Carbazole-based polymer and organic electroluminescence element using same

Abstract

A polymer including a structural unit represented by the following formula (A). In the formula (A), P is independently a group represented by the following formula (P), a is an integer of 2 to 5, and b is an integer of 0 to 5. In the formula (P), A is independently a nitrogen atom or CR; X is a single bond, O, S, C(R).sub.2 or NR. R is independently a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 20 carbon atoms or the like, or a single bond used for bonding to another P or L, provided that at least one R contained in (P)a is represented by any one of the following formulas (3) to (7). ##STR00001##

Claims

1. A polymer comprising a structural unit represented by the following formula (A):
(P).sub.a-(L).sub.b(A) wherein in the formula (A), P is independently a substituted or unsubstituted carbazole residue; a is an integer of 2 to 5, (P)a means that a Ps are bonded sequentially in which a is the number of Ps, one P contained in (P)a is bonded with (L)b at the 9th position of the carbazole residue of the P and the a Ps may be the same or different; when the carbazole residue contained in (P)a has a substituent, the substituent is independently a substituted or unsubstituted alkyl group including 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group including 3 to 10 ring carbon atoms, a substituted or unsubstituted aryl group including 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group including 3 to 30 ring atoms, a substituted or unsubstituted arylamino group, or a substituted or unsubstituted arylsily group; provided that at least one carbazole residue contained in (P)a has a substituent represented by any one of the following formulas (3) to (7); ##STR00194## wherein R.sub.1 to R.sub.13 are independently a substituted or unsubstituted alkyl group including 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group including 3 to 10 ring carbon atoms, a substituted or unsubstituted aryl group including 6 to 30 ring carbon atoms, a substituted or unsubstituted alkoxy group including 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group including 3 to 10 ring carbon atoms, a substituted or unsubstituted aryloxy group including 6 to 30 ring carbon atoms, a substituted or unsubstituted aralkyl group including 7 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group including 3 to 30 ring atoms, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a silyl group substituted by one or more selected from alkyl groups and aryl groups, a halogen atom, a nitro group, a cyano group or a hydroxyl group, a1, c, d, f, g and i are independently an integer of 0 to 4; b1, e, h and j are independently an integer of 0 to 3; T.sub.1 to T.sub.5 are independently a single bond or a substituted or unsubstituted arylene group including 6 to 50 ring carbon atoms; L is a linkage group; b is an integer of 0 to 5, (L)b means, when b is 2 or more, b Ls are bonded sequentially in which b is the number of L, and in this case, b Ls may be the same or different, and bonding position of Ls is not limited; and when b is 0, (L)b is a single bond.

2. The polymer according to claim 1, wherein bonding position of adjacent carbazole residues in the a carbazole residues being bonded sequentially in which a is the number of the carbazole residues is one selected from the 3.sup.rd-3.sup.rd position, the 3.sup.rd-2.sup.rd position and the 2.sup.nd-the 2.sup.nd position.

3. The polymer according to claim 1, wherein a is 2 or 3.

4. The polymer according to claim 1, which has a structure represented by any of the following formulas (10) to (14) and (23) to (36): ##STR00195## ##STR00196## ##STR00197## ##STR00198## ##STR00199## ##STR00200## wherein in the formulas (10) to (14) and (23) to (36), R is independently a substituted or unsubstituted alkyl group including 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group including 3 to 10 ring carbon atoms, a substituted or unsubstituted aryl group including 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group including 3 to 30 ring atoms, a substituted or unsubstituted arylamino group or an arylsilyl group; and provided that, in each of the formulas, at least one R is independently represented by any of the following formulas (3) to (7): ##STR00201## wherein R.sub.1 to R.sub.13 are independently a substituted or unsubstituted alkyl group including 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group including 3 to 10 ring carbon atoms, a substituted or unsubstituted aryl group including 6 to 30 ring carbon atoms, a substituted or unsubstituted alkoxy group including 1 to 20 ring carbon atoms, a substituted or unsubstituted cycloalkoxy group including 3 to 10 ring carbon atoms, a substituted or unsubstituted aryloxy group including 6 to 30 ring caron atoms, a substituted or unsubstituted aralkyl group including 7 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group including 3 to 30 ring atoms, a substituted amino group, a substituted silyl group, a halogen atom, a nitro group, a cyano group or a hydroxyl group; a1, c, d, f, g and i are independently an integer of 0 to 4; b1, e, h and j are independently an integer of 0 to 3; T.sub.1 to T.sub.5 are independently a single bond or a substituted or unsubstituted arylene group including 6 to 50 ring carbon atoms; l is 0 or 1; n is the repeating number; and L is a linkage group.

5. A coating liquid comprising the polymer according to claim 1 and a solvent.

6. The coating liquid according to claim 5, wherein at least one of the solvents is an organic solvent.

7. A method for producing an electronic device, wherein at least one film constituting an electronic device is formed into a film by a wet method by using the coating liquid according to claim 5.

8. The method for producing an electronic device according to claim 7, wherein the electronic device is an electroluminescence device, a photoelectronic conversion device or a transistor.

9. The method for producing an electronic device according to claim 7, wherein the electronic device is an organic electroluminecence device.

10. An organic electroluminecence device comprising: an anode and a cathode; and one or more organic thin film layers between the anode and the cathode, wherein at least one of the organic thin film layers is an emitting layer, and at least one of the organic thin film layers comprises the polymer according to claim 1.

11. The organic electroluminecence device according to claim 10, wherein at least one of the organic thin film layers is a hole-injecting layer or a hole-transporting layer.

12. The organic electroluminecence device according to claim 11, wherein the hole-injecting layer or the hole-transporting layer is in contact with the emitting layer.

13. The organic electrolumnecence device according to claim 10, wherein the emitting layer is formed by a wet film formation method.

14. The polymer according to claim 1, wherein at least one carbazole residue contained in (P)a has a substituent represented by any one of the formulas (3) to (6).

15. The polymer according to claim 1, wherein bonding position of adjacent carbazole residues in the a carbazole residues being bonded sequentially in which a is the number of the carbazole residues is one selected from the 3.sup.rd-2.sup.nd position and the 2.sup.nd-the 2.sup.nd position.

