Composition containing polymer compound and light-emitting device using the same
09691983 ยท 2017-06-27
Assignee
Inventors
- Masayuki Soga (Tokyo, JP)
- Osamu Goto (Ibaraki, JP)
- Kazuei Ohuchi (Ibaraki, JP)
- Nobuhiko Akino (Ibaraki, JP)
Cpc classification
C08L65/00
CHEMISTRY; METALLURGY
C08K3/11
CHEMISTRY; METALLURGY
H10K85/111
ELECTRICITY
C08G2261/3142
CHEMISTRY; METALLURGY
C08K3/11
CHEMISTRY; METALLURGY
C08G61/10
CHEMISTRY; METALLURGY
C08G2261/312
CHEMISTRY; METALLURGY
International classification
Abstract
It is an object of the present invention to provide a composition using a polymer compound, which is useful for manufacturing a blue phosphorescent light-emitting device excellent in luminous efficiency. The present invention provides a composition including: a polymer compound substantially consisting of a constitutional unit selected from a constitutional unit represented by Formula (1)-1 below, a constitutional unit represented by Formula (1)-2 below, a constitutional unit represented by Formula (2)-1 below, a constitutional unit represented by Formula (2)-2 below, and a constitutional unit derived from a phosphorescent light-emitting compound having a light-emitting spectrum peak at smaller than 480 nm and the polymer compound containing at least both of the constitutional unit represented by Formula (1)-1 and the constitutional unit represented by Formula (1)-2; and a phosphorescent light-emitting compound having a light-emitting spectrum peak at smaller than 480 nm. ##STR00001##
Claims
1. A composition comprising a polymer compound, a phosphorescent light-emitting compound that has a light-emitting spectrum peak at smaller than 480 nm, a phosphorescent light-emitting compound that has a light-emitting spectrum peak at 480 nm or larger and smaller than 580 nm, and a phosphorescent light-emitting compound that has a light-emitting spectrum peak at 580 nm or larger and smaller than 680 nm, wherein: the polymer compound comprises greater than 50% (by molarity) of constitutional units that are selected from among a constitutional unit represented by Formula (1)-1, a constitutional unit represented by Formula (1)-2, a constitutional unit represented by Formula (2)-1, and a constitutional unit represented by Formula (2)-2; the polymer compound contains at least both the constitutional unit represented by Formula (1)-1 and the constitutional unit represented by Formula (1)-2; and a ratio of a total weight of the phosphorescent light-emitting compound that has a light-emitting spectrum peak at 480 nm or larger and smaller than 580 nm and the phosphorescent light-emitting compound that has a light-emitting spectrum peak at 580 nm or larger and smaller than 680 nm relative to a weight of the phosphorescent light-emitting compound that has a light-emitting spectrum peak at smaller than 480 nm is 0.01 to 0.3; ##STR00074## wherein R.sup.1 represents an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, an aryloxy group, an aralkyl group, an arylalkoxy group, a substituted amino group, a substituted carbonyl group, a formyl group, a substituted carboxyl group, or a cyano group, and two or more R.sup.1s that are present in the polymer compound may be the same as or different from each other; R.sup.2 represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, an alkoxy group, an aryloxy group, an aralkyl group, an arylalkoxy group, a substituted amino group, a substituted carbonyl group, a formyl group, a substituted carboxyl group, a fluorine atom, or a cyano group, and two or more R.sup.2s that are present in the polymer compound may be the same as or different from each other; R.sup.3 represents an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, or an aralkyl group, and when two or more R.sup.3s are present in the polymer compound, R.sup.3s may be the same as or different from each other; R.sup.4 and R.sup.5 each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, an alkoxy group, an aryloxy group, an aralkyl group, an arylalkoxy group, a substituted amino group, a substituted carbonyl group, a formyl group, a substituted carboxyl group, a fluorine atom, or a cyano group, and when two or more R.sup.4s are present in the polymer compound, R.sup.4s may be the same as or different from each other, and two or more R.sup.5s that are present in the polymer compound may be the same as or different from each other; R.sup.6 represents a hydrogen atom, an alkoxy group, or a fluorine atom, and two or more R.sup.6s that are present in the polymer compound may be the same as or different from each other; and R.sup.7 represents a hydrogen atom, an alkoxy group, an aryloxy group, an arylalkoxy group, a substituted amino group, a substituted carbonyl group, a formyl group, a substituted carboxyl group, or a fluorine atom, and when two or more R.sup.7s are present in the polymer compound, R.sup.7s may be the same as or different from each other.
2. The composition according to claim 1, wherein R.sup.1 is an alkyl group, an aryl group, or an aralkyl group.
3. The composition according to claim 1, wherein R.sup.2 is a hydrogen atom.
4. The composition according to claim 1, wherein R.sup.3 is an alkyl group, an aryl group, or an aralkyl group.
5. The composition according to claim 4, wherein R.sup.3 is a methyl group.
6. The composition according to claim 1, wherein R.sup.5 is a hydrogen atom.
7. The composition according to claim 1, wherein R.sup.4 is a group represented by Formula (3) and/or a group represented by Formula (4): ##STR00075## wherein R.sup.8 and R.sup.9 each independently represent an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, or an aralkyl group; two R.sup.8s that are present in Formula (3) are optionally linked together; two or more R.sup.8s that are present in the polymer compound may be the same as or different from each other; two R.sup.9s that are present in Formula (4) are optionally linked together; and two or more R.sup.9s that are present in the polymer compound, may be the same as or different from each other.
8. The composition according to claim 1, wherein a ratio of a total number of moles of the constitutional unit represented by Formula (1)-2 and the constitutional unit represented by Formula (2)-2 relative to a total number of moles of the constitutional unit represented by Formula (1)-1 and the constitutional unit represented by Formula (2)-1 is 0.1 to 9.0.
9. The composition according to claim 7, wherein a ratio of a total number of moles of: the constitutional unit represented by Formula (1)-2 and the constitutional unit represented by Formula (2)-2 in which R.sup.4 is the group represented by Formula (3); and the constitutional unit represented by Formula (1)-2 and the constitutional unit represented by Formula (2)-2 in which R.sup.4 is the group represented by Formula (4), relative to a total number of moles of: the constitutional unit represented by Formula (1)-1; the constitutional unit represented by Formula (2)-1; the constitutional unit represented by Formula (1)-2 in which R.sup.4 is neither the group represented by Formula (3) nor the group represented by Formula (4); and the constitutional unit represented by Formula (2)-2 in which R.sup.4 is neither the group represented by Formula (3) nor the group represented by Formula (4), is 0.1 to 9.0.
10. The composition according to claim 7, wherein a ratio of a total number of moles of the constitutional unit represented by Formula (1)-2 and the constitutional unit represented by Formula (2)-2 in which R.sup.4 is the group represented by Formula (3), relative to a total number of moles of the constitutional unit represented by Formula (1)-2 and the constitutional unit represented by Formula (2)-2 in which R.sup.4 is the group represented by Formula (4), is 0.1 to 9.0.
11. The composition according to claim 1, wherein constitutional units represented by Formula (2)-1 are not substantially adjacent to each other; constitutional units represented by Formula (2)-2 are not substantially adjacent to each other; and the constitutional unit represented by Formula (2)-1 and the constitutional unit represented by Formula (2)-2 are not substantially adjacent to each other.
12. The composition according to claim 1, wherein the phosphorescent light-emitting compound that has a light-emitting spectrum peak at smaller than 480 nm is an iridium complex.
13. The composition according to claim 12, wherein the iridium complex has a fluorine atom or a trifluoromethyl group.
14. The composition according to claim 12, wherein the iridium complex has an alkyl group.
15. The composition according to claim 1, wherein a ratio of a weight of the phosphorescent light-emitting compound that has a light-emitting spectrum peak at smaller than 480 nm relative to a weight of the polymer compound is 0.05 to 0.5.
16. The composition according to claim 1, further comprising: one or more types of material selected from the group consisting of a hole transport material, an electron transport material, and a light-emitting material except for a phosphorescent light-emitting material.
17. The composition according to claim 16, wherein the electron transport material is an electron transport material having a structure represented by Formula (5): ##STR00076## wherein R.sup.10 represents an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, or an aralkyl group; three R.sup.10s are optionally linked together; and three R.sup.10s that are present in the polymer compound may be the same as or different from each other.
18. A liquid composition comprising: the composition according to claim 1 and a solvent.
19. A film comprising: the composition according to claim 1.
20. A light-emitting device comprising: an anode and a cathode; and a layer that is provided between the anode and the cathode and that comprises the composition according to claim 1.
21. The light-emitting device according to claim 20, wherein the layer is a light-emitting layer.
22. A surface light source comprising the light-emitting device according to claim 20.
23. A display device comprising the light-emitting device according to claim 20.
24. The composition according to claim 1, wherein the polymer compound consists of constitutional units that are selected from among the constitutional unit represented by Formula (1)-1, the constitutional unit represented by Formula (1)-2, the constitutional unit represented by Formula (2)-1, and the constitutional unit represented by Formula (2)-2.
25. The composition according to claim 1, wherein the ratio of the total weight of the phosphorescent light-emitting compound that has a light-emitting spectrum peak at 480 nm or larger and smaller than 580 nm and the phosphorescent light-emitting compound that has a light-emitting spectrum peak at 580 nm or larger and smaller than 680 nm relative to the weight of the phosphorescent light-emitting compound that has a light-emitting spectrum peak at smaller than 480 nm is 0.01 to 0.2.
26. The composition according to claim 1, wherein the ratio of the total weight of the phosphorescent light-emitting compound that has a light-emitting spectrum peak at 480 nm or larger and smaller than 580 nm and the phosphorescent light-emitting compound that has a light-emitting spectrum peak at 580 nm or larger and smaller than 680 nm relative to the weight of the phosphorescent light-emitting compound that has a light-emitting spectrum peak at smaller than 480 nm is 0.03 to 0.2.
Description
EXAMPLES
(1) For describing the present invention more in detail, examples will now be given; however, the present invention is not limited to these examples.
(2) The number average molecular weight and the weight average molecular weight were measured by size exclusion chromatography (SEC) as the polystyrene-equivalent number average molecular weight and the polystyrene-equivalent weight average molecular weight Among SEC, a chromatography in which the mobile phase is an organic solvent refers to gel permeation chromatography (GPC). As analysis conditions for GPC, methods illustrated in the analysis condition below were used.
(3) [Analysis Condition]
(4) The measurement sample was dissolved in tetrahydrofuran in a concentration of about 0.05% by weigh and 10 L of the resultant sample solution was injected into GPC (manufactured by Shimadzu Corporation; trade name: LC-10Avp). As the mobile phase of GPC, tetrahydrofuran was flowed at a flow rate of 2.0 mL/min. As the column, PLgel MIXED-B (manufactured by Polymer Laboratories Ltd.) was used. As the detector, UV-VIS detector (manufactured by Shimadzu Corporation; trade name: SPD-10Avp) was used.
(5) The LC-MS measurement was performed by a method below. The measurement sample was dissolved in chloroform or tetrahydrofuran so that the concentration of the sample became about 2 mg/mL and 1 L of the resultant sample solution was injected into LC-MS (manufactured by Agilent Technologies, Inc.; trade name: 1100LCMSD). As the mobile phase for LC-MS, ion-exchanged water, acetonitrile, tetrahydrofuran, and a solvent mixture thereof were used and if necessary, acetic acid was added thereto. As the column, L-column 2 ODS (3 m) (manufactured by Chemicals Evaluation and Research Institute, Japan; inner diameter: 2.1 mm, length; 100 mm, particle diameter: 3 m) was used.
(6) The TLC-MS measurement was performed by a method below. The measurement sample was dissolved in chloroform or tetrahydrofuran and a small amount of the resultant sample solution was applied onto the surface of a TLC glass plate (Merck & Co., Inc.; trade name: Silica gel 60 F.sub.254) that was cut beforehand. The resultant sample was measured by TLC-MS (manufactured by JEOL Ltd.; trade name: JMS-T100TD) using a helium gas heated to 240 to 350 C.
(7) The NMR measurement was performed, unless defined otherwise, by a method including: dissolving 5 to 20 mg of the measurement sample in about 0.5 mL of deuterated chloroform; and using NMR (manufactured by Varian, Inc. trade name: MERCURY 300).
(8) In Examples, the evaluation of the light-emitting spectrum peak of the phosphorescent light-emitting compound was performed, unless defined otherwise, by a method below. The phosphorescent light-emitting compound was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)). At this time, the solution was prepared so that the concentration of the solid content became 0.0008% by weight. This solution was excited using a fluorescence spectrophotometer (manufactured by JASCO Corporation; FP-6500) at a wavelength of 350 nm to measure the PL spectrum of the solution to evaluate the light-emitting spectrum peak.
(9) In Examples, the measurement of the luminous efficiency, voltage, and light-emitting chromaticity of the light-emitting device was performed using OLED TEST SYSTEM (manufactured by Tokyo Systems Development Co., Ltd.)
(10) ##STR00048##
(11) Into a four-neck flask, 8.08 g of 1,4-dihexyl-2,5-dibromobenzene, 12.19 g of bis(pinacolate)diboron, and 11.78 g of potassium acetate were charged and a gas inside the flask was purged with an argon gas. Thereto, 100 mL of dehydrated 1,4-dioxane was charged and the inside of the flask was deaerated with an argon gas. Thereto, 0.98 g of [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium (II) (Pd(dppf).sub.2Cl.sub.2) was charged and further, the inside of the flask was deaerated with argon. The resultant reaction mixture was heated-refluxed for 6 hours. To the reaction mixture, toluene was added and the resultant reaction mixture was washed with ion-exchanged water. To the washed organic phase, sodium sulfate anhydride and an activated carbon were added and the resultant organic phase was filtered by a funnel pre-coated with celite. The resultant filtrate was concentrated to obtain 11.94 g of a dark brown crystal. This crystal was recrystallized in n-hexane and the resultant crystal was washed with methanol. The crystal was dried under reduced pressure, thus obtaining 4.23 g of a white capillary crystal of a compound M-1. The yield was 42%.
(12) The results of the .sup.1H-NMR analysis and the LC-MS analysis of the compound M-1 are illustrated below. .sup.1H-NMR (300 MHz, CDCl.sub.3): (ppm)=0.88 (t, 6H), 1.23-1.40 (m, 36H), 1.47-1.56 (m, 4H), 2.81 (t, 4H), 7.52 (s, 2H) LC-MS (ESI, positive) m/z.sup.+=573 [M+K].sup.+
(13) ##STR00049##
(14) Commercially available 1,4-dibromo-2,5-dimethylbenzene was recrystallized to be purified and dried under reduced pressure. The resultant compound that exhibited an HPLC area percent value of 99.5% or more was used as a compound M-2.
(15) ##STR00050##
(16) In an argon gas atmosphere, in a flask equipped with a Dean-Stark dehydrator, 3,5-dibromo-4-ethylaniline (5.30 g, 20.0 mmol), copper (I) chloride (0.99 g, 10 mmol), 1,10-phenanthroline (1.80 g, 10 mmol), potassium hydroxide 8.98 g, 160 mmol) 4-tert-butyliodobenzene (16.1 g, 62 mmol), and dehydrated toluene (40 mL) were mixed. The reaction mixture is dehydrated while heating the resultant reaction mixture on an oil bath of 130 C., refluxing and stirring the reaction mixture for about 8 hours. The reaction mixture was diluted with toluene and the resultant reaction mixture was cooled down to room temperature. The reaction mixture was passed through a celite pre-coated filter to filter off insoluble matters. To the filtrate, an activated white clay (manufactured by Wako Pure Chemical Industries, Ltd.) was added and the resultant reaction mixture was stirred at room temperature for 1 hour to filter off a deposit solid. The above operation of filtering was repeated for three times. Then, the filtrate was concentrated, followed by adding hexane to the concentrate to deposit and filter a solid. The resultant solid was recrystallized in toluene-methanol, was further recrystallized in toluene-ethanol, and then, was purified by medium pressure silica gel column chromatography (hexane). Then, the solid was recrystallized again in toluene-methanol, thus obtaining an objective compound M-3 (5.70 g, HPLC area percent (ultraviolet ray wavelength; 254 nm)>99.9%, yield: 54%) as a white crystal.
(17) The result of the .sup.1H-NMR analysis of the compound M-3 is illustrated below.
(18) .sup.1H-NMR (300 MHz, THF-d.sub.8): (ppm)=1.33 (s, 18H), 2.49 (s, 3H), 7.01 (d, 4H), 7.16 (s, 2H), 7.36 (d, 4H)
(19) ##STR00051##
(20) (Step (4a))
(21) In an argon gas atmosphere, in a flask, 3,5-dibromo-4-methylaniline (47.0 g, 177 mmol), 35% by weight hydrochloric acid (111 mL), and ion-exchanged water (111 mL) were mixed and the resultant reaction mixture was cooled down in an ice bath. Into the reaction mixture, a solution in which sodium nitrite (12.9 g, 186 mmol) was dissolved in ion-exchanged water (about 130 mL) was drooped over about 30 minutes. After the completion of dropping, the reaction mixture was stirred at room temperature for about 1 hour and was cooled down in an ice bath again and into the reaction mixture, a solution in which potassium iodide (30.9 g, 186 mmol) was dissolved in ion-exchanged water (about 130 mL) was dropped over about 33 minutes. After the completion of dropping, the reaction mixture was stirred at room temperature for about 3 hours and while stirring the reaction mixture, the reaction mixture was slowly added to a separately prepared 10% by weight sodium hydrogen carbonate aqueous solution (about 1,200 mL). The reaction mixture was extracted by adding ethyl acetate thereto and the organic chase was washed with a 21% by weight sodium sulfite aqueous solution, was dried over magnesium sulfate anhydride, and was filtered and the filtrate was concentrated to obtain a crude product (77 g). The crude product was dissolved in acetone and to the resultant solution, an activated car-bon was added. The resultant reaction mixture was stirred and then, filtered and the filtrate was concentrated. The concentrate was dissolved in acetone again and to the resultant solution, an activated carbon was added, followed by stirring the resultant reaction mixture. The reaction mixture was filtered and the filtrate was concentrated, followed by drying a deposited solid under reduced pressure to obtain a yellow brown solid (about 50 g). The obtained solid was dissolved in hexane and to the resultant solution, ethanol was added to crystallize the resultant reaction mixture, followed by filtering and drying under reduced pressure the resultant crystal, thus obtaining intermediate 2,6-dibromo-4-iodotoluene (28.4 g, yield; 43%, compound M4a) as a white crystal.
(22) The result of the .sup.1H-NMR analysis of the compound M4a is illustrated below.
(23) .sup.1H-NMR (300 MHz, CDCl.sub.3): (ppm)=2.51 (s, 3H), 7.83 (s, 2H)
(24) (Step (4b))
(25) In an argon gas atmosphere, in a flask, into a solution in which the compound M4a (22.6 g, 60.0 mmol) was dissolved in dehydrated tetrahydrofuran (300 mL), a tetrahydrofuran solution of isopropylmagnesium chloride (manufactured by Sigma Aldrich Corp., concentration: 2.0 M, 60 mL) was dropped at room temperature over 10 minutes and the resultant reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was cooled down in an ice bath and thereto, 2-isopropyloxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolan (22.3 g, 120 mmol) as added. The resultant reaction mixture was stirred at room temperature for 2 hours and was cooled down in an ice bath again and into the reaction mixture, 0.1 N hydrochloric acid (180 mL) was dropped. The resultant reaction mixture was extracted with ethyl acetate and the organic phase was washed with a 15% by weight brine twice, was dried over sodium sulfate anhydride, and was filtered. The filtrate was concentrated and thereto, methanol was added to deposit a solid. The deposited solid was filtered and was dried under reduced pressure, thus obtaining intermediate 2,6-dibromo-4-(4,4,5,5-tetraethyl-1,3,2-dioxaborolan-2-yl)toluene (16.3 g, yield 72%, compound M4b) as a white crystal.
(26) The result of the .sup.1H-NMR analysis of the compound M4b is illustrated below.
(27) .sup.1H-NMR (300 MHz, CDCl.sub.3): (ppm)=1.33 (s, 12H), 2.58 (s, 3H), 7.90 (s, 2H)
(28) (Step (4c)
(29) In an argon gas atmosphere, in a flask, 4-bromo-tert-butylbenzene (125 g, 587 mmol) was dissolved in dehydrated tetrahydrofuran (470 mL) and the resultant reaction solution was cooled down to 70 C. Into the reaction solution, an n-butyllithium/hexane solution (1.6 M, 367 mL, 587 mmol) was dropped over 90 minutes and then, the resultant reaction mixture was stirred for 2 hours to prepare a 4-tert-butylphenyllithium/tetrahydrofuran solution.
(30) Separately, in an argon gas atmosphere, in a flask, cyanur chloride (50.8 g, 276 mmol) was dissolved in dehydrated tetrahydrofuran (463 mL) and the resultant solution was cooled down to 70 C. Thereinto, the whole amount of the thus-prepared 4-tert-butylphenyllithium/tetrahydrofuran solution was dropped at a rate by which the internal temperature of the flask maintained 60 C. or less. After the completion of dropping, the resultant reaction mixture was stirred at 40 C. for 4 hour and then, at room temperature for 4 hours. To the reaction mixture, ion-exchanged water (50 mL) was slowly added and then, the solvent was distilled off under reduced pressure. To the resultant residue, ion-exchanged water and chloroform were added to extract the residue into an organic phase and further, the organic phase was washed with ion-exchanged water, followed by distilling off the solvent from the organic phase under reduced pressure. To the resultant residue, acetonitrile was added and the resultant reaction mixture was stirred while heating-refluxing the reaction mixture, followed by filtering insoluble matters by filtration during heating the reaction mixture. The filtrate was concentrated under reduced pressure and further, the concentrated filtrate was cooled down to 70 C. to deposit and filter a solid. The resultant solid was dissolved in a solvent mixture of chloroform/hexane and the resultant solution was purified by silica gel column chromatography (eluent: chloroform/hexane), followed by recrystallizing the solution in acetonitrile, thus obtaining the objective intermediate 4,6-bis(4-tert-butylphenyl)-2-chloro-1,3,5-triazine (41.3 g, 109 mmol, yield: 39%, compound M4c) as a white crystal.
(31) The results or the .sup.1H-NMR analysis and the LC-MS analysis of the compound M4c are illustrated below.
(32) .sup.1H-NMR (300 MHz, CDCl.sub.3): (ppm)=1.39 (s, 18H), 7.56 (d, 4H), 8.54 (d, 4H)
(33) LC/MS (APPI, positive) m/z.sup.+=380 [M+H].sup.+
(34) (Step (4d))
(35) In a nitrogen gas atmosphere, in a flask, the compound M4b (7.52 g, 20.01 mmol), the compound M4c (9.12 g, 24.0 mmol), tetrakis(triphenylphosphine) palladium (0) (2.32 g, 2.0 mmol), silver carbonate (16.5 g, 60 mmol), and dehydrated tetrahydrofuran (160 mL) were mixed and while shading and heating-refluxing the resultant reaction mixture, the reaction mixture was stirred for 33 hours. After the completion of the reaction, the reaction mixture was diluted with toluene (400 mL) and therefrom, insoluble matters were filtered off. The filtrate was concentrated and thereto, acetonitrile (200 mL) was added, followed by stirring the resultant reaction mixture for 1 hour while refluxing the reaction mixture. Then, the reaction mixture was cooled down to room temperature and a deposited solid was filtered and was dried under reduced pressure to obtain a crude product. The crude product was purified by medium pressure silica gel chromatography (hexane/chloroform=98/2 to 70/30) and was subjected to recrystallization in toluene-acetonitrile repeatedly for three times, thus obtaining an objective compound M-4 (2.46 g, HPLC area percent (ultraviolet ray wavelength: 254 nm): 99.6%, yield: 21%) as a white crystal.
(36) The result of the .sup.1H-NMR analysis of the compound M-4 is illustrated below.
(37) .sup.1H-NMR (300 MHz, THF-d.sub.6): (ppm)=1.43 (s, 18H), 2.68 (s, 3H), 7.65 (d, 4H), 8.67 (d, 4H), 8.89 (s, 2H)
(38) <Step 1: Synthesis of Compound (A)>
(39) ##STR00052##
(40) 3.89 g of 2-chloro-5-n-decylpyrimidine, 2.65 g of 2,4-difluorophenylboronic acid, 35 mL of 1,2-dimethoxyethan, and 42 mL of a 2 M potassium carbonate aqueous solution were charged into a two-neck flask to prepare a reaction solution. An argon gas was passed through the reaction solution for 20 minutes and to the reaction solution, 0.88 g of tetrakistriphenylphosphine palladium (0) complex was added, followed by heating and refluxing the resultant reaction solution using an oil bath in an argon atmosphere for 16 hours. The organic phase was separated and recovered and was separated and purified by silica gel chromatography (elution: solvent mixture of dichloromethane and hexane), thus obtaining 4.1 g of a compound (A).
(41) The result of the .sup.1H-NMR analysis of the compound (A) is illustrated below.
(42) .sup.1H-NMR (400 MHz, CDCl.sub.3): (ppm)=8.66 (s, 2H), 8.08-8.15 (m, 1H), 6.91-7.00 (m, 2H), 2.63 (t, 2H), 1.18-1.68 (m, 16H), 0.88 (t, 3H)
(43) <Step 2: Synthesis of Compound (B)>
(44) ##STR00053##
(45) 800 mg of iridium trichloride n-hydrate, 1.58 g of the compound (A), 64 mL of 2-ethoxyethanol, and 22 mL of water were charged into a two-neck flask and the resultant reaction solution was heated in an argon atmosphere for 14 hours to be refluxed. The resultant reaction solution was cooled down to room temperature and thereto, water was added, followed by filtering a generated solid, thus obtaining a compound (B). The isolation yield was 57%.
(46) The result of the .sup.1H-NMR analysis of the compound (B) is illustrated below.
(47) .sup.1H-NMR (400 MHz, CDCl.sub.3): (ppm)=9.03 (s, 4H), 8.79 (s, 4H), 6.42 (t, 4H), 5.25 (d, 4H), 2.52 (m, 4H), 2.11 (m, 4H), 1.18-1.70 (m, 64H), 0.87 (t, 12H)
(48) <Step 3: Synthesis of Phosphorescent Light-Emitting Compound A>
(49) ##STR00054##
(50) 111 mg of the compound (B), 45 mg of sodium picolinate, and 40 mL of 2-ethoxyethanol were charged into an eggplant-shaped flask and the resultant reaction solution was irradiated with a microwave (2,450 MHz) In an argon atmosphere for 10 minutes. The resultant reaction solution was cooled down to room temperature and the solvent was concentrated under reduced pressure to obtain a solid. The solid was recrystallized in dichloromethane-hexane, thus obtaining the phosphorescent light-emitting compound A. The isolation yield thereof was 74%.
(51) The result of the .sup.1H-NMR analysis of the phosphorescent light-emitting compound A is illustrated below.
(52) .sup.1H-NMR (400 MHz, CDCl.sub.3: (ppm)=8.68-8.72 (m, 3H), 8.36 (d, 1H), 8.01 (t, 1H), 7.83 (d, 1H), 7.49 (dd, 1H), 7.26 (d, 1H), 6.54 (dd, 1H), 6.47 (dd, 1H), 5.83 (d, 1H) 5.60 (d, 1H), 2.60-2.67 (m, 2H), 2.39-2.48 (m, 2H), 1.23-1.60 (m, 32H), 0.88 (t, 6H)
(53) The phosphorescent light-emitting compound A had a light-emitting spectrum peak at 472 nm.
(54) ##STR00055##
(55) 4-tert-butylbenzonitrile (10.0 g) and dehydrated chloroform (75 mL) were charged into a round bottom flask and a gas in the flask was charged with a nitrogen, gas. To the resultant reactor solution, trifluoromethanesulfonic acid (11 mL) was added while stirring the reaction solution and the resultant reaction solution was stirred at room temperature for 48 hours. After the completion of the reaction, the reaction solution was cooled down to room temperature and the reaction solution was washed with 10% by weight ammonia water and ion-exchanged water each for one time. The retrieved organic phase was dehydrated over magnesium sulfate and therefrom, and then the solvent was distilled off under reduced pressure. The resultant residue was repeatedly recrystallized in a solvent mixture of chloroform/hexane, thus obtaining 4.2 g of an electron transport material ET-A.
(56) The result of the .sup.1H-NMR analysis of the electron transport material ET-A is illustrated below.
(57) .sup.1H-NMR (300 MHz, CDCl.sub.3): (ppm)=1.40 (s, 27H), 7.59 (d, J=7.5 Hz, 6H), 8.68 (d, J=7.5 Hz, 6H)
(58) In an inert atmosphere, 5.20 g of 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene, 5.42 g of bis(4-bromophenyl)-(4-sec-butylphenyl)-amine, 2.2 mg of palladium acetate, 15.1 mg of tris(2-methylphenyl)phosphine, 1.91 g of trioctylmethylammonium chloride (trade name: Aliquat 336; manufactured by Sigma Aldrich Corp.), and 70 mL of toluene were mixed and the resultant reaction solution was heated to 105 C. Into the reaction solution, 19 mL of a 2M sodium carbonate aqueous solution was dropped and the resultant reaction solution was refluxed for 4 hours. After the completion of the reaction, 121 mg of phenylboronic acid was added to the reaction solution and further, the resultant reaction solution was refluxed for 3 hours. Next, to the reaction solution, an aqueous solution of sodium N,N-diethyldithiocarbamate trihydrate was added and the resultant reaction solution was stirred at 80 C. for 2 hours. The reaction solution was cooled down and then, the reaction solution was washed with water, a 3% by weight acetic acid aqueous solution, and water in this order, followed by passing the resultant toluene solution through an alumina column and a silica gel column to be purified. The resultant toluene solution was dropped into a large amount of methanol and the resultant reaction solution was stirred. The resultant precipitate was filtered and was dried, thus obtaining a polymer compound HP-1. The polystyrene-equivalent number average molecular weight Xn and The polystyrene-equivalent weight average molecular weight Mw of the polymer compound HP-1 that were measured under the above-described analysis conditions, were 8.410.sup.4 and 3.410.sup.5 respectively.
(59) It is presumed from the charging ratios of the monomers that the polymer compound HP-1 is a polymer compound having a constitutional unit below and a mole fraction below in which the constitutional, units are alternately polymerized.
(60) ##STR00056##
(61) In an inert gas atmosphere, the compound M-1 (0.770 g), the compound M-2 (0.244 g), the compound M-3 (0.326 g), and 15.2 mL of toluene were mixed and while heating the resultant reaction solution, the reaction solution was stirred. To the reaction solution, palladium (II) acetate (0.5 mg) and tris(2-methoxyphenyl)phosphine (3.4 mg) were added and the resultant reaction solution was heated to 100 C. Then, to the reaction solution, a 20% by weight tetraethylammonium hydroxide aqueous solution (5.3 mL) was added and the resultant reaction solution was refluxed for 4.5 hours.
(62) Next, to the reaction mixture, 2-isopropylphenylboric acid (25.5 mg), palladium (II) acetate (0.5 mg), tris(2-methoxyphenyl)phosphine (3.3 mg), and a 20% by weight tetraethylammonium hydroxide aqueous solution (5.2 mL) were added and further, the resultant reaction solution was refluxed for 17 hours.
(63) From the reaction solution, the aqueous phase was removed and to the resultant reaction mixture, a solution in which sodium N,N-diethyldithiocarbamate trihydrate (0.86 g) was dissolved in ion-exchanged water (17 mL) was added, followed by stirring the resultant reaction mixture at 85 C. for 2 hours. The reaction mixture was cooled down to room temperature and was washed with water twice, with a 3% by weight acetic acid aqueous solution twice, and with water four times and the resultant toluene solution was dropped into methanol. A precipitate was deposited and then, the precipitate was filtered and dried. The thoroughly dried precipitate (solid) was dissolved in toluene and the resultant toluene solution was passed through a column filled with silica gel and alumina to be purified. The resultant toluene solution was dropped into methanol and a precipitate was deposited, followed by filtering and drying this precipitate. The yield of this precipitate (hereinafter, called polymer compound P-1) was 0.58 g. The polystyrene-equivalent number average molecular weight and the polystyrene-equivalent weight average molecular weight of the polymer compound P-1 measured under the above-described analysis conditions were Mn=1.010.sup.5 and Mw=3.810.sup.5.
(64) It is presumed from the charging ratios of the monomers that the polymer compound P-1 is a polymer compound having a constitutional unit below and a mole fraction below in which a constitutional unit of (PA) and a constitutional unit selected from (PB) are alternately polymerized.
(65) ##STR00057##
(66) In an inert gas atmosphere, the compound M-1 (0.724 g), the compound M-2 (0.231 g, the compound M-4 (0.347 g), and 15.6 of toluene were mixed and while heating the resultant reaction solution, the reaction solution was stirred. To the reaction solution, palladium (II) acetate (0.5 mg) and tris(2-methoxyphenyl)phosphine (3.1 mg) were added and the resultant reaction solution was heated to 100 C. Then, to the reaction solution, a 20% by weight tetraethylammonium hydroxide aqueous solution (4.9 mL) was added and the resultant reaction solution was refluxed for hours.
(67) Next, to the reaction solution, 2-isopropylphenylboric acid (24.1 mg), palladium (II) acetate (0.5 mg), tris(2-methoxyphenyl)phosphine (3.1 mg), and a 20% by weight tetraethylammonium hydroxide aqueous solution (4.9 mL) were added and further, the resultant reaction solution was refluxed for 18 hours.
(68) From the reaction solution, the aqueous phase was removed and to the resultant reaction mixture, a solution in which sodium N,N-diethyldithiocarbamate trihydrate (0.81 g) was dissolved in ion-exchanged water (16 mL) was added, followed by stirring the resultant reaction mixture at 85 C. for 2 hours. The reaction mixture was cooled down to room temperature and was washed with water twice, with a 3% by weight acetic acid aqueous solution twice, and with water five times and the resultant toluene solution was dropped into methanol. A precipitate was deposited and then, the precipitate was filtered and dried. The thoroughly dried precipitate (solid) was dissolved in toluene and the resultant toluene solution was passed through a column filled with silica gel and alumina to be purified. The resultant toluene solution was dropped into methanol and a precipitate was deposited, followed by filtering and drying this precipitate. The yield of this precipitate (hereinafter, called polymer compound P-2) was 0.63. The polystyrene-equivalent number average molecular weight and the polystyrene-equivalent weight average molecular weight of the polymer compound P-2 measured under the above-described analysis conditions were Mn=4.210.sup.4 and Mw=1.210.sup.5.
(69) It is presumed from the charging ratios of the monomers that the polymer compound P-2 is a polymer compound having a constitutional unit below and a mole fraction below in which a constitutional unit of (PA) and a constitutional unit selected from (PB) are alternately polymerized.
(70) ##STR00058##
(71) In an inert gas atmosphere, the compound M-1 (0.537 g), the compound M-3 (0.227 g), the compound M-4 (0.384 g), and 15 mL of toluene were mixed and while heating the resultant reaction solution, the reaction solution was stirred. To the reaction solution, palladium (II) acetate (0.4 mg) and tris(2-methoxyphenyl)phosphine (2.3 mg) were added and the resultant reaction solution was heated to 100 C. Then, to the reaction solution, a 20% by weight tetraethylammonium hydroxide aqueous solution (5.5 mL) was added and the resultant reaction solution was refluxed for 5 hours.
(72) Next, to the reaction Solution, 2-isopropylphenylboric acid (17.9 mg), palladium (II) acetate 0.4 mg), tris(2-methoxyphenyl)phosphine (2.3 mg), and a 20% by weight tetraethylammonium hydroxide aqueous solution (3.6 mL) were added and further, the resultant reaction solution was refluxed for 17 hours.
(73) From the reaction solution, the aqueous phase was removed and to the resultant reaction mixture, a solution in which sodium N,N-diethyldithiocarbamate trihydrate (0.60 g) was dissolved in ion-exchanged water (12 mL) was added, followed by stirring the resultant reaction mixture at 85 C. for 2 hours. The reaction mixture was cooled down to room temperature and was washed with water twice, with a 3% by weight acetic acid aqueous solution twice, and with water twice and the resultant toluene solution was dropped into methanol. A precipitate was deposited and then, the precipitate was filtered and dried. The thoroughly dried precipitate (solid) was dissolved in toluene and the resultant toluene solution was passed through a column filled with silica gel and alumina to be purified. The resultant toluene solution was dropped into methanol and a precipitate was deposited, followed by filtering and drying this precipitate. The yield of this precipitate (hereinafter, called polymer compound P-3) was 0.56 g. The polystyrene-equivalent number average molecular weight and the polystyrene-equivalent weight average molecular weight of the polymer compound P-3 measured under the above-described analysis conditions were Mn=2.510.sup.4 and Mw=1.110.sup.5.
(74) It is presumed from the charging ratios of the monomers that the polymer compound P-3 is a polymer compound having a constitutional unit below and a mole fraction below in which a constitutional unit of (PA) and a constitutional unit selected from (PB) are alternately polymerized.
(75) ##STR00059##
(76) In an inert gas atmosphere, the compound M-1 (3.13 g), 2,7-dibromo-9,9-dioctylfluorene (3.47 g), and 80.0 mL of toluene were mixed and while heating the resultant reaction solution, the reaction solution was stirred. To the reaction solution, palladium (II) acetate (2.2 mg) and tris(2-methoxyphenyl)phosphine (13.4 ng) were added and the resultant reaction solution was heated to 100 C. Then, into the reaction solution, a 20% by weight tetraethylammonium hydride aqueous solution (22.0 mL) was dropped and the resultant reaction solution was refluxed for 4.5 hours. After the completion of the reaction, to the reaction solution, phenylboric acid (78 mg), palladium (II) acetate (2.2 mg), tris(2-methoxyphenyl)phosphine (13.4 mg), and a 20% by weight tetraethylarsonium hydroxide aqueous solution (22.0 mL) were added and further, the resultant reaction solution was refluxed for 15 hours. From the reaction solution, the aqueous phase was removed and to the resultant reaction mixture, a 0.2M sodium diethyldithiocarbamate aqueous solution (70 mL) was added, followed by stirring the resultant reaction mixture at 85 C. for 2 hours. The reaction mixture was cooled down to room temperature and was washed with water three times, with a 3% by weight acetic acid aqueous solution three times, and with water three times and the resultant toluene solution was dropped into methanol. A precipitate was deposited and then, the precipitate was filtered and dried. The thoroughly dried precipitate (solid) was dissolved in toluene and the resultant toluene solution was passed through a column filled with silica gel and alumina to be purified. The resultant toluene solution was dropped into methanol and a precipitate was deposited, followed by filtering an drying this precipitate. The yield of this precipitate (hereinafter called polymer compound CP-1) was 3.52 g. The polystyrene-equivalent number average molecular weight and the polystyrene-equivalent weight average molecular weight of the polymer compound CP-1 measured under the above-described analysis conditions were Mn=3.610.sup.5 and Mw=9.410.sup.5.
(77) It is presumed from the charging ratios of the monomers that the polymer compound CP-1 is a polymer compound having a constitutional unit below and a mole fraction below in which the constitutional units are alternately polymerized.
(78) ##STR00060##
(79) In a nitrogen atmosphere, in a flask, a mixture of 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (1.5915 g, 3.000 mmol), the compound M-3 (1.5881 g, 3.000 mmol), and toluene (30 mL) was heated to 90 C. and to the resultant reaction mixture, palladium acetate (1.0 mg, 4.5 mol), tris(2-methoxyphenyl)phosphine (6.3 mg, 18 mol), and a 20% by weight tetraethylammonium hydroxide aqueous solution (10 mL, 14 mmol) were added. The resultant reaction mixture was further stirred for about 20 hours while refluxing the reaction mixture by heating.
(80) Next, to the reaction mixture, phenylboric acid (0.366 g, 3.0 mmol), palladium acetate (1.0 mg, 4.5 mol), and tris(2-methoxyphenyl)phosphine (6.3 mg, 18 mol) were added and while heating the resultant reaction mixture to 105 C. and refluxing the reaction mixture, the reaction mixture was stirred for about 4 hours.
(81) Next, to the reaction mixture, bromobenzene (0.66 g, 4.2 mmol), palladium acetate (1.0 mg, 4.5 mol), and tris(2-methoxyphenyl)phosphine (6.3 mg, 18 mol) were added and while heating the resultant reaction mixture to 105 C. and refluxing the reaction mixture, the reaction mixture was stirred for about 4 hours.
(82) Furthermore, to the reaction mixture, a solution in which sodium N,N-diethyldithiocarbamate trihydrate (1.83 g) was dissolved in ion-exchanged water (18 mL) was added and while hearing the resultant reaction solution to 85 C., the reaction solution was stirred for 2 hours.
(83) The organic phase was separated from the aqueous phase and was sequentially washed with ion-exchanged water twice, with a 3% by weight acetic acid aqueous solution twice, and with ion-exchanged water twice. The organic phase was dropped into methanol to precipitate a polymer compound and the polymer compound was filtered and dried to obtain a solid. This solid was dissolved in toluene and the resultant toluene solution was passed through a silica gel column and an alumina column through which toluene was passed beforehand. The resultant toluene solution was dropped into methanol to precipitate a polymer compound and the polymer compound was filtered and dried, thus obtaining a polymer compound CP-2 (1.87 g). The number polystyrene-equivalent average molecular weight (Mn) and the polystyrene-equivalent weight average molecular weight (Mw) of the polymer compound CP-2 measured under the above-described analysis conditions were Mn=2.610.sup.4 and Mw=3.510.sup.4.
(84) It is presumed from the charging ratios of the monomers that the polymer compound CP-2 is a polymer compound having a constitutional unit below and a mole fraction below in which the constitutional units are alternately polymerized.
(85) ##STR00061##
(86) In a nitrogen atmosphere, in a flask, a mixture of 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (1.2851 mg, 2.000 mmol), 1,4-dihexyl-2,5-dibromobenzene (646.8 mg, 1.600 mmol), the compound M-3 (211.7 mg, 0.400 mmol), and toluene (40 mL) was heated to 90 C. and to the resultant reaction mixture, palladium acetate (0.9 mg, 4 mol), tris(2-methoxyphenyl)phosphine 5.6 mg, 16 mol), and a 20% by weight tetraethylammonium hydroxide aqueous solution (6.6 mL, 9.4 mmol) were added. The resultant reaction mixture was further stirred for about 6 hours while refluxing the reaction mixture by heating.
(87) Next, to the reaction mixture, phenylboric acid (25.7 mg, 0.200 mmol), palladium acetate (0.9 mg, 4 mol) and tris(2-methoxyphenyl)phosphine (5.6 mg, 16 mol) that were dissolved in toluene (20 mL), and a 20% by weight tetraethylammonium hydroxide aqueous solution (6.6 mL, 9.4 mmol) were added and while heating the resultant reaction mixture to 105 C., the reaction mixture was stirred for about 16 hours while refluxing the reaction mixture.
(88) Furthermore, to the reaction mixture, a solution in which sodium N,N-diethyldithiocarbamate trihydrate (1.22 g) was dissolved in ion-exchanged water (20 mL) was added and while heating the resultant reaction mixture to 850 C., the reaction mixture was stirred for 2 hours.
(89) The organic phase was separated from the aqueous phase and was sequentially washed with ion-exchanged water twice, with a 3% by weight acetic acid aqueous solution twice, and with ion-exchanged water twice. The organic phase was dropped into methanol to precipitate a polymer compound and the polymer compound was filtered and dried to obtain a solid. This solid was dissolved an toluene and the resultant toluene solution was passed through a silica gel column and an alumina column through which toluene was passed beforehand. The resultant toluene solution was dropped into methanol to precipitate a polymer compound and the polymer compound was filtered and dried, thus obtaining a polymer compound CP-3 (1.14 g). The polystyrene-equivalent number average molecular weight (Mn) and the polystyrene-equivalent weight average molecular weight (Mw) of the polymer compound CP-3 measured under the above-described analysis conditions were Mn=4.310.sup.4 and Mw=1.010.sup.5.
(90) It is presumed from the charging ratios of the monomers that the polymer compound CP-3 is a polymer compound having a constitutional unit below and a mole fraction below in which a constitutional unit of (PA) and a constitutional unit selected from (PB) are alternately polymerized.
(91) ##STR00062##
(92) In a nitrogen atmosphere, in a flask, a mixture of 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (1.2851 mg, 2.000 mmol), 1,4-dihexyl-2,5-dibromobenzene (646.8 mg, 1600 mmol), the compound M-4 (238.3 mg, 0.400 mol), and toluene (40 mL) was heated to 90 C. and to the resultant reaction mixture, palladium acetate (0.9 mg, 4 mol), tris(2-methoxyphenyl)phosphine (5.6 mg, 16 mol), and a 20% by weight tetraethylammonium hydroxide aqueous solution (6.6 mL, 9.4 mmol) were added. The resultant reaction mixture was further stirred for about 6 hours while refluxing the reaction mixture by heating.
(93) Next, to the reaction mixture, phenylboric acid (25.7 mg, 0.200 mmol), palladium acetate (0.9 mg, 4 mol) and tris(2-methoxyphenyl)phosphine (5.6 mg, 16 mol) that were dissolved in toluene (20 mL), and a 20% by weight tetraethylammonium hydroxide aqueous solution (6.6 mL, 9.4 mmol) were added and while heating the resultant reaction mixture to 105 C., the reaction mixture was stirred for about 16 hours while refluxing the reaction mixture.
(94) Furthermore, to the reaction mixture, a solution in which sodium N,N-diethyldithiocarbamate trihydrate (1.22 g) was dissolved in ion-exchanged water (20 mL) was added and while heating the resultant reaction mixture to 85 C., the reaction mixture was stirred for 2 hours.
(95) The organic phase was separated from the aqueous phase and was sequentially washed with ion-exchanged water twice, with a 3% by weight acetic acid aqueous solution twice, and with ion-exchanged water twice. The organic phase was dropped into methanol to precipitate a polymer compound and the polymer compound was filtered and dried to obtain a solid. This solid was dissolved in toluene and the resultant toluene solution was passed through a silica gel column and an alumina column through which toluene was passed beforehand. The resultant toluene solution was dropped into methanol to precipitate a polymer compound and the polymer compound was filtered and dried, thus obtaining a polymer compound CP-4 (1.14 g). The polystyrene-equivalent number average molecular weight (Mn) and the polystyrene-equivalent weight average molecular weight (Mw) of the polymer compound CP-4 measured under the above-described analysis conditions were Mn=5.610.sup.4 and Mw=1.410.sup.5.
(96) It is presumed from the charging ratios of the monomers that the polymer compound CP-4 is a polymer compound having a constitutional unit below and a mole fraction below in which a constitutional unit of (PA) and a constitutional unit selected from (PB) are alternately polymerized.
(97) ##STR00063##
(98) ##STR00064##
(99) Commercially available 1,4-dibromobenzene was recrystallized to be purified and dried under reduced pressure. The resultant compound that exhibited an HPLC area percent value of 99.5% or more was used as a compound M-5.
(100) ##STR00065##
(101) Commercially available 1,3-dibromobenzene was purified by distillation under reduced pressure. The resultant compound that exhibited an HPLC area percent value of 99.2% or more was used as a compound M-6.
(102) ##STR00066##
(103) As the phosphorescent light-emitting compound Ir-1, trade name: ADS065BE (manufactured by American Dye Source, Inc.) was purchased to be used.
(104) The phosphorescent light-emitting compound Ir-1 had a light-emitting spectrum peak at 470 nm.
(105) ##STR00067##
(106) Light-Emitting Material T
(107) The light-emitting material T was synthesized through a synthesis method described in Japanese Patent Application Laid-open No. 2006-188673.
(108) The light-emitting material T had a light-emitting spectrum peak at 619 nm.
(109) ##STR00068##
(110) Light-Emitting Material U
(111) The light-emitting material U was synthesized through a synthesis method described in Journal of American Chemical Society, Vol. 107, pp. 1431-1432 (1985).
(112) The light-emitting material U had a light-emitting spectrum peak at 508 nm.
(113) In an inert gas atmosphere, the compound M-1 (1.0317 g), the Compound M-5 (0.0978 g), the compound M-3 (0.4396 g), the compound M-4 (0.4906 g), and toluene (35 mL) were mixed and while heating the resultant reaction solution at 100 C. the reaction solution was stirred. To the reaction solution, palladium (II) acetate (0.9 mg) and tris(2-methoxyphenyl)phosphine (6.0 mg) were added and while continuing heating at 100 C., a 20% by weight tetraethylammonium hydroxide aqueous solution (7.0 mL) was dropped into the reaction solution, followed by refluxing the resultant reaction solution for 7 hours. Next, to the reaction solution, 2-isopropylphenylboric acid (51 mg), palladium (II) acetate (0.5 mg), tris(2-methoxyphenyl)phosphine (2.9 mg), and a 20% by weight tetraethylammonium hydroxide aqueous solution (7.0 mL) were added and further, the resultant reaction solution was refluxed for 16 hours. From the reaction solution, the aqueous phase was removed and to the resultant reaction mixture, a solution in which sodium N,N-diethyldithiocarbamate trihydrate (0.58 g) was dissolved in ion-exchanged water (11.6 mL) was added, followed by stirring the resultant reaction mixture for 2.5 hours while heating the reaction mixture to 85 C.
(114) The organic phase was separated from the aqueous phase and was washed with 3.6% by weight hydrochloric acid twice, with a 2.5% by weight ammonia aqueous solution twice, and with water our times. The washed organic phase (toluene solution) was dropped into methanol to generate a precipitate and this precipitate was filtered and dried. The thoroughly dried precipitate (solid) was dissolved in toluene (68 mL) and the resultant toluene solution was passed through a column filled with silica gel and alumina to be purified. The resultant toluene solution was dropped into methanol to generate a precipitate and this precipitate was filtered and dried. The yield of the precipitate (hereinafter, called polymer compound P-4) was 0.99 g. The polystyrene-equivalent number average molecular weight and the polystyrene-equivalent weight average molecular weight of the polymer compound P-4 measured under the above-described analysis conditions were Mn=1.410.sup.4 and Mw=3.210.sup.4.
(115) It is presumed from the charging ratios of the monomers that the polymer compound P-4 is a polymer compound having a constitutional unit below and a mole fraction below in which the constitutional units are alternately polymerized.
(116) ##STR00069##
(117) In an inert gas atmosphere, the compound M-1 (1.0318 g), the compound M-6 (0.0978 g), the compound M-3 (0.4396 g), the compound M-4 (0.4907 g, and toluene (35 mL) were mixed and while heating the resultant reaction solution at 100 C., the reaction solution was stirred. To the reaction solution, palladium (II) acetate (0.9 mg) and tris(2-methoxyphenyl)phosphine (5.8 mg) were added and while continuing heating at 100 C., a 20% by weight tetraethylammonium hydroxide aqueous solution (7.0 mL) was dropped into the reaction solution, followed by refluxing the resultant reaction solution for 7.5 hours. Next, to the reaction solution, 2-isopropylphenylboric acid (102 mg), palladium (II) acetate (0.5 mg), tris(2-methoxyphenyl)phosphine (29 mg), and a 20% by weight tetraethylammonium hydroxide aqueous solution (7.0 mL) were added and further, the resultant reaction solution was refluxed for 16 hours. From the reaction solution, the aqueous phase was removed and to the resultant reaction mixture, a solution in which sodium N,N-diethyldithiocarbamate trihydrate (0.58 g) was dissolved in ion-exchanged water (11.6 mL) was added, followed by stirring the resultant reaction mixture for 8 hours while heating the reaction mixture to 85 C.
(118) The organic phase was separated from the aqueous phase and was washed with 3.6% by weight hydrochloric acid twice, with a 2.5% by weight ammonia aqueous solution twice, and with water four times. The washed organic phase (toluene solution) was passed through a column filled with silica gel and alumina to be purified. The resultant toluene solution was dropped into methanol to generate a precipitate and this precipitate was filtered and dried. The yield of the precipitate (hereinafter, called polymer compound P-5) as 0.93 g. The polystyrene-equivalent number average molecular weight and the polystyrene-equivalent weight average molecular weight of the polymer compound P-5 measured under the above-described analysis conditions were Mn=7.310.sup.3 and Mw=1.310.sup.4.
(119) It is presumed from the charging ratios of the monomers that the polymer compound P-5 is a polymer compound having a constitutional unit below and a mole fraction below in which the constitutional units are alternately polymerized.
(120) ##STR00070##
(121) In an inert gas atmosphere, the compound M-1 (1.0464 g), the compound M-2 (0.1660 g), the compound M-3 (0.1113 g), the compound M-4 (0.7464 g), and toluene (35 mL) were mixed and while heating the resultant reaction solution at 100 C., the reaction solution was stirred. To the reaction solution, palladium (II) acetate (0.9 mg) and tris(2-methoxyphenyl)phosphine (6.0 mg) were added and while continuing heating at 100 C., a 20% by weight tetraethylammonium hydroxide aqueous solution (7.1 mL) was dropped into the reaction solution, followed by refluxing the resultant reaction solution for 7.5 hours. Next, to the reaction solution, 2-isopropylphenylboric acid (51 mg), palladium (II) acetate (0.5 mg), tris(2-methoxyphenyl)phosphine (2.9 mg), and a 20% by weight tetraethylammonium hydroxide aqueous solution (7.1, mL) were added and further, the resultant reaction solution was refluxed for 15 hours. From the reaction solution, the aqueous phase was removed and to the resultant reaction mixture, a solution in which sodium N,N-diethyldithiocarbamate trihydrate (0.60 g) was dissolved in ion-exchanged water (12 mL) was added, followed by stirring the resultant reaction mixture for 2.5 hours while heating the reaction mixture to 85 C.
(122) The organic phase was separated from the aqueous phase and was washed with 3.6% by weight hydrochloric acid twice, with a 2.5% by weight ammonia aqueous solution twice, and with water five times. The washed organic phase (toluene solution) was passed through a column filled with silica gel and alumina to be purified. The resultant toluene solution was dropped into methanol to generate a precipitate and this precipitate was filtered and dried. The yield of the precipitate (hereinafter, called polymer compound P-6) was 0.87 g. The polystyrene-equivalent number average molecular weight and the polystyrene-equivalent weight average molecular weight of the polymer compound P-6 measured under the above-described analysis conditions were Mn=8.910.sup.3 and Mw=1.7010.sup.4.
(123) It is presumed from the charging ratios of the monomers that the polymer compound P-6 is a polymer compound having a constitutional unit below and a mole fraction below in which the constitutional units are alternately polymerized.
(124) ##STR00071##
(125) In an inert gas atmosphere, the compound M-1 (1.0002 g), the compound M-2 (0.1059 g), the compound M-3 (0.2131 g), the compound M-4 (0.7133 g) and toluene (35 mL) were mixed and while heating the resultant reaction solution at 100 C., the reactor solution was stirred. To the reaction solution, palladium (II) acetate (0.9 mg) and tris(2-methoxyphenyl)phosphine (5.6 mg) were added and while continuing heating at 100 C., a 20% by weight tetraethylammonium hydroxide aqueous solution (6.8 mL) was dropped into the resultant reaction solution, followed by refluxing the resultant reaction solution for 6.5 hours. Next, to the reaction solution, 2-isopropylphenylboric acid (6 mg), palladium (II) acetate (0.5 mg), tris(2-methoxyphenyl)phosphine (2.8 mg), and a 20% by weight tetraethylammonium hydroxide aqueous solution (6.8 mL) were added and further, the resultant reaction solution was refluxed for 16.5 hours. From the reaction solution, the aqueous phase was removed and to the resultant reaction mixture, a solution in which sodium N,N-diethyldithiocarbamate trihydrate (0.57 g) was dissolved in ion-exchanged water (11.9 mL) was added, followed by stirring the resultant reaction mixture for 2 hours while heating the reaction mixture to 85 C.
(126) The organic phase was separated from the aqueous phase and was washed with 3.6% by weight hydrochloric acid twice, with a 2.5% by weight ammonia aqueous solution twice, and with water four times. The washed organic phase (toluene solution) was passed through a column filled with silica gel and alumina to be purified. The resultant toluene solution was dropped into methanol to generate a precipitate and this precipitate was filtered and dried. The yield of the precipitate (hereinafter, called polymer compound P-7) was 98 g. The polystyrene-equivalent number average molecular weight and the polystyrene-equivalent weight average molecular weight of the polymer compound P-7 measured under the above-described analysis conditions were Mn=5.310.sup.3 and Mw=1.010.sup.4.
(127) It is presumed from the charging ratio of the monomers that the polymer compound P-7 is a polymer compound having a constitutional unit below and a mole fraction below in which the constitutional units are alternately polymerized.
(128) ##STR00072##
(129) In an inert gas atmosphere, the compound M-1 (2.8051 g), the compound M-6 (1.3324 g), and toluene (41 mL) were mixed and while heating the resultant reaction solution at 100 C., the reaction solution was stirred. To the reaction solution, palladium (II) acetate (1.2 mg) and tris(2-methoxyphenyl)phosphine (8.0 g) were added and while continuing heating at 100 C., a 20% by weight tetraethylammonium hydroxide aqueous solution (19.1 mL, was dropped into the resultant reaction solution, followed by refluxing the resultant reaction solution for 5.5 hours. Next, to the reaction solution, 2-isopropylphenylboric acid (92 mg), palladium (II) acetate (1.4 mg), tris(2-methoxyphenyl)phosphine (7.9 mg) and a 20% by weight tetraethylammonium hydroxide aqueous solution (19.1 mL) were added and further, the resultant reaction solution was refluxed for 16 hours. From the reaction solution, the aqueous phase was removed and to the resultant reaction mixture, a solution in which sodium N,N-diethyldithiocarbamate trihydrate (1.60 g) was dissolved in ion-exchanged water (32 mL) was added, followed by stirring the resultant reaction mixture for 2 hours while heating the reaction mixture to 85 C.
(130) The organic phase was separated from the aqueous phase and was washed with 3.6% by weight hydrochloric acid twice, with a 2.5% by weight ammonia aqueous solution twice, and with water four times. The washed organic phase (toluene solution) was dropped into methanol to generate a precipitate and this precipitate was filtered and dried. The thoroughly dried precipitate (solid) was dissolved in toluene and the resultant toluene solution was passed through a column filled with silica gel and alumina to be purified. The resultant toluene solution was dropped into methanol to generate a precipitate and this precipitate was filtered and dried. The yield of the precipitate (hereinafter, called polymer compound CP-5) was 1.49 g. The polystyrene-equivalent number average molecular weight and the polystyrene-equivalent weight average molecular weight of the polymer compound C-5 measured under the above-described analysis conditions were Mn=1.510.sup.4 and Mw=6.110.sup.4.
(131) It is presumed from the charging ratios of the monomers that the polymer compound CP-5 is a polymer compound having a constitutional, unit below and a mole fraction below in which the constitutional units are alternately polymerized.
(132) ##STR00073##
(133) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of poly(3,4)ethylenedioxythiophene/polystyrenesulfonic acid (manufactured by H. C. Starck GmbH; trade name: CLEVIOS P AI4083) (hereinafter, called CLEVIOS P) was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound P-1, the phosphorescent light-emitting compound A, and the electron transport material ET-A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 1.2% by weight of the above-described materials (in a weight ratio of polymer compound P-1/phosphorescent light-emitting compound A/electron transport material ET-A=85/5/10). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer 1 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer 1 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device 1.
(134) When a voltage of until 20 V was applied to the light-emitting device 1, electroluminescence (EL) emitting blue color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 2.39 cd/A and at this time, the voltage was 6.1 V. The luminous efficiency at a brightness of 50 cd/m.sup.2 was 2.05 cd/A and at this time, the voltage was 6.6 V. The luminous efficiency at a brightness of 100 cd/m.sup.2 was 1.83 cd/A and at this time, the voltage was 7.1 V.
(135) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot place at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical. Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound P-2 and the phosphorescent light-emit-zing compound A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 1.6% by weight of the above-described materials (in a weight ratio of polymer compound P-2/phosphorescent light-emitting compound A=95/5). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer 2 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer 2 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium level in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device 2.
(136) When a voltage of until 20 V was applied to the light-emitting device 2, electroluminescence (EL) emitting blue color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 1.72 cd/A and at this time, the voltage was 5.2 V. The luminous efficiency at a brightness of 50 cd/m.sup.2 was 1.67 cd/A and at this time, the voltage was 5.8 V. The luminous efficiency at a brightness of 100 cd/m.sup.2 was 1.62 cd/A and at this time, the voltage was 6.3 V.
(137) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound P-3 and the phosphorescent light-emitting compound A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 1.7% by weight of the above-described materials (in a weight ratio of polymer compound P-3/phosphorescent light-emitting compound A=95/5). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer 3 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer 3 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device 3.
(138) When a voltage of until 20 V was applied to the light-emitting device 3, electroluminescence (EL) emitting blue color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 4.08 cd/A and at this time, the voltage was 4.1 V and the luminescent chromaticity was (0.16, 0.31). The luminous efficiency at a brightness of 50 cd/m.sup.2 was 4.74 cd/A and at this time, the voltage was 4.3 V and the luminescent chromaticity was (0.16, 0.30). The luminous efficiency at a brightness of 100 cd/m.sup.2 was 5.30 cd/A and at this time, the voltage was 4.5 V and the luminescent chromaticity was (0.15, 0.30).
(139) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so that the resultant coating film has a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound CP-1 and the phosphorescent light-emitting compound A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight of the above-described materials (in a weight ratio of polymer compound CP-1/phosphorescent light-emitting compound A=95/5). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer C1 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer C1 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device C1.
(140) When a voltage of until 20 V was applied to the light-emitting device C1, electroluminescence (EL) emitting blue color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 0.01 cd/A and at this time, the voltage was 18.8 V. The brightness could not reach 50 cd/m.sup.2 and 100 cd/m.sup.2.
(141) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound CP-1, the phosphorescent light-emitting compound A, and the electron transport material ET-A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight of the above-described materials (in a weight ratio of polymer compound CP-1/phosphorescent light-emitting compound A/electron transport material ET-A=85/5/10). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer C2 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer C2 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device C2.
(142) When a voltage of until 20 V was applied to the light-emitting device C2, electroluminescence (EL) emitting blue color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 0.01 cd/A and at this time, the voltage was 18.4 V. The brightness could not reach 50 cd/m.sup.2 and 100 cd/m.sup.2.
(143) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound CP-2 and the phosphorescent light-emitting compound A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 2.3% by weight of the above-described materials (in a weight ratio of polymer compound CP-2/phosphorescent light-emitting compound A=95/5). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer C3 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer C3 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device C3.
(144) When a voltage of until 20 V was applied to the light-emitting device C3, electroluminescence (EL) emitting blue color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 0.01 cd/A and at this time, the voltage was 13.1 V. The brightness could nor reach 50 cd/m.sup.2 and 100 cd/m.sup.2.
(145) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 20 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound CP-2, the phosphorescent light-emitting compound A, and the electron transport material ET-A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 2.3% by weight of the above-described materials (in a weight ratio of polymer compound CP-2/phosphorescent light-emitting compound A/electron transport material ET-A=85/5/10). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer C4 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer C4 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device C4.
(146) When a voltage of until 20 V was applied to the light-emitting device C4, electroluminescence (EL) emitting blue color light was observed. The luminous efficiency at a a brightness of 20 cd/m.sup.2 was 0.03 cd/A and at this time, the voltage was 10.2 V. The luminous efficiency at a brightness of 50 cd/m.sup.2 was 0.02 cd/A and at this time, the voltage was 13.1 V. The luminous efficiency at a brightness of 10 cd/m.sup.2 was 0.02 cd/A and at this time, the voltage was 19.3 V.
(147) Onto a glass substrate coated with an ITO film by a sputtering method an a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co, Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed Onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound CP-3 and the phosphorescent light-emitting compound A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 1.7% by weight of the above-described materials (in a weight ratio of polymer compound CP-3/phosphorescent light-emitting compound A=95/5). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer C5 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer C5 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device C5.
(148) When a voltage of until 20 V was applied to the light-emitting device C5, electroluminescence (EL) emitting blue color light was observed. However, the brightness could not reach 20 cd/m.sup.2, 50 cd/m.sup.2, and 100 cd/m.sup.2.
(149) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weigh, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound CP-3, the phosphorescent light-emitting compound. A, and the electron transport material ET-A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 1.7% by weight of the above-described materials (in a weight ratio of polymer compound CP-3/phosphorescent light-emitting compound A/electron transport material ET-A=85/5/10). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer C6 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer C6 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device C6.
(150) When a voltage of until 20 V was applied to the light-emitting device C6, electroluminescence (EL) emitting blue color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 0.01 cd/A and at this time, the voltage was 19.6 V. The brightness could not reach 50 cd/m.sup.2 and 100 cd/m.sup.2.
(151) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound CP-4 and the phosphorescent light-emitting compound A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 1.7% by weight of the above-described materials (in a weight ratio of polymer compound CP-4/phosphorescent light-emitting compound A=95/5). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer C7 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer C7 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device C7.
(152) When a voltage of until 20 V was applied to the light-emitting device C7, electroluminescence (EL) emitting blue color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 0.04 cd/A and at this time, the voltage was 15.2 V. The luminous efficiency at a brightness of 50 cd/m.sup.2 was 0.03 cd/A and at this time, the voltage was 18.4 V. The brightness could nor reach 100 cd/m.sup.2.
(153) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound P-4 and the phosphorescent light-emitting compound A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 2.6% by weight of the above-described materials (in a weight ratio of polymer compound P-4/phosphorescent light-emitting compound A=95/5). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer 4 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer 4 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device 4.
(154) When a voltage of until 20 V was applied to the light-emitting device 4, electroluminescence (EL) emitting blue color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 3.02 cd/A and at this time, the voltage was 4.0 V. The luminous efficiency at a brightness of 50 cd/m.sup.2 was 3.44 cd/A and at this time, the voltage was 4.2 V. The luminous efficiency at a brightness of 100 cd/m.sup.2 was 3.79 cd/A and at this time, the voltage was 4.4 V.
(155) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus containing a thermally treated film. Next, the polymer compound P-5 and the phosphorescent light-emitting compound A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 2.6% by weight of the above-described materials (in a weight ratio of polymer compound P-5/phosphorescent light-emitting compound A=95/5). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer 5 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or Less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer 5 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device 5.
(156) When a voltage of until 20 V was applied to the light-emitting device 5, electroluminescence (EL) emitting blue color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 4.78 cd/A and at this time, the voltage was 4.2 V. The luminous efficiency at a brightness of 50 cd/m.sup.2 was 5.28 cd/A and at this time, the voltage was 4.4 V. The luminous efficiency at a brightness of 100 cd/m.sup.2 was 5.71 cd/A and at this time, the voltage was 4.6 V,
(157) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and, was made a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound P-6 and the phosphorescent light-emitting compound A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentrator of 2.6% by weight of the above-described materials (in a weight ratio of polymer compound P-6/phosphorescent light-emitting compound A=95/5). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer 6 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C.for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited deposited on the film the light-emitting layer 6 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device 6.
(158) When a voltage of until 20 V was applied to the light-emitting device 6, electroluminescence (EL) emitting blue color light was observed. The luminous efficient at a brightness of 20 cd/m.sup.2 was 5.23 cd/A and at this time, the voltage was 4.5 V. The luminous efficiency at a brightness of 50 cd/m.sup.2 was 5.88 cd/A and at this time, the voltage was 4.9 V. The luminous efficiency at a brightness of 100 cd/m.sup.2 was 6.04 cd/A and at this time, the voltage was 5.3 V.
(159) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes thus obtaining a thermally treated film. Next, the polymer compound P-7 and the phosphorescent light-emitting compound. A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 2.7% by weight of the above-described materials in a weight ratio of polymer compound P-7/phosphorescent light-emitting compound A=95/5). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer 7 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer 7 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device 7.
(160) When a voltage of until 20 V was applied to the light-emitting device 7, electroluminescence (EL) emitting blue color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 5.21 cd/A and at this time, the voltage was 4.1 V. The luminous efficiency at a brightness of 50 cd/m.sup.2 was 6.73 cd/A and at this time, the voltage was 4.3 V. The luminous efficiency at a brightness of 100 cd/m.sup.2 was 7.79 cd/A and at this time, the voltage was 4.5 V.
(161) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound P-3 and the phosphorescent light-emitting compound Ir-1 were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 1.8% by weight of the above-described materials (in a weight ratio of polymer compound P-3/phosphorescent light-emitting compound Ir-1=95/5). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer 8 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer 8 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacture a light-emitting device 8.
(162) When a voltage of until 20 V was applied to the light-emitting device 8, electroluminescence (EL) emitting blue color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 1.64 cd/A and at this time, the voltage was 4.6 V. The luminous efficiency at a brightness of 50 cd/m.sup.2 was 2.00 cd/A and at this time, the voltage was 4.8 V. The luminous efficiency at a brightness of 100 cd/m.sup.2 was 2.30 cd/A and at this time, the voltage was 4.9 V.
(163) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound P-3 and the phosphorescent light-emitting compound A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 1.8% by weight of the above-described materials (in a weight ratio of polymer compound P-3/phosphorescent light-emitting compound A=90/10). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer 9 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer 9 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device 9.
(164) When a voltage of until 20 V was applied to the light-emitting device 9, electroluminescence (EL) emitting blue color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 6.31 cd/A and at this time, the voltage was 4.2 V. The luminous efficiency at a brightness of 50 cd/m.sup.2 was 7.06 cd/A and at this time, the voltage was 4.5 V. The luminous efficiency at a brightness of 100 cd/m.sup.2 was 7.66 cd/A and at this time, the voltage was 4.7 V.
(165) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm and the resultant coating film was dried on a hot plate as 200 C., for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was laced onto the film of CLEVIOS P and was made a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound P-3 and the phosphorescent light-emitting compound A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 1.9% by weight of the above-described materials (in a weight ratio of polymer compound P-3/phosphorescent light-emitting compound A=80/20). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer 10 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer 10 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device 10.
(166) When a voltage of until 20 V was applied to the light-emitting device 10, electroluminescence (EL) emitting blue color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 8.27 cd/A and at this time, the voltage was 4.6 V. The luminous efficiency at a brightness of 50 cd/m.sup.2 was 9.26 cd/A and at this time, the voltage was 4.9 V. The luminous efficiency at a brightness of 100 cd/m.sup.2 was 10.07 cd/A and at this time, the voltage was 5.2 V.
(167) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a ho-t plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound P-3 and the phosphorescent light-emitting compound A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade); in a concentration of 1.9% by weight of the above-described materials (in a weight ratio of polymer compound P-3/phosphorescent light-emitting compound A=70/30). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer 11 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer 11 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device 11.
(168) When a voltage of until 20 V was applied to the light-emitting device 11, electroluminescence (EL) emitting blue color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 8.22 cd/A and at this time, the voltage was 4.8 V. The luminous efficiency at a brightness of 50 cd/m.sup.2 was 9.21 cd/A and at this time, the voltage was 5.2 V. The luminous efficiency at