-7.51 (34H), 7.06-7.11 (3H)

##STR00330##

Example 37

Synthesis of N-(biphenyl-4-yl)-N-(9,9-diphenylfluoren-2-yl)-N-{6-(biphenyl-3-yl)biphenyl-3-yl}amine (Compound 1-175)

[0365] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 3-biphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-(9,9-diphenylfluoren-2-yl)-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(biphenyl-4-yl)-N-(9,9-diphenylfluoren-2-yl)-N-{6-(biphenyl-3-yl)biphenyl-3-yl}amine (Compound 1-175, 8.0 g, yield: 87%) was obtained.

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

[0367] .sup.1H-NMR (CDCl.sub.3) detected 43 hydrogen signals, as follows.

[0368] δ (ppm)=7.70-7.76 (2H), 7.63-7.65 (2H), 7.18-7.54 (36H), 7.08-7.12 (3H)

##STR00331##

Example 38

Synthesis of N,N-bis(9,9-dimethylfluoren-2-yl)-N-{6-(biphenyl-3-yl)biphenyl-3-yl}amine (Compound 1-176)

[0369] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 3-biphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N,N-bis(9,9-dimethylfluoren-2-yl)-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N,N-bis(9,9-dimethylfluoren-2-yl)-N-{6-(biphenyl-3-yl)biphenyl-3-yl}amine (Compound 1-176, 17.0 g, yield: 85%) was obtained.

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

[0371] .sup.1H-NMR (CDCl.sub.3) detected 43 hydrogen signals, as follows.

[0372] δ (ppm)=7.30-7.62 (4H), 7.48-7.14 (27H), 1.50 (12H)

##STR00332##

Example 39

Synthesis of N,N-bis(biphenyl-4-yl)-N-{6-(biphenyl-2-yl)-p-terphenyl-3-yl}amine (Compound 1-179)

[0373] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 2-biphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N,N-bis(biphenyl-4-yl)-N-(6-bromo-p-terphenyl-3-yl)amine, whereby a white powder of N,N-bis(biphenyl-4-yl)-N-{6-(biphenyl-2-yl)-p-terphenyl-3-yl}amine (Compound 1-179, 9.6 g, yield: 86%) was obtained.

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

[0375] .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

[0376] δ (ppm)=7.54-7.66 (10H), 7.08-7.49 (25H), 6.63-6.74 (4H)

##STR00333##

Example 40

Synthesis of N-(biphenyl-4-yl)-N-(9,9-diphenylfluoren-2-yl)-N-{6-(biphenyl-2-yl)biphenyl-3-yl}amine (Compound 1-180)

[0377] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 2-biphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-(9,9-diphenylfluoren-2-yl)-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(biphenyl-4-yl)-N-(9,9-diphenylfluoren-2-yl)-N-{6-(biphenyl-2-yl)biphenyl-3-yl}amine (Compound 1-180, 5.2 g, yield: 57%) was obtained.

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

[0379] .sup.1H-NMR (CDCl.sub.3) detected 43 hydrogen signals, as follows.

[0380] δ (ppm)=7.60-7.74 (4H), 6.95-7.49 (35H), 6.68-6.71 (2H), 6.54-6.57 (2H)

##STR00334##

Example 41

Synthesis of N-(9,9-dimethylfluoren-2-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-183)

[0381] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-biphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(9,9-dimethylfluoren-2-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(9,9-dimethylfluoren-2-yl)-N-{4-(naphthalen-1-yl)phenyl}-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-183, 19.9 g, yield: 89%) was obtained.

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

[0383] .sup.1H-NMR (CDCl.sub.3) detected 41 hydrogen signals, as follows.

[0384] δ (ppm)=8.10 (1H), 7.93 (1H), 7.88 (1H), 7.71 (2H), 7.65-7.15 (30H), 1.53 (6H)

##STR00335##

Example 42

Synthesis of N-(9,9-diphenylfluoren-2-yl)-N-{6-(biphenyl-4-yl)biphenyl-3-yl}aniline (Compound 1-217)

[0385] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-biphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(9,9-diphenylfluoren-2-yl)-N-(6-bromobiphenyl-3-yl)aniline, whereby a white powder of N-(9,9-diphenylfluoren-2-yl)-N-{6-(biphenyl-4-yl)biphenyl-3-yl}aniline (Compound 1-217, 4.2 g, yield: 37%) was obtained.

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

[0387] .sup.1H-NMR (CDCl.sub.3) detected 39 hydrogen signals, as follows.

[0388] δ (ppm)=7.76-7.62 (4H), 7.44-7.03 (35H)

##STR00336##

Example 43

Synthesis of N,N-bis{4-(naphthalen-2-yl)phenyl}-N-[6-{4-(naphthalen-1-yl)phenyl}biphenyl-3-yl]amine (Compound 1-185)

[0389] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-(naphthalen-1-yl)phenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N,N-bis{4-(naphthalen-2-yl)phenyl}-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N,N-bis{4-(naphthalen-2-yl)phenyl}-N-[6-{4-(naphthalen-1-yl)phenyl}biphenyl-3-yl]amine (Compound 1-185, 6.5 g, yield: 73%) was obtained.

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

[0391] .sup.1H-NMR (CDCl.sub.3) detected 41 hydrogen signals, as follows.

[0392] δ (ppm)=8.11 (2H), 7.98-7.68 (18H), 7.59-7.23 (21H)

##STR00337##

Example 44

Synthesis of N-(biphenyl-4-yl)-N-(phenanthren-9-yl)-N-(6-phenylbiphenyl-3-yl)amine (Compound 1-187)

[0393] The reaction was carried out under the same conditions as those of Example 1, except that N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-(phenanthren-9-yl)-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(biphenyl-4-yl)-N-(phenanthren-9-yl)-N-(6-phenylbiphenyl-3-yl)amine (Compound 1-187, 3.5 g, yield: 22%) was obtained.

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

[0395] .sup.1H-NMR (CDCl.sub.3) detected 31 hydrogen signals, as follows.

[0396] δ (ppm)=8.81-8.70 (2H), 8.17 (1H), 7.83 (1H), 7.78 (1H), 7.74-7.72 (26H)

##STR00338##

Example 45

Synthesis of N-(biphenyl-4-yl)-N-(phenanthren-9-yl)-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-188)

[0397] The reaction was carried out under the same conditions as those of Example 1, except that phenylboronic acid was replaced with 4-biphenylboronic acid, and N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-(phenanthren-9-yl)-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(biphenyl-4-yl)-N-(phenanthren-9-yl)-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-188, 13.0 g, yield: 77%) was obtained.

[0398] The structure of the obtained white powder was identified by NMR.

[0399] .sup.1H-NMR (CDCl.sub.3) detected 35 hydrogen signals, as follows.

[0400] δ (ppm)=8.82-8.73 (2H), 8.17 (1H), 7.85 (1H), 7.78 (1H), 7.75-7.09 (30H)

##STR00339##

Example 46

Synthesis of N-(biphenyl-4-yl)-N-(9-phenylcarbazol-2-yl)-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-189)

[0401] The reaction was carried out under the same conditions as those of Example 19, except that 4-bromobiphenyl was replaced with 2-bromo-9-phenylcarbazole, and 2-{4-(naphthalen-1-yl)phenyl)}-4-aminobiphenyl was replaced with N-(biphenyl-4-yl)-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine, whereby a white powder of N-(biphenyl-4-yl)-N-(9-phenylcarbazol-2-yl)-N-{6-(biphenyl-4-yl)biphenyl-3-yl}amine (Compound 1-189, 18.0 g, yield: 85%) was obtained.

[0402] The structure of the obtained white powder was identified by NMR.

[0403] .sup.1H-NMR (CDCl.sub.3) detected 38 hydrogen signals, as follows.

[0404] δ (ppm)=8.13-8.06 (2H), 7.65-7.59 (4H), 7.57-7.50 (6H), 7.49-7.10 (26H)

##STR00340##

Example 47

Synthesis of N-(biphenyl-4-yl)-N-(9,9′-spirobi[9H-fluoren]-2-yl)-N-(6-phenylbiphenyl-3-yl)amine (Compound 1-190)

[0405] The reaction was carried out under the same conditions as those of Example 1, except that N,N-bis(biphenyl-4-yl)-N-(6-bromobiphenyl-3-yl)amine was replaced with N-(biphenyl-4-yl)-N-(9,9′-spirobi[9H-fluoren]-2-yl)-N-(6-bromobiphenyl-3-yl)amine, whereby a white powder of N-(biphenyl-4-yl)-N-(9,9′-spirobi[9H-fluoren]-2-yl)-N-(6-phenylbiphenyl-3-yl)amine (Compound 1-190, 6.0 g, yield: 52%) was obtained.

[0406] The structure of the obtained white powder was identified by NMR.

[0407] .sup.1H-NMR (CDCl.sub.3) detected 37 hydrogen signals, as follows.

[0408] δ (ppm)=7.85-7.72 (4H), 7.57 (2H), 7.49-7.29 (8H), 7.23-6.95 (17H), 6.88-6.82 (4H), 6.80-6.66 (2H)

##STR00341##

Example 48

[0409] 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 2 242° C. 103° C. Compound of Example 3 No melting point observed 115° C. Compound of Example 4 No melting point observed 104° C. Compound of Example 5 No melting point observed 117° C. Compound of Example 6 No melting point observed 107° C. Compound of Example 7 240° C. 127° C. Compound of Example 8 No melting point observed 116° C. Compound of Example 9 No melting point observed 119° C. Compound of Example 10 No melting point observed 101° C. Compound of Example 11 No melting point observed 112° C. Compound of Example 12 No melting point observed 102° C. Compound of Example 13 No melting point observed 109° C. Compound of Example 14 237° C. 108° C. Compound of Example 15 No melting point observed 119° C. Compound of Example 16 No melting point observed 109° C. Compound of Example 17 No melting point observed 113° C. Compound of Example 18 No melting point observed 121° C. Compound of Example 19 No melting point observed 111° C. Compound of Example 20 246° C. 132° C. Compound of Example 21 No melting point observed 117° C. Compound of Example 22 No melting point observed 119° C. Compound of Example 23 245° C. 120° C. Compound of Example 24 240° C. 125° C. Compound of Example 25 No melting point observed 107° C. Compound of Example 26 244° C. 113° C. Compound of Example 27 No melting point observed 112° C. Compound of Example 28 No melting point observed 110° C. Compound of Example 29 No melting point observed 112° C. Compound of Example 30 No melting point observed 115° C. Compound of Example 31 No melting point observed 125° C. Compound of Example 32 No melting point observed 114° C. Compound of Example 33 No melting point observed 122° C. Compound of Example 34 No melting point observed 111° C. Compound of Example 35 No melting point observed 119° C. Compound of Example 36 No melting point observed 137° C. Compound of Example 37 No melting point observed 125° C. Compound of Example 38 233° C. 120° C. Compound of Example 39 232° C. 110° C. Compound of Example 40 No melting point observed 126° C. Compound of Example 41 No melting point observed 122° C. Compound of Example 42 No melting point observed 125° C. Compound of Example 43 No melting point observed 116° C. Compound of Example 44 No melting point observed 115° C. Compound of Example 45 No melting point observed 129° C. Compound of Example 46 No melting point observed 121° C. Compound of Example 47 No melting point observed 129° C.

[0410] 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 49

[0411] 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 5.68 eV Compound of Example 2 5.72 eV Compound of Example 3 5.66 eV Compound of Example 4 5.67 eV Compound of Example 5 5.70 eV Compound of Example 6 5.71 eV Compound of Example 7 5.66 eV Compound of Example 8 5.62 eV Compound of Example 9 5.55 eV Compound of Example 10 5.72 eV Compound of Example 11 5.75 eV Compound of Example 12 5.62 eV Compound of Example 13 5.62 eV Compound of Example 14 5.62 eV Compound of Example 15 5.63 eV Compound of Example 16 5.73 eV Compound of Example 17 5.69 eV Compound of Example 18 5.71 eV Compound of Example 19 5.72 eV Compound of Example 20 5.55 eV Compound of Example 21 5.72 eV Compound of Example 22 5.73 eV Compound of Example 23 5.72 eV Compound of Example 24 5.73 eV Compound of Example 25 5.73 eV Compound of Example 26 5.63 eV Compound of Example 27 5.64 eV Compound of Example 28 5.69 eV Compound of Example 29 5.69 eV Compound of Example 30 5.67 eV Compound of Example 31 5.66 eV Compound of Example 32 5.61 eV Compound of Example 33 5.62 eV Compound of Example 34 5.70 eV Compound of Example 35 5.71 eV Compound of Example 36 5.67 eV Compound of Example 37 5.68 eV Compound of Example 38 5.58 eV Compound of Example 39 5.72 eV Compound of Example 40 5.64 eV Compound of Example 41 5.63 eV Compound of Example 42 5.71 eV Compound of Example 43 5.68 eV Compound of Example 44 5.76 eV Compound of Example 45 5.74 eV Compound of Example 46 5.60 eV Compound of Example 47 5.64 eV

[0412] 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 50

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

[0413] 5′,9′-dibromospiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran) (5.0 g), bis{4-(tert-butyl)phenyl}amine (6.0 g), palladium acetate (0.08 g), sodium tert-butoxide (3.4 g), tri-tert-butylphosphine (0.07 g), and toluene (60 mL) were added into a nitrogen-substituted reaction vessel and the mixture was heated and stirred for 2 hours under reflux. The mixture was cooled to a room temperature, dichloromethane and water were added, and an organic layer was collected by liquid separation. After the organic layer was concentrated, purification by column chromatography was performed to obtain a powder of N5′,N5′,N9′,N9′-tetrakis{4-(tert-butyl)phenyl}spiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran)-5′,9′-diamine (Compound 7-1; 3.1 g; yield 36%)

##STR00342##

Example 51

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 7-2)

[0414] The reaction was carried out under the same conditions as those of Example 50, except that 5′,9′-dibromospiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran) was replaced with 2,7-dibromospiro(dibenzo[5,6:7,8]fluoreno[4,3-b]benzofuran-5,9′-fluorene). As a result, a powder of N2,N2,N7,N7-tetrakis{4-(tert-butyl)phenyl}spiro(dibenzo[5,6:7,8]fluoreno[4,3-b]benzofuran-5,9′-fluorene)-2,7-diamine (Compound 7-2; 2.5 g; yield 31%) was obtained.

##STR00343##

Example 52

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 7-3)

[0415] The reaction was carried out under the same conditions as those of Example 50, except that 5′,9′-dibromospiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran) was replaced with 5,9-dibromospiro(benzo[5,6]fluoreno[4,3-b]benzofuran-7,9′-fluorene). As a result, a powder of N5,N5,N9,N9-tetrakis{4-(tert-butyl)phenyl}spiro(benzo[5,6]fluoreno[4,3-b]benzofuran-7,9′-fluorene)-5,9-diamine (Compound 7-3; 3.0 g; yield 36%) was obtained.

##STR00344##

Example 53

Synthesis of N6′,N6′,N10′,N10′-tetrakis{4-(tert-butyl)phenyl}spiro(fluorene-9,8′-fluoreno[3,4-b]benzofuran)-6′,10′-diamine (Compound 7-4)

[0416] The reaction was carried out under the same conditions as those of Example 50, except that 5′,9′-dibromospiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran) was replaced with 6′,10′-dibromospiro(fluorene-9,8′-fluoreno[3,4-b]benzofuran). As a result, a powder of N6′,N6′,N10′,N10′-tetrakis{4-(tert-butyl)phenyl}spiro(fluorene-9,8′-fluoreno[3,4-b]benzofuran)-6′,10′-diamine (Compound 7-4; 2.5 g; yield 34%) was obtained.

##STR00345##

Example 54

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

[0417] The reaction was carried out under the same conditions as those of Example 50, except that 5′,9′-dibromospiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran) was replaced with 5,9-dibromospiro(fluoreno[4,3-b]benzofuran-7,9′-xanthene). As a result, a powder of N5,N5,N9,N9-tetrakis{4-(tert-butyl)phenyl}spiro(fluoreno[4,3-b]benzofuran-7,9′-xanthene)-5,9-diamine (Compound 7-5; 2.4 g; yield 28%) was obtained.

##STR00346##

Example 55

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 7-6)

[0418] The reaction was carried out under the same conditions as those of Example 50, except that 5′,9′-dibromospiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran) was replaced with 5′,9′-dibromo-2-fluorospiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran), and bis{4-(tert-butyl)phenyl}amine was replaced with (biphenyl-4-yl)-{4-(tert-butyl)phenyl}amine. As a result, a powder of N5′,N9′-bis(biphenyl-4-yl)-N5′,N9′-bis{4-(tert-butyl)phenyl}-2-fluorospiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran)-5′,9′-diamine (Compound 7-6; 2.4 g; yield 28%) was obtained.

##STR00347##

Example 56

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 7-7)

[0419] The reaction was carried out under the same conditions as those of Example 50, except that 5′,9′-dibromospiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran) was replaced with 5,9-dibromospiro(benzo[5,6]fluoreno[4,3-b]benzofuran-7,9′-fluorene), and bis{4-(tert-butyl)phenyl}amine was replaced with {4-(tert-butyl)phenyl}-{4-(trimethylsilyl)phenyl}amine. As a result, a powder of N5,N9-bis{4-(tert-butyl)phenyl}-N5,N9-bis{4-(trimethylsilyl)phenyl}spiro(benzo[5,6]fluoreno[4,3-b]benzofuran-7,9′-fluorene)-5,9-diamine (Compound 7-7; 3.0 g; yield 35%) was obtained.

##STR00348##

Example 57

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 7-8)

[0420] The reaction was carried out under the same conditions as those of Example 50, except that 5′,9′-dibromospiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran) was replaced with 5′,9′-dibromospiro(fluorene-9,7′-fluoreno[4,3-b]benzothiophene), and bis{4-(tert-butyl)phenyl}amine was replaced with {4-(tert-butyl)phenyl}-{4-(trimethylsilyl)phenyl}amine. As a result, a powder of N5′,N9′-bis{4-(tert-butyl)phenyl}-N5′,N9′-bis{4-(trimethylsilyl)phenyl}spiro(fluorene-9,7′-fluoreno[4,3-b]benzothiophene)-5′,9′-diamine (Compound 7-8; 3.2 g; yield 37%) was obtained.

##STR00349##

Example 58

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 7-9)

[0421] The reaction was carried out under the same conditions as those of Example 50, except that 5′,9′-dibromospiro(fluorene-9,7′-fluoreno[4,3-b]benzofuran) was replaced with 5,9-dibromospiro(benzo[4′,5′]thieno[2′,3′:5,6]fluoreno[4,3-b]benzofuran-7,9′-fluorene), and bis{4-(tert-butyl)phenyl}amine was replaced with {4-(tert-butyl)phenyl}-(biphenyl-4-yl)amine. As a result, a powder of N5,N9-bis(biphenyl-4-yl)-N5,N9-bis{4-(tert-butyl)phenyl}spiro(benzo[4′,5′]thieno[2′,3′:5,6]fluoreno[4,3-b]benzofuran-7,9′-fluorene)-5,9-diamine (Compound 7-9; 2.8 g; yield 34%) was obtained.

##STR00350##

Example 59

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

[0422] The reaction was carried out under the same conditions as those of Example 50, 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, a powder of N5′,N5′,N9′,N9′-tetrakis{4-(tert-butyl)phenyl}-12′,12′-dimethyl-12′H-spiro(fluorene-9,7′-indeno[1,2-a]fluorene)-5′,9′-diamine (Compound 7-10; 1.8 g; yield 49%) was obtained.

##STR00351##

Example 60

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 7-11)

[0423] The reaction was carried out under the same conditions as those of Example 50, 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, a 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 7-11; 2.3 g; yield 41%) was obtained.

##STR00352##

Example 61

[0424] The organic EL device, as shown in FIG. 1, was fabricated by vapor-depositing a hole injection layer 3, a hole transport layer 4, a light 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.

[0425] Specifically, the glass substrate 1 having ITO (film thickness of 150 nm) formed thereon was subjected to ultrasonic washing in isopropyl alcohol for 20 minutes and then dried for 10 minutes on a hot plate heated to 200° C. After UV ozone treatment for 15 minutes, the glass substrate with ITO was installed in a vacuum vapor deposition apparatus, and the pressure was reduced to 0.001 Pa or lower. The hole injection layer 3 was formed so as to cover the transparent anode 2 in a film thickness of 30 nm by dual vapor deposition of the electron acceptor (Acceptor-1) of the structural formula below and the compound (1-2) of Example 1 at a vapor deposition rate ratio of Acceptor-1: the compound (1-2)=3:97. The hole transport layer 4 was formed on the hole injection layer 3 by forming the compound (1-2) of Example 1 in a film thickness of 40 nm. The light emitting layer 5 was formed on the hole transport layer 4 in a film thickness of 20 nm by dual vapor deposition of Compound EMD-1 of the structural formula below and Compound EMH-1 of the structural formula below at a vapor deposition rate ratio of EMD-1:EMH-1=5:95. The electron transport layer 6 was formed on the light emitting layer 5 in a film thickness of 30 nm by dual vapor deposition of the compound (3b-1) of the structural formula below having an anthracene ring structure and Compound ETM-1 of the structural formula below at a vapor deposition rate ratio of the compound (3b-1): ETM-1=50:50. The electron injection layer 7 was formed on the electron transport layer 6 by forming lithium fluoride in a film thickness of 1 nm. Finally, the cathode 8 was formed by vapor-depositing aluminum in a thickness of 100 nm. The characteristics of the thus fabricated organic EL device were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of emission characteristics measurements performed by applying a DC voltage to the fabricated organic EL device.

##STR00353## ##STR00354##

Example 62

[0426] An organic EL device was fabricated under the same conditions as those of Example 61, except that the compound (3b-1) having an anthracene ring structure was replaced with the compound (4-125) having a pyrimidine ring structure as the material of the electron transport layer 6, and the layer was formed in a film thickness of 30 nm by dual vapor deposition of the compound (4-125) and the compound ETM-1 of the above structural formula at a vapor deposition rate ratio of the compound (4-125): ETM-1=50:50. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

##STR00355##

Example 63

[0427] An organic EL device was fabricated under the same conditions as those of Example 61, except that the compound (3b-1) having an anthracene ring structure was replaced with the compound (6-55) having a benzotriazole ring structure as the material of the electron transport layer 6, and the layer was formed in a film thickness of 30 nm by dual vapor deposition of the compound (6-55) and the compound ETM-1 of the above structural formula at a vapor deposition rate ratio of the compound (6-55): ETM-1=50:50. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

##STR00356##

Example 64

[0428] An organic EL device was fabricated under the same conditions as those of Example 61, except that the compound EMD-1 of the above structural formula was replaced with an amine derivative (7-1) having a condensed ring structure as the material of the light emitting layer 5, and the layer was formed in a film thickness of 25 nm by dual vapor deposition of the amine derivative (7-1) having a condensed ring structure and the compound EMH-1 of the above structural formula at a vapor deposition rate ratio of the amine derivative (7-1): EMH-1=5:95. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

##STR00357##

Example 65

[0429] An organic EL device was fabricated under the same conditions as those of Example 62, except that the compound EMD-1 of the above structural formula was replaced with an amine derivative (7-1) having a condensed ring structure as the material of the light emitting layer 5, and the layer was formed in a film thickness of 25 nm by dual vapor deposition of the amine derivative (7-1) having a condensed ring structure and the compound EMH-1 of the above structural formula at a vapor deposition rate ratio of the amine derivative (7-1): EMH-1=5:95. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

Example 66

[0430] An organic EL device was fabricated under the same conditions as those of Example 63, except that the compound EMD-1 of the above structural formula was replaced with the amine derivative (7-1) having a condensed ring structure as the material of the light emitting layer 5, and the layer was formed in a film thickness of 25 nm by dual vapor deposition of the amine derivative (7-1) having a condensed ring structure and the compound EMH-1 of the above structural formula at a vapor deposition rate ratio of the amine derivative (7-1): EMH-1=5:95. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

Example 67

[0431] An organic EL device was fabricated under the same conditions as those of Example 61, except that the compound (1-2) of Example 1 was replaced with the compound (1-4) of Example 4 as the material of the hole injection layer 3, and the layer was formed in a film thickness of 30 nm by dual vapor deposition of the electron acceptor (Acceptor-1) of the above structural formula and the compound (1-4) of Example 4 at a vapor deposition rate ratio of Acceptor-1: the compound (1-4)=3:97, and the compound (1-2) of Example 1 was replaced with the compound (1-4) of Example 4 as the material of the hole transport layer 4, and the layer was formed in a film thickness of 40 nm. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

##STR00358##

Example 68

[0432] An organic EL device was fabricated under the same conditions as those of Example 62, except that the compound (1-2) of Example 1 was replaced with the compound (1-4) of Example 4 as the material of the hole injection layer 3, and the layer was formed in a film thickness of 30 nm by dual vapor deposition of the electron acceptor (Acceptor-1) of the above structural formula and the compound (1-4) of Example 4 at a vapor deposition rate ratio of Acceptor-1: the compound (1-2)=3:97, and the compound (1-2) of Example 1 was replaced with the compound (1-4) of Example 4 as the material of the hole transport layer 4, and the layer was formed in a film thickness of 40 nm. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

Example 69

[0433] An organic EL device was fabricated under the same conditions as those of Example 63, except that the compound (1-2) of Example 1 was replaced with the compound (1-4) of Example 4 as the material of the hole injection layer 3, and the layer was formed in a film thickness of 30 nm by dual vapor deposition of the electron acceptor (Acceptor-1) of the above structural formula and the compound (1-4) of Example 4 at a vapor deposition rate ratio of Acceptor-1: the compound (1-2)=3:97, and the compound (1-2) of Example 1 was replaced with the compound (1-4) of Example 4 as the material of the hole transport layer 4, and the layer was formed in a film thickness of 40 nm. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

Example 70

[0434] An organic EL device was fabricated under the same conditions as those of Example 64, except that the compound (1-2) of Example 1 was replaced with the compound (1-4) of Example 4 as the material of the hole injection layer 3, and the layer was formed in a film thickness of 30 nm by dual vapor deposition of the electron acceptor (Acceptor-1) of the above structural formula and the compound (1-4) of Example 4 at a vapor deposition rate ratio of Acceptor-1: the compound (1-4)=3:97, and the compound (1-2) of Example 1 was replaced with the compound (1-4) of Example 4 as the material of the hole transport layer 4, and the layer was formed in a film thickness of 40 nm. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

Example 71

[0435] An organic EL device was fabricated under the same conditions as those of Example 65, except that the compound (1-2) of Example 1 was replaced with the compound (1-4) of Example 4 as the material of the hole injection layer 3, and the layer was formed in a film thickness of 30 nm by dual vapor deposition of the electron acceptor (Acceptor-1) of the above structural formula and the compound (1-4) of Example 4 at a vapor deposition rate ratio of Acceptor-1: the compound (1-4)=3:97, and the compound (1-2) of Example 1 was replaced with the compound (1-4) of Example 4 as the material of the hole transport layer 4, and the layer was formed in a film thickness of 40 nm. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

Example 72

[0436] An organic EL device was fabricated under the same conditions as those of Example 66, except that the compound (1-2) of Example 1 was replaced with the compound (1-4) of Example 4 as the material of the hole injection layer 3, and the layer was formed in a film thickness of 30 nm by dual vapor deposition of the electron acceptor (Acceptor-1) of the above structural formula and the compound (1-4) of Example 4 at a vapor deposition rate ratio of Acceptor-1: the compound (1-4)=3:97, and the compound (1-2) of Example 1 was replaced with the compound (1-4) of Example 4 as the material of the hole transport layer 4, and the layer was formed in a film thickness of 40 nm. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

Comparative Example 1

[0437] For comparison, an organic EL device was fabricated under the same conditions as those of Example 61, except that the compound (1-2) of Example 1 was replaced with a compound HTM-1 of the structural formula below as the material of the hole injection layer 3, and the layer was formed in a film thickness of 30 nm by dual vapor deposition of the electron acceptor (Acceptor-1) of the above structural formula and the compound HTM-1 of the structural formula below at a vapor deposition rate ratio of Acceptor-1: HTM-1=3:97, and the compound (1-2) of Example 1 was replaced with the compound HTM-1 of the structural formula below as the material of the hole transport layer 4, and the layer was formed in a film thickness of 40 nm. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

##STR00359##

Comparative Example 2

[0438] For comparison, an organic EL device was fabricated under the same conditions as those of Example 62, except that the compound (1-2) of Example 1 was replaced with the compound HTM-1 of the structural formula below as the material of the hole injection layer 3, and the layer was formed in a film thickness of 30 nm by dual vapor deposition of the electron acceptor (Acceptor-1) of the above structural formula and the compound HTM-1 of the above structural formula at a vapor deposition rate ratio of Acceptor-1: HTM-1=3:97, and the compound (1-2) of Example 1 was replaced with the compound HTM-1 of the above structural formula as the material of the hole transport layer 4, and the layer was formed in a film thickness of 40 nm. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

Comparative Example 3

[0439] For comparison, an organic EL device was fabricated under the same conditions as those of Example 63, except that the compound (1-2) of Example 1 was replaced with the compound HTM-1 of the structural formula below as the material of the hole injection layer 3, and the layer was formed in a film thickness of 30 nm by dual vapor deposition of the electron acceptor (Acceptor-1) of the above structural formula and the compound HTM-1 of the above structural formula at a vapor deposition rate ratio of Acceptor-1: HTM-1=3:97, and the compound (1-2) of Example 1 was replaced with the compound HTM-1 of the above structural formula as the material of the hole transport layer 4, and the layer was formed in a film thickness of 40 nm. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

Comparative Example 4

[0440] For comparison, an organic EL device was fabricated under the same conditions as those of Example 64, except that the compound (1-2) of Example 1 was replaced with the compound HTM-1 of the structural formula below as the material of the hole injection layer 3, and the layer was formed in a film thickness of 30 nm by dual vapor deposition of the electron acceptor (Acceptor-1) of the above structural formula and the compound HTM-1 of the above structural formula at a vapor deposition rate ratio of Acceptor-1: HTM-1=3:97, and the compound (1-2) of Example 1 was replaced with the compound HTM-1 of the above structural formula as the material of the hole transport layer 4, and the layer was formed in a film thickness of 40 nm. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

Comparative Example 5

[0441] For comparison, an organic EL device was fabricated under the same conditions as those of Example 65, except that the compound (1-2) of Example 1 was replaced with the compound HTM-1 of the structural formula below as the material of the hole injection layer 3, and the layer was formed in a film thickness of 30 nm by dual vapor deposition of the electron acceptor (Acceptor-1) of the above structural formula and the compound HTM-1 of the above structural formula at a vapor deposition rate ratio of Acceptor-1: HTM-1=3:97, and the compound (1-2) of Example 1 was replaced with the compound HTM-1 of the above structural formula as the material of the hole transport layer 4, and the layer was formed in a film thickness of 40 nm. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

Comparative Example 6

[0442] For comparison, an organic EL device was fabricated under the same conditions as those of Example 66, except that the compound (1-2) of Example 1 was replaced with the compound HTM-1 of the structural formula below as the material of the hole injection layer 3, and the layer was formed in a film thickness of 30 nm by dual vapor deposition of the electron acceptor (Acceptor-1) of the above structural formula and the compound HTM-1 of the above structural formula at a vapor deposition rate ratio of Acceptor-1: HTM-1=3:97, and the compound (1-2) of Example 1 was replaced with the compound HTM-1 of the above structural formula as the material of the hole transport layer 4, and the layer was formed in a film thickness of 40 nm. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

Comparative Example 7

[0443] For comparison, an organic EL device was fabricated under the same conditions as those of Example 62, except that the compound (1-2) of Example 1 was replaced with the electron acceptor (Acceptor-1) of the above structural formula and the compound (1-2) of Example 1 as the material of the hole transport layer 4, and the layer was formed in a film thickness of 40 nm by dual vapor deposition of the electron acceptor (Acceptor-1) of the above structural formula and the compound (1-2) of Example 1 at a vapor deposition rate ratio of Acceptor-1: the compound (1-2)=3:97. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

Comparative Example 8

[0444] For comparison, an organic EL device was fabricated under the same conditions as those of Example 68, except that the compound (1-4) of Example 4 was replaced with the electron acceptor (Acceptor-1) of the above structural formula and the compound (1-4) of Example 4 as the material of the hole transport layer 4, and the layer was formed in a film thickness of 40 nm by dual vapor deposition of the electron acceptor (Acceptor-1) of the above structural formula and the compound (1-1) of Example 1 at a vapor deposition rate ratio of Acceptor-1: the compound (1-4)=3:97. The characteristics of the organic EL device thus fabricated were measured in the atmosphere at an ordinary temperature. Table 1 summarizes the results of measurement of emission characteristics when applying a DC voltage to the fabricated organic EL device.

[0445] Table 1 summarizes the results of measurement of a device lifetime using the organic EL devices fabricated in Examples 61 to 72 and Comparative Examples 1 to 8. The device lifetime was measured as a 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 95% when taking the initial luminance as 100%: Attenuation to 95%) when carrying out constant current driving.

TABLE-US-00003 TABLE 1 Voltage Current Power Device Hole Hole Light Electron [V] Luminance efficiency efficiency lifetime injection transport emitting transport (@10 mA/ [cd/m.sup.2] [cd/A] [lm/W] (Attenuation layer layer layer layer cm.sup.2) (@10 mA/cm.sup.2) (@10 mA/cm.sup.2) (@10 mA/cm.sup.2) to 95%) Ex. 61 Compound Compound EMD-1/ Compound 4.01 725 7.25 5.68 235 h 1-2/ 1-2 EMH-1 3b-1/ Acceptor-1 ETM-1 Ex. 62 Compound Compound EMD-1/ Compound 4.00 791 7.91 6.21 204 h 1-2/ 1-2 EMH-1 4-125/ Acceptor-1 ETM-1 E.x 63 Compound Compound EMD-1/ Compound 4.13 753 7.53 5.69 211 h 1-2/ 1-2 EMH-1 6-55/ Acceptor-1 ETM-1 Ex. 64 Compound Compound Compound Compound 4.05 774 7.74 6.13 322 h 1-2/ 1-2 7-1/ 3b-1/ Acceptor-1 EMH-1 ETM-1 Ex. 65 Compound Compound Compound Compound 4.05 826 8.26 6.42 314 h 1-2/ 1-2 7-1/□EMH-1 4-125/ Acceptor-1 ETM-1 Ex. 66 Compound Compound Compound Compound 4.07 822 8.22 6.34 280 h 1-2/ 1-2 7-1/ 6-55/ Acceptor-1 EMH-1 ETM-1 Ex. 67 Compound Compound EMD-1/ Compound 4.05 740 7.39 5.75 239 h 1-4/ 1-4 EMH-1 3b-1/ Acceptor-1 ETM-1 Ex. 68 Compound Compound EMD-1/ Compound 3.95 778 7.77 6.18 246 h 1-4/ 1-4 EMH-1 4-125/ Acceptor-1 ETM-1 Ex. 69 Compound Compound EMD-1/ Compound 4.10 806 8.06 6.11 203 h 1-4/ 1-4 EMH-1 6-55/ Acceptor-1 ETM-1 Ex. 70 Compound Compound Compound Compound 4.04 756 7.56 5.92 311 h 1-4/ 1-4 7-1/ 3b-1/ Acceptor-1 EMH-1 ETM-1 Ex. 71 Compound Compound Compound Compound 4.00 795 7.95 6.19 306 h 1-4/ 1-4 7-1/ 4-125/ Acceptor-1 EMH-1 ETM-1 Ex. 72 Compound Compound Compound Compound 4.10 826 8.26 6.38 275 h 1-4/ 1-4 7-1/ 6-55/ Acceptor-1 EMH-1 ETM-1 Com. Ex. 1 HTM-1/ HTM-1 EMD-1/ Compound 4.00 671 6.71 5.28 72 h Acceptor-1 EMH-1 3b-1/ ETM-1 Com. Ex. 2 HTM-1/ HTM-1 EMD-1/ Compound 3.95 700 7.00 5.58 62 h Acceptor-1 EMH-1 4-125/ ETM-1 Com. Ex. 3 HTM-1/ HTM-1 EMD-1/ Compound 4.03 708 7.08 5.42 48 h Acceptor-1 EMH-1 6-55/ ETM-1 Com. Ex. 4 HTM-1/ HTM-1 Compound Compound 3.99 705 7.05 5.36 85 h Acceptor-1 7-1/ 3b-1/ EMH-1 ETM-1 Com. Ex. 5 HTM-1/ HTM-1 Compound Compound 3.96 703 7.03 5.55 78 h Acceptor-1 7-1/ 4-125/ EMH-1 ETM-1 Com. Ex. 6 HTM-1/ HTM-1 Compound Compound 3.99 711 7.11 5.42 75 h Acceptor-1 7-1/ 6-55/ EMH-1 ETM-1 Com. Ex. 7 Compound Compound EMD-1/ Compound 4.00 60 0.60 0.50 1 h 1-2/ 1-2/ EMH-1 4-125/ Acceptor-1 Acceptor-1 ETM-1 Com. Ex. 8 Compound Compound EMD-1/ Compound 3.95 65 0.65 0.62 1 h 1-4/ 1-4/ EMH-1 4-125/ Acceptor-1 Acceptor-1 ETM-1

[0446] As shown in Table 1, the luminous efficiency when passing a current with a current density of 10 mA/cm.sup.2 was 6.71 to 7.11 cd/A for the organic EL devices of Comparative Examples 1 to 6 including the hole transport layer undoped with an electron acceptor, which was higher than 0.60 to 0.65 cd/A for the organic EL devices of Comparative Examples 7 to 8 including the hole transport layer also doped with an electron acceptor. Then, the luminous efficiency was 7.25 to 8.26 cd/A, which was further higher, for the organic EL devices of Examples 61 to 72 using the arylamine compounds represented by the general formula (1) in the hole injection layer. Further, also the power efficiency was 5.28 to 5.58 lm/W for the organic EL devices of Comparative Examples 1 to 6 including the hole transport layer undoped with an electron acceptor, which was higher than 0.50 to 0.62 lm/W for the organic EL devices of Comparative Examples 7 to 8 including the hole transport layer also doped with an electron acceptor. Then, the power efficiency was 5.68 to 6.42 lm/W, which was further higher, for the organic EL devices of Examples 61 to 72 using the arylamine compounds represented by the general formula (1) in the hole injection layer. On the other hand, the device lifetime (attenuation to 95%) was 45 to 85 hours for the organic EL devices of Comparative Examples 1 to 6 including the hole transport layer undoped with an electron acceptor, which was longer than 1 hour for the organic EL devices of Comparative Examples 7 to 8 including the hole transport layer also doped with an electron acceptor. Then, it is found that the device lifetime was 203 to 322 hours, which was further greatly increased, for the organic EL devices of Examples 61 to 72 using the arylamine compounds represented by the general formula (1) in the hole injection layer.

[0447] It was found that the organic EL device of the present invention can achieve an organic EL device having higher luminous efficiency and a longer lifetime compared to the conventional organic EL devices by selecting a specific arylamine compound (having a specific structure) as a material of a hole injection layer and p-doping the compound with an electron acceptor so that holes can be efficiently injected and transported into a hole transport layer from an electrode, and by further selecting a specific arylamine compound (having a specific structure) without p-doping as a material of the hole transport layer so as to improve the carrier balance inside the organic EL device.

INDUSTRIAL APPLICABILITY

[0448] The organic EL device of the present invention in which a specific arylamine compound (having a specific structure) and an electron acceptor are combined so as to be able to refine the carrier balance inside the organic EL device can enhance luminous efficiency and also can improve durability of the organic EL device, and therefore can be applied to, for example, home electric appliances and illuminations.

DESCRIPTION OF REFERENCE NUMERAL

[0449] 1 Glass substrate [0450] 2 Transparent anode [0451] 3 Hole injection layer [0452] 4 Hole transport layer [0453] 5 Light emitting layer [0454] 6 Electron transport layer [0455] 7 Electron injection layer [0456] 8 Cathode