16. The polymer according to claim 1, wherein b is 0.

17. The polymer according to claim 1, wherein b is an integer of 1 to 5.

18. The polymer according to claim 1, wherein T.sub.1 to T.sub.5 in the formulas (3) to (7) are a single bond.

19. A polymer comprising a structural unit represented by the following formula (A):
(P).sub.a-(L).sub.b(A), wherein in the formula (A), P is independently a substituted or unsubstituted carbazole residue; a is an integer of 2 to 5, (P)a means that a P's are bonded sequentially in which a is the number of P's, the bonding position of adjacent carbazole residues in the a substituted or unsubstituted carbazole residues being bonded sequentially is one selected from the 3rd position-2nd position and the 2nd position-2nd position, and the a P's may be the same or different; when the carbazole residue contained in (P)a has a substituent, the substituent is independently a substituted or unsubstituted alkyl group including 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group including 3 to 10 ring carbon atoms, a substituted or unsubstituted aryl group including 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group including 3 to 30 ring atoms, a substituted or unsubstituted arylamino group, or a substituted or unsubstituted arylsily group; provided that at least one carbazole residue contained in (P)a has a substituent on at least one of the 1.sup.st and 8.sup.th position of the carbazole residue and the substituent is represented by any one of the following formulas (3) to (6); ##STR00202## wherein R.sub.1 to R.sub.9 are independently a substituted or unsubstituted alkyl group including 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group including 3 to 10 ring carbon atoms, a substituted or unsubstituted aryl group including 6 to 30 ring carbon atoms, a substituted or unsubstituted alkoxy group including 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkoxy group including 3 to 10 ring carbon atoms, a substituted or unsubstituted aryloxy group including 6 to 30 ring carbon atoms, a substituted or unsubstituted aralkyl group including 7 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group including 3 to 30 ring atoms, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a silyl group substituted by one or more selected from alkyl groups and aryl groups, a halogen atom, a nitro group, a cyano group or a hydroxyl group, a1, c, d, f, and g are independently an integer of 0 to 4; b1, e, and h are independently an integer of 0 to 3; T.sub.1 to T.sub.4 are independently a single bond or a substituted or unsubstituted arylene group including 6 to 50 ring carbon atoms; L is a linkage group; b is an integer of 0 to 5, (L)b means, when b is 2 or more, b L's are bonded sequentially in which b is the number of L, and in this case, b L's may be the same or different, and bonding position of L's is not limited; and when b is 0, (L)b is a single bond.

Description

EXAMPLES

Example 1

(1) P-1 was synthesized by the following synthesis scheme.

(2) ##STR00169## ##STR00170## ##STR00171##
(1) Synthesis of Intermediate M-1-1

(3) Under a nitrogen atmosphere, 10.0 g (59.8 mmol) of carbazole and 100 mL of dimethylformamide (DMF) were placed in a 500 mL three-necked flask equipped with a cooling tube. The mixture was cooled to 0? C. in an ice water bath. After cooling, a solution obtained by dissolving 10.6 g (59.8 mmol) of N-bromosuccinimide (NBS) in 100 mL of DMF was added dropwise slowly. After completion of the addition, the flask was taken from the ice water bath, returned to room temperature and stirred for 8 hours.

(4) A reaction liquid was dropped in water to precipitate solids. By filtration, a precipitate was obtained. The resulting crude product was purified by means of silica-gel chromatography (toluene). The resulting solids were dried under reduced pressure to obtain 12.2 g of white solids (yield: 83%).

(5) By .sup.1H-NMR spectrum and Field Desorption Mass Spectrometry (hereinafter referred to as FD-MS) analysis, the white powder obtained was confirmed to be intermediate M-1-1.

(6) (2) Synthesis of Intermediate M-1-2

(7) Under a nitrogen atmosphere, 6.0 g (24.3 mmol) of M-1-1, 5.4 g (26.7 mmol) of iodobenzene, 1.4 g (7.29 mmol) of CuI, 0.8 g (7.29 mmol) of trans-cyclohexanediamine, 10.3 g (48.6 mmol) of potassium phosphate and 120 mL of dioxane were placed in a 300 mL three-necked flask equipped with a cooling tube. The mixture was heated under reflux for 8 hours.

(8) After completion of the reaction, the solvent was removed under reduced pressure. Then, 100 mL of dichloromethane and 100 mL of water were added to extract an intended substance to take out an organic phase. MgSO.sub.4 was added to the organic phase thus taken out for drying. MgSO.sub.4 was removed by filtration. The solvent was removed under reduced pressure, and the crude product obtained was purified by means of silica-gel chromatography (toluene:hexane=1:10). The resulting solids were dried under reduced pressure to obtain 6.7 g of white solids (yield: 85%). By .sup.1H-NMR spectrum and FD-MS analysis, the white powder obtained was confirmed to be intermediate M-1-2.

(9) (3) Synthesis of Intermediate M-1-3

(10) Under a nitrogen atmosphere, 4.0 g (12.5 mmol) of M-1-2, 2.8 g (15.0 mmol) of triisopropyl borate and 60 mL of dehydrated tetrahydrofuran (THF) were placed in a 300 mL three-necked flask equipped with a cooling tube. The mixture was stirred and cooled to ?78? C. in a methanol/dry ice bath. After cooling, 38 mL (60.9 mmol) of n-butyllithium (1.61M) was added dropwise slowly. After the dropwise addition, the mixture was cooled and stirred for an hour. Then, the mixture was returned to room temperature and stirred for 7 hours. After completion of the reaction, 10 mL of methanol was added dropwise, and further 30 mL of a 1N aqueous solution of HCl was added dropwise. By adding methylene chloride and water, an intended substance was extracted to take out an organic phase. MgSO.sub.4 was added to the organic phase thus taken out for drying. MgSO.sub.4 was removed by filtration. The solvent was removed under reduced pressure and isolated by means of column chromatography to obtain 2.1 g of white solids (yield: 60%). By .sup.1H-NMR spectrum and FD-MS analysis, the white powder obtained was confirmed to be intermediate M-1-3.

(11) (4) Synthesis of Intermediate M-1-4

(12) Under a nitrogen atmosphere, 4 g (10.0 mmol) of M-1-1, 3.7 g (10.0 mmol) of M-1-3, 0.2 g (0.2 mol) of Pd(PPh.sub.3).sub.4, 2.1 g (20.0 mmol) of sodium carbonate, 40 mL of DME and 20 mL of water were placed in a 300 mL three-necked flask equipped with a cooling tube. The mixture was heated under reflux for 8 hours. After completion of the reaction, the solvent was removed under reduced pressure. Then, 100 mL of dichloromethane and 100 mL of water were added to extract an intended substance to take out an organic phase. MgSO.sub.4 was added to the organic phase thus taken out for drying. MgSO.sub.4 was removed by filtration. The solvent was removed under reduced pressure, and the crude product obtained was purified by means of silica-gel chromatography. The resulting solids were dried under reduced pressure to obtain 3.0 g of white solids (yield: 74%). By .sup.1H-NMR spectrum and FD-MS analysis, the white powder obtained was confirmed to be intermediate M-1-4.

(13) (5) Synthesis of Intermediate M-1-5

(14) Under a nitrogen atmosphere, 2.5 g (6.1 mmol) of M-1-4, 2.0 g (6.1 mmol) of 4-(4-bromophenyl)-dibenzofuran, 0.4 g (1.8 mmol) of CuI, 0.2 g (1.8 mmol) of trans-cyclohexanediamine, 2.6 g (12.2 mmol) of potassium phosphate and 30 mL of dioxane were mixed, and heated under reflux for 8 hours.

(15) After completion of the reaction, the solvent was removed under reduced pressure. Then, 100 mL of dichloromethane and 100 mL of water were added to extract an intended substance to take out an organic phase. MgSO.sub.4 was added to the organic phase thus taken out for drying. MgSO.sub.4 was removed by filtration. The solvent was removed under reduced pressure, and the crude product obtained was purified by means of silica-gel chromatography. The resulting solids were dried under reduced pressure to obtain 2.8 g of white solids (yield: 70%). By .sup.1H-NMR spectrum and FD-MS analysis, the white powder obtained was confirmed to be intermediate M-1-5.

(16) (6) Synthesis of Monomer M-1

(17) Under a nitrogen atmosphere, 2.5 g (3.8 mmol) of M-1-5 and 40 mL of DMF were mixed and cooled to 0? C. in an ice water bath.

(18) After cooling, a solution obtained by dissolving 1.4 g (8.0 mmol) of N-bromosuccinimide in 40 mL of DMF was added dropwise slowly. After completion of the addition, the flask was taken from the ice water bath, returned to room temperature and stirred for 8 hours. The reaction liquid was dropped in water to precipitate solids. The resulting solids were collected by suction filtration.

(19) The resulting crude product was purified by means of silica-gel chromatography. The resulting solids were dried under reduced pressure to obtain 2.5 g of white solids (yield: 80%).

(20) By .sup.1H-NMR spectrum and FD-MS analysis, the white powder obtained was confirmed to be intermediate M-1.

(21) (7) Synthesis of Polymer P-1

(22) Under a nitrogen atmosphere, 4.1 g (6.2 mmol) of 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9,9-di-n-octylfluorene, 5.0 g (6.2 mmol) of M-1, 0.01 g (0.04 mmol) of Pd(OAc).sub.2, 0.06 g (0.2 mmol) of P(o-Tol).sub.3, 6.6 g (30.9 mmol) of potassium phosphate, 50 mL of dioxane, 12 mL of toluene and 11 mL of water were mixed and heated under reflux for 16 hours.

(23) After completion of the reaction, the solvent was removed under reduced pressure. By addition of 150 mL of toluene and 100 mL of water, an intended substance was extracted to take out an organic phase. MgSO.sub.4 was added to the organic phase thus taken out for drying. MgSO.sub.4 was removed by filtration. The solvent was concentrated under reduced pressure to obtain a concentrated liquid. Filtration was conducted by passing the concentrated liquid through silica gel. The collected solution was concentrated under reduced pressure. The concentrated liquid was added dropwise to methanol to precipitate solids. The solids were filtrated and dried under reduced pressure.

(24) Under a nitrogen atmosphere, the resulting crude product, 0.3 g (1.9 mmol) of bromobenzene, 0.03 g (0.04 mmol) of Pd(OAc).sub.2, 0.01 g (0.05 mmol) of P(t-Bu).sub.3, 2.0 g (9.5 mmol) of potassium phosphate and 50 mL of toluene were mixed, and heated under reflux for 8 hours. Next, 0.2 g (1.9 mmol) of phenylboronic acid was added, followed by heating further for 8 hours.

(25) After completion of the reaction, an intended substance was extracted by adding 100 mL of water to take out an organic phase. MgSO.sub.4 was added to the organic phase thus taken out for drying. MgSO.sub.4 was removed by filtration. The collected filtrate was filtered through silica gel. The collected solution was concentrated, followed by addition of an aqueous solution of diethyldithiacarbamate. The mixture was stirred at 80? C. for 8 hours. After cooling, an organic phase was washed with water. The resulting solution was dropped in methanol to obtain a precipitate by filtration.

(26) The precipitate was dissolved in toluene and purified through a silica-gel column. The solution obtained was dropped in methanol and stirred. Then, the precipitate obtained was filtered and dried to obtain 3.4 g of polymer P-1. P-1 had a number average molecular weight of 1.0?10.sup.4 in terms of polystyrene and a weight average molecular weight of 2.3?10.sup.4 in terms of polystyrene.

(27) As the method for measuring the molecular weight, size exclusion chromatography (SEC) was used. Specifically, the measurement was conducted as follows. 10 mg of a sample was dissolved in 10 ml of THF. 100 ?l of the solution thus obtained was injected into a column, and the measurement was conducted. The flow rate was set to 1 ml per minute. The column temperature was set to 40? C. As a size exclusion chromatography (SEC) apparatus, HLC-8220 manufactured by TOSO CORPORATION was used. As a detector, a refractive index (RI) detector or an ultraviolet-visible (UV) detector was used. As for columns, 2 of TSKgel GMH-XL and 1 of TSKgel G2000-XL manufactured by TOSO CORPORATION were used. As the polystyrene as a standard sample, TSK standard polystyrene manufactured by TOSO CORPORATION was used.

Example 2

(28) P-2 was synthesized by the following synthesis scheme.

(29) ##STR00172## ##STR00173## ##STR00174##
(1) Synthesis of Intermediate M-2-1

(30) M-2-1 was synthesized in the same manner as in the synthesis of M-1-2, except that carbazole was used as the raw material and 2-bromodibenzofuran was used instead of iodobenzene. 4.0 g of an intended substance was obtained (yield: 68%). By .sup.1H-NMR spectrum and FD-MS analysis, the substance obtained was confirmed to be M-2-1.

(31) (2) Synthesis of intermediate M-2-2

(32) M-2-2 was synthesized in the same manner as in the synthesis of intermediate M-1-1 by using M-2-1 as the raw material. 3.2 g of an intended substance was obtained (yield: 59%). By .sup.1H-NMR spectrum and FD-MS analysis, the substance obtained was confirmed to be M-2-2.

(33) (3) Synthesis of intermediate M-2-3

(34) M-2-3 was synthesized in the same manner as in the synthesis of M-1-3 by using M-2-2 as the raw material. 5.4 g of an intended substance was obtained (yield: 66%). By .sup.1H-NMR spectrum and FD-MS analysis, the substance obtained was confirmed to be M-2-3.

(35) (4) Synthesis of Intermediate M-2-4

(36) M-2-4 was synthesized in the same manner as in the synthesis of intermediate M-1-1, except that N-iodosuccinimide (NIS) was used instead of NBS. 5.6 g of an intended substance was obtained (yield: 79%). By .sup.1H-NMR spectrum and FD-MS analysis, the substance obtained was confirmed to be M-2-4.

(37) (5) Synthesis of Intermediate M-2-5

(38) The intermediate M-2-5 was synthesized in the same manner as in the synthesis of intermediate M-1-1, except that M-2-4 was used as the raw material. 3.7 g of an intended substance was obtained (yield: 82%). By .sup.1H-NMR spectrum and FD-MS analysis, the substance obtained was confirmed to be M-2-5.

(39) (6) Synthesis of intermediate M-2-6

(40) M-2-6 was synthesized in the same manner as in the synthesis of intermediate M-1-4, except that M-2-5 was used as the raw material and M-2-3 was used instead of 3-bromo-9H-carbazole. 5.2 g of an intended substance was obtained (yield: 76%). By .sup.1H-NMR spectrum and FD-MS analysis, the substance obtained was confirmed to be M-2-6.

(41) (7) Synthesis of Monomer M-2

(42) M-2 was synthesized in the same manner as in the synthesis of intermediate M-1-2, except that M-2-6 was used as the raw material and 1-bromo-4-iodobenzene was used instead of iodobenzene. 4.9 g of an intended substance was obtained (yield: 66%). By .sup.1H-NMR spectrum and FD-MS analysis, the substance obtained was confirmed to be M-2.

(43) (8) Synthesis of Polymer P-2

(44) P-2 was synthesized in the same manner as in the synthesis of P-1, except that M-2 was used instead of M-1. 2.2 g of an intended substance was obtained. Polymer P-2 had a number average molecular weight of 1.2?10.sup.4 in terms of polystyrene and a weight average molecular weight of 3.3?10.sup.4 in terms of polystyrene.

Example 3

(45) P-3 was synthesized by the following synthesis scheme.

(46) ##STR00175## ##STR00176##
(1) Synthesis of Intermediate M-3-1

(47) M-3-1 was synthesized in the same manner as in the synthesis of intermediate M-1-3, except that 2-bromodibenzofuran was used as the raw material. 6.1 g of an intended substance was obtained (yield: 63%). By .sup.1H-NMR spectrum and FD-MS analysis, the substance obtained was confirmed to be M-3-1

(48) (2) Synthesis of Intermediate M-3-2

(49) Under a nitrogen atmosphere, a solution obtained by dissolving 10 g (59.8 mmol) of 9-H-carbazole in 75 ml of chloroform was cooled to 0? C. in an ice water bath. Next, a solution obtained by dispersing 38.8 g (239.2 mmol) of FeCl.sub.3 in about 60 ml of chloroform was added dropwise slowly. After the addition, the resulting mixture was returned to room temperature, and stirred for 24 hours. The reaction liquid was added to a large quantity of methanol dropwise to precipitate solids. The solids were collected by filtration. Then, the collected solids were washed with a large quantity of methanol and water repeatedly to obtain 7.8 g of solids by filtration (yield: 82%). By .sup.1H-NMR spectrum and FD-MS analysis, the white powder obtained was confirmed to be M-3-2.

(50) (3) Synthesis of Intermediate M-3-3

(51) M-3-3 was synthesized in the same manner as in the synthesis of intermediate M-1-1, except that M-3-2 was used as the raw material. 4.1 g of an intended substance was obtained (yield: 56%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-3-3.

(52) (4) Synthesis of Monomer M-3

(53) M-3 was synthesized in the same manner as in the synthesis of intermediate M-1-4, except that M-3-3 was used as the raw material and M-3-1 was used instead of 3-bromo-9H-carbazole. 3.4 g of an intended substance was obtained (yield: 48%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-3.

(54) (7) Synthesis of Polymer P-3

(55) Under a nitrogen atmosphere, 5.8 g (10.0 mmol) of 9,9-dioctyl-2,7-dibromofluorene, 7.0 g (10.5 mmol) of M-3, 0.2 g (0.2 mmol) of Pd.sub.2(dba).sub.3, 0.06 g (0.3 mmol) of P(t-Bu).sub.3, 3.0 g (31.5 mmol) of sodium-t-butoxide and 40 mL of toluene were mixed. The mixture was heated under reflux for 20 hours.

(56) After completion of the reaction, the solvent was removed under reduced pressure. An intended substance was extracted by adding 100 mL of water to take out an organic phase. The organic phase thus taken out was dried by adding MgSO.sub.4. MgSO.sub.4 was removed by filtration. The solvent was concentrated under reduced pressure. The concentrated liquid was filtered through silica gel. The collected solution was concentrated under reduced pressure. The concentrated solution was added to methanol dropwise to precipitate solids. The solids were collected by suction filtration and dried under reduced pressure.

(57) Under a nitrogen atmosphere, the crude product, 0.5 g (3.2 mmol) of bromobenzene, 0.04 g (0.2 mmol) of Pd(OAc).sub.2, 0.06 g (0.3 mmol) of P(t-Bu).sub.3, 1.1 g (5.2 mmol) of potassium phosphate and 40 mL of toluene were mixed. The mixture was heated for 8 hours under reflux. Next, 0.4 g (3.2 mmol) of phenyl boronic acid was added thereto, and heated for further 8 hours.

(58) After completion of the reaction, an intended substance was extracted by adding 100 mL of water to take out an organic phase. MgSO.sub.4 was added to the organic phase thus taken out for drying. MgSO.sub.4 was removed by filtration. The collected filtrate was filtered through silica gel. The collected solution was concentrated, followed by addition of an aqueous solution of sodium diethyldithiacarbamate. The mixture was stirred at 80? C. for 2 hours. After cooling, an organic phase was washed with water. The solution obtained was added to methanol dropwise to obtain a precipitate by filtration.

(59) The precipitate was dissolved in toluene and purified through a silica-gel column. The solution obtained was added to methanol dropwise and stirred. Then, the precipitate obtained was filtered and dried to obtain 5.3 g of polymer P-3. Polymer P-3 had a number average molecular weight of 1.4?10.sup.4 in terms of polystyrene and a weight average molecular weight of 2.9?10.sup.4 in terms of polystyrene.

Example 4

(60) P-4 was synthesized by the following synthesis scheme.

(61) ##STR00177## ##STR00178##
(1) Synthesis of Intermediate M-4-1

(62) M-4-1 was synthesized in the same manner as in the synthesis of monomer M-1 by using 9-phenylcarbazole as the raw material. 2.9 g of an intended substance was obtained (yield: 73%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-4-1.

(63) (4) Synthesis of Intermediate M-4-2

(64) M-4-2 was synthesized in the same manner as in the synthesis of intermediate M-1-4, except that M-2-3 was used as the raw material and M-4-1 was used instead of 3-bromo-9H-carbazole. 2.7 g of an intended substance was obtained (yield: 61%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-4-2.

(65) (5) Synthesis of Monomer M-4

(66) Synthesis was conducted in the same manner as in the synthesis of monomer M-1, except that M-4-2 was used as the raw material. 3.9 g of an intended substance was obtained (yield: 56%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-4.

(67) (6) Synthesis of Polymer P-4

(68) P-4 was synthesized in the same manner as in the synthesis of P-1, except that M-4 was used instead of M-1. 3.6 g of an intended substance was obtained. Polymer P-4 had a number average molecular weight of 1.4?10.sup.4 in terms of polystyrene and a weight average molecular weight of 3.5?10.sup.4 in terms of polystyrene.

Example 5

(69) P-5 was synthesized by the following synthesis scheme.

(70) ##STR00179## ##STR00180##
(1) Synthesis of Intermediate M-5-1

(71) M-5-1 was synthesized in the same manner as in the synthesis of the intermediate M-1-1 by using 2-(9H-carbazole-9-yl)dibenzofuran as the raw material. 4.6 g of an intended substance was obtained (yield: 87%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-5-1.

(72) (2) Synthesis of Intermediate M-5-2

(73) M-5-2 was synthesized in the same manner as in the synthesis of intermediate M-1-3 by using M-5-1 as the raw material. 1.9 g of an intended substance was obtained (yield: 43%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-5-2.

(74) (3) Synthesis of Monomer M-5

(75) M-5 was synthesized in the same manner as in the synthesis of intermediate M-1-4 by using M-5-2 as the raw material. 3.5 g of an intended substance was obtained (yield: 56%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-5.

(76) (4) Synthesis of Polymer P-5

(77) Polymer P-5 was synthesized in the same manner as in the synthesis of P-3 by using M-5 instead of M-3. 6.2 g of an intended substance was obtained. Polymer P-5 had a number average molecular weight of 1.7?10.sup.4 in terms of polystyrene and a weight average molecular weight of 3.3?10.sup.4 in terms of polystyrene.

Example 6

(78) P-6 was synthesized by the following synthesis scheme.

(79) ##STR00181## ##STR00182##
(1) Synthesis of Intermediate M-6-1

(80) M-6-1 was synthesized in the same manner as in the synthesis of intermediate M-1-1 by using 3-(9H-carbazole-3-yl)carbazole as the raw material. 3.5 g of an intended substance was obtained (yield: 66%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-6-1.

(81) (2) Synthesis of Intermediate M-6

(82) M-6 was synthesized in the same manner as in the synthesis of intermediate M-1-4, except that M-6-1 was used as the raw material and (9-(dibenzofuran-2-yl)-carbazole-3-yl)boronic acid was used instead of 3-bromo-9H-carbazole. 4.9 g of an intended substance was obtained (yield: 72%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-6.

(83) (3) Synthesis of Polymer P-6

(84) P-6 was synthesized in the same manner as in the synthesis of P-3 by using M-6 instead of M-3. 2.4 g of an intended substance was obtained. Polymer P-6 had a number average molecular weight of 1.3?10.sup.4 in terms of polystyrene and a weight average molecular weight of 3.0?10.sup.4 in terms of polystyrene.

Example 7

(85) P-7 was synthesized by the following synthesis scheme.

(86) ##STR00183## ##STR00184## ##STR00185##
(1) Synthesis of Intermediate M-7-1

(87) M-7-1 was synthesized in the same manner as in the synthesis of intermediate M-1-4, except that (9-(dibenzofuran-2-yl)-carbazole-3-yl-boronic acid was used as the raw material and 3-bromo-9-(dibenzofuran-2-yl)-carbazole was used instead of 3-bromo-9H-carbazole. 3.6 g of an intended substance was obtained (yield: 82%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-7-1.

(88) (2) Synthesis of Intermediate M-7-2

(89) M-7-2 was synthesized in the same manner as in the synthesis of intermediate M-1-1 by using except that M-7-1 as the raw material. 3.5 g of an intended substance was obtained (yield: 66%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-7-2.

(90) (3) Synthesis of Intermediate M-7-3

(91) M-7-3 was synthesized in the same manner as in the synthesis of intermediate M-1-3 by using M-7-2 as the raw material. 4.1 g of an intended substance was obtained (yield: 62%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-7-3.

(92) (4) Synthesis of Intermediate M-7-4

(93) M-7-4 was synthesized in the same manner as in the synthesis of intermediate M-1-4, except that M-7-3 was used as the raw material and 3-bromo-6-iodo-9H-carbazole was used instead of 3-bromo-9H-carbazole. 1.8 g of an intended substance was obtained (yield: 76%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-7-4.

(94) (5) Synthesis of Monomer M-7

(95) M-7 was synthesized in the same manner as in the synthesis of intermediate M-1-2, except that M-7-4 was used as the raw material and 1-bromo-4-iodobenzene was used instead of iodobenzene. 2.7 g of an intended substance was obtained (yield: 70%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-7.

(96) (6) Synthesis of Polymer P-7

(97) P-7 was synthesized in the same manner as in the synthesis of P-1 by using M-7 instead of M-1. 3.1 g of an intended substance was obtained. Polymer P-7 had a number average molecular weight of 1.1?10.sup.4 in terms of polystyrene and a weight average molecular weight of 2.7?10.sup.4 in terms of polystyrene.

Example 8

(98) P-8 was synthesized by the following synthesis scheme.

(99) ##STR00186## ##STR00187##
(1) Synthesis of Intermediate M-8-1

(100) Under a nitrogen atmosphere, a reaction was conducted by using a stirrer while keeping a homogenous state.

(101) 10.03 g (2.50?10.sup.?2 mol) of 9-phenyl-3,6-dibromocarbazole and 125 mL of THF as a solvent were placed in a 300 mL three-necked flask. The mixture was cooled to ?78? C. in a dry ice/methanol bath. 34.4 mL (2.50?10.sup.?2 mol) of a hexane solution of n-butyllithium (1.6M) was added dropwise slowly. After completion of the dropwise addition, stirring was conducted for one hour, whereby 9-phenyl-3,6-dilithiocarbazole (dilithio body) was obtained.

(102) Then, while keeping at ?78? C., to the reaction solution, 11.2 g (6.00?10.sup.?2 mol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborane was added slowly, and the resultant was returned to room temperature slowly. A reaction was conducted by stirring for further 5 hours. After completion of the reaction, the reaction liquid was poured to 500 mL of water, extraction was conducted with methylene chloride by using a separating funnel. Methylene chloride was removed by distillation under reduced pressure to obtain a crude product. Finally, purification was conducted by silica gel column chromatography (a mixed solvent of methylene chloride and hexane; solvent:volume ratio 1:1, or methylene chloride alone), whereby 8.20 g of M-8-1 as an intended product was isolated (yield: 66%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-8-1.

(103) (2) Synthesis of Intermediate M-8-2

(104) Synthesis was conducted in the same manner as in the synthesis of monomer M-1 by using M-2-1 as the raw material. 4.86 g of an intended substance was obtained (yield: 75%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-8-2.

(105) (3) Synthesis of Polymer P-8

(106) Under a nitrogen atmosphere, a reaction was conducted by using a stirrer while keeping a homogenous state.

(107) In a 100 mL-three neck flask equipped with a cooling tube (reflux condenser), 0.69 g (1.40?10.sup.?3 mol) of M-8-1, 0.69 g (1.40?10.sup.?3 mol) of M-8-2, 1.53 g (7.21?10.sup.?3 mmol) of tripotassium phosphate, 0.0122 g (4.00?10.sup.?5 mol) of tri(o-tolyl)phosphine, 17 mL of dioxane, 4 mL of toluene and 2.7 mL of water were placed, and the resulting mixture was sufficiently stirred. To this, 0.0225 g (1.00?10.sup.?5 mol) of palladium acetate was added, and a polymerization reaction was conducted at 90? C. for 8 hours. Subsequently, to this reaction liquid, 0.0297 g (6.00?10.sup.?5 mol) of M-8-1 was added, and refluxed for 4 hours. Further, 0.100 g (6.37?10.sup.?4 mol) of benzene bromide was added and refluxed for 4 hours. Finally, 1.26 g (5.60?10.sup.?3 mol) of sodium N,N-diethyldithiocarbamate was added, and a reaction was conducted at 80? C. for 8 hours.

(108) To the resulting reaction solution, 100 mL of dioxane was put to allow soluble components and insoluble components to be separated by filtration. The soluble components were concentrated under reduced pressure, and the resultant was poured to 500 mL of methanol to conduct re-precipitation. The formed solid components were taken out by filtration, and the solvent was fully dried under reduced pressure, whereby 0.12 g (recovery: 15%) of polymer P-8 as an intended product was obtained. Polymer P-8 had a weight average molecular weight of 1500 in terms of polystyrene and a number average molecular weight of 1200 in terms of polystyrene. Subsequently, 100 mL of toluene was added to the insoluble components and refluxed, and the toluene-soluble components were concentrated under reduced pressure. Then, the resultant was poured to 500 mL of methanol to conduct re-precipitation. The formed solid components were collected by filtration, and the solvent was sufficiently dried under reduced pressure, whereby 0.27 g (recovery: 33%) of polymer P-8 as an intended product was obtained. Polymer P-8 had a number average molecular weight of 1700 in terms of polystyrene and a weight average molecular weight of 1200 in terms of polystyrene.

Comparative Example 1

(109) P-9 was synthesized by the following synthesis scheme.

(110) ##STR00188##
(1) Synthesis of P-9

(111) P-9 was synthesized in the same manner as in the synthesis of P-1 by using 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9,9-di-n-octylfluorene and M-9. An intended product was obtained in a yield of 5.6 g. Polymer P-9 had a weight average molecular weight of 2.4?10.sup.4 in terms of polystyrene and a number average molecular weight of 7.8?10.sup.3 in terms of polystyrene.

Comparative Example 2

(112) P-10 was synthesized by the following synthesis scheme.

(113) ##STR00189##
(1) Synthesis of monomer M-10

(114) Under a nitrogen atmosphere, 10.0 g (18.2 mmol) of 9,9-dioctyl-2,7-dibromofluorene, 1.7 g (18.2 mmol) of anilline, 0.6 g (0.6 mmol) of Pd.sub.2(dba).sub.3, 1.7 g (0.8 mmol) of rac-BINAP (2,2-bis(diphenylphosphino)-1,1-binaphthyl), 5.0 g (72.8 mmol) of sodium-t-butoxide and 500 mL of toluene were mixed. The mixture was heated under reflux for 16 hours.

(115) After completion of the reaction, the solvent was removed under reduced pressure. An intended substance was extracted by adding 100 mL of water to take out an organic phase. The organic phase thus taken out was dried by adding MgSO.sub.4. MgSO.sub.4 was removed by filtration. The solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography. The resulting solids were dried under reduced pressure, whereby 6.8 g (yield: 65%) of white solids were obtained.

(116) By .sup.1H-NMR spectrum and FD-MS analysis, the resulting white solids were confirmed to be intermediate M-10.

(117) (4) Synthesis of Polymer P-10

(118) P-10 was synthesized in the same manner as in the synthesis of P-4 by using 4,4-dibromobiphenyl and M-10. An intended product was obtained in a yield of 4.5 g. Polymer P-10 had a weight average molecular weight of 1.3?10.sup.4 in terms of polystyrene and a number average molecular weight of 3.6?10.sup.4 in terms of polystyrene.

Comparative Example 3

(119) P-11 was synthesized by the following synthesis scheme.

(120) ##STR00190## ##STR00191##
(1) Synthesis of Intermediate M-11-1

(121) Under a nitrogen atmosphere, 1.3 g (8.0 mmol) of 9H-carbazole, 3.1 g (16 mmol) of, and 1.7 g (12 mmol) of potassium carbonate were placed, and 20 mL of DMF was added. Further, 3.0 g (11.4 mmol) of 1-bromooctane was added, and the resultant was stirred at 80? C. for 16 hours. After completion of the reaction, the solvent was removed under reduced pressure. 100 mL of water was added to extract an intended product and an organic phase was taken out. The organic phase thus taken out was dried by adding MgSO.sub.4. MgSO.sub.4 was removed by filtration. The solvent was removed under reduced pressure. The resulting crude product was purified by silica gel chromatography. The resulting solids were dried under reduced pressure, whereby 1.9 g (yield: 86%) of white solids were obtained.

(122) By .sup.1H-NMR spectrum and FD-MS analysis, the resulting white solids were confirmed to be intermediate M-11-1.

(123) (2) Synthesis of Intermediate M-11-2

(124) Synthesis was conducted in the same manner as in the synthesis of intermediate M-1-1 by using M-11-1 as the raw material. An intended product was obtained in a yield of 5.3 g (yield: 83%). By .sup.1H-NMR spectrum and FD-MS analysis, the intended product was confirmed to be M-11-2.

(125) (3) Synthesis of Intermediate M-11-3

(126) Synthesis was conducted in the same manner as in the synthesis of intermediate M-1-4 by using M-11-2 instead of 3-bromocarbazole as the raw material. 4.4 g of an intended substance was obtained (yield: 78%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-11-3.

(127) (4) Synthesis of Monomer M-11

(128) Synthesis was conducted in the same manner as in the synthesis of monomer M-1 by using M-11-3 as the raw material. 4.9 g of an intended substance was obtained (yield: 75%). By .sup.1H-NMR spectrum and FD-MS analysis, it was confirmed to be M-11.

(129) (7) Polymer P-11

(130) Synthesis was conducted in the same manner as in the synthesis of P-1 by using M-11 instead of M-1. 3.3 g of an intended substance was obtained. Polymer P-11 had a weight average molecular weight of 1.9?10.sup.4 in terms of polystyrene and a number average molecular weight of 4.1?10.sup.4 in terms of polystyrene.

Example 9

Fabrication and Evaluation of Organic EL Device

(131) A glass substrate, measuring 25 mm?75 mm?1.1 mm thick, with an ITO transparent electrode (manufactured by Geomatics Co.) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes and then UV ozone cleaning for 30 minutes. On the cleaned glass substrate with a transparent electrode, a mixture of polyethylenedioxythiophene/polystyrenesulfonate (PEDOT:PSS (acceptor)) was formed into a 10 nm-thick film as a hole-injecting layer by spin coating.

(132) Subsequently, a xylene solution (1.0% by weight) of P-1 obtained in Example 1 was formed into a 25 nm-thick film by spin coating. Next, the resulting thin film was dried under reduced pressure at 120? C. for an hour to form a hole-transporting layer.

(133) Further, the following compound EM1 was formed into a 40 nm-thick film by deposition. At the same time, as light emitting molecules, the following amine compound D1 including a styryl group was deposited such that the ratio by weight of EM1 to D1 became 95:5 to form an emitting layer. On the film obtained, the following compound Alq was deposited to form a 10 nm-thick film. The layer obtained served as an electron-injecting layer.

(134) Subsequently, Li as a reducing dopant (Li source: manufactured by SAES Getters Co., Ltd.) and compound Alq were co-deposited to form an Alq:Li film (film thickness: 10 nm) as an electron-injecting layer (cathode). On the Alq:Li film, metal Al was deposited to form a metallic cathode. Glass sealing was conducted in nitrogen to fabricate an organic EL device. The fabricated organic EL device was evaluated for luminous efficiency (cd/A) by applying an electric current. The results are shown in Table 1.

(135) ##STR00192##

Example 10

(136) An organic EL device was fabricated and evaluated in the same manner as in Example 9, except that the following arylamine compound D2 was used instead of amine compound D1 including a styryl group as a material for an emitting layer. The results are shown in Table 1.

(137) ##STR00193##

Comparative Example 4

(138) An organic EL device was fabricated and evaluated in the same manner as in Example 9, except that P-9 obtained in Comparative Example 1 was used instead of P-1 as a hole-transporting material. The results are shown in Table 1.

Comparative Example 5

(139) An organic EL device was fabricated and evaluated in the same manner as in Example 9, except that P-10 obtained in Comparative Example 2 was used instead of P-1 as a hole-transporting material. The results are shown in Table 1.

Comparative Example 6

(140) An organic EL device was fabricated and evaluated in the same manner as in Example 9, except that P-11 obtained in Comparative Example 3 was used instead of P-1 as a hole-transporting material. The results are shown in Table 1.

(141) TABLE-US-00111 TABLE 1 Hole-transporting Emitting layer Emitting Luminous efficiency Relative layer Host Dopant color (cd/A) lifetime* Example 9 P-1 EM1 D1 Blue 3.9 1.0 Example 10 P-1 EM1 D2 Blue 4.0 1.0 Com. Ex. 4 P-9 EM1 D1 Blue 1.0 0.5 Com. Ex. 5 P-10 EM1 D1 Blue 1.2 0.3 Com. Ex. 6 P-11 EM1 D1 Blue 2.3 0.7 *In the table, the relative lifetime is a value calculated by taking the lifetime of the device of Example 9 as 1.

(142) The results of Examples 9 and 10 and Comparative Examples 4 to 6 show that an organic EL device using a bis- or triscarbazole polymer of the invention which has a specific substituent represented by the formulas (3) to (7) has superior luminous efficiency and longer lifetime as compared with an organic EL device using a comparative compound as an aromatic amine derivative.

Example 11 (Fabrication and Evaluation of Organic EL Device)

(143) An organic EL device was fabricated and evaluated in the same manner as in Example 9, except that a hole-transporting layer and an emitting layer were formed according to the following procedure. The results are shown in Table 2.

(144) On a hole-injecting layer, a xylene solution (1.0% by weight) of polymer P-1 obtained in Example 1 was formed into a 25 nm-thick film by spin coating. The resulting thin film was dried and hardened by heat treatment at 230? C. for 30 minutes to form a hole-transporting layer.

(145) Next, a xylene solution (1.0% by weight) in which the compound EM1 (host) and amine compound D1 including a styryl group (dopant) were mixed at the solid matter weight ratio of 95:5 was formed into a 40 nm-thick film by spin coating, dried at 150? C. for 30 minutes to obtain an emitting layer. On the film obtained, Alq was deposited to form a 10 nm-thick film. The layer obtained served as an electron-injecting layer.

Example 12

(146) An organic EL device was fabricated and evaluated in the same manner as in Example 11, except that P-2 obtained in Example 2 was used instead of P-1 as a hole-transporting material. The results are shown in Table 2.

Example 13

(147) An organic EL device was fabricated and evaluated in the same manner as in Example 11, except that P-3 obtained in Example 3 was used instead of P-1 as a hole-transporting material. The results are shown in Table 2.

Example 14

(148) An organic EL device was fabricated and evaluated in the same manner as in Example 11, except that P-4 obtained in Example 4 was used instead of P-1 as a hole-transporting material. The results are shown in Table 2.

Example 15

(149) An organic EL device was fabricated and evaluated in the same manner as in Example 11, except that P-5 obtained in Example 5 was used instead of P-1 as a hole-transporting material. The results are shown in Table 2.

Example 16

(150) An organic EL device was fabricated and evaluated in the same manner as in Example 11, except that P-6 obtained in Example 6 was used instead of P-1 as a hole-transporting material. The results are shown in Table 2.

Example 17

(151) An organic EL device was fabricated and evaluated in the same manner as in Example 11, except that P-7 obtained in Example 7 was used instead of P-1 as a hole-transporting material. The results are shown in Table 2.

Example 18

(152) An organic EL device was fabricated and evaluated in the same manner as in Example 11, except that arylamine compound D2 was used instead of amine compound D1 including a styryl group as a material for an emitting layer. The results are shown in Table 2.

Comparative Example 7

(153) An organic EL device was fabricated and evaluated in the same manner as in Example 11, except that P-9 obtained in Comparative Example 1 was used instead of P-1 as a hole-transporting material. The results are shown in Table 2.

Comparative Example 8

(154) An organic EL device was fabricated and evaluated in the same manner as in Example 11, except that P-10 obtained in Comparative Example 2 was used instead of P-1 as a hole-transporting material. The results are shown in Table 2.

Comparative Example 9

(155) An organic EL device was fabricated and evaluated in the same manner as in Example 11, except that P-11 obtained in Comparative Example 3 was used instead of P-1 as a hole-transporting material. The results are shown in Table 2.

(156) TABLE-US-00112 TABLE 2 Hole-transporting Emitting layer Emitting Luminous efficiency Relative Examples layer Host Dopant color (cd/A) lifetime* Example 11 P-1 EM1 D1 Blue 2.9 1.0 Example 12 P-2 EM1 D1 Blue 3.1 0.9 Example 13 P-3 EM1 D1 Blue 3.0 1.1 Example 14 P-4 EM1 D1 Blue 3.0 1.1 Example 15 P-5 EM1 D1 Blue 2.9 1.0 Example 16 P-6 EM1 D1 Blue 3.0 1.1 Example 17 P-7 EM1 D1 Blue 2.8 0.9 Example 18 P-1 EM1 D2 Blue 3.1 0.9 Com. Ex. 7 P-9 EM1 D1 Blue 0.3 0.1 Com. Ex. 8 P-10 EM1 D1 Blue 0.3 0.2 Com. Ex. 9 P-11 EM1 D1 Blue 1.3 0.3 *In the table, the relative lifetime is a value calculated by taking the lifetime of the device of Example 11 as 1.

INDUSTRIAL APPLICABILITY

(157) The organic EL device of the invention can be used in a planar luminous body such as a flat panel display of a wall-hanging TV, a copier, a printer, a backlight of a crystal liquid display, or a light source of instruments, a displaying board, sign lighting or the like.

(158) Although only some exemplary embodiments and/or examples of this invention have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments and/or examples without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are intended to be included within the scope of this invention.

(159) The documents described in the specification and the Japanese application specification claiming priority under the Paris Convention are incorporated herein by reference in its entirety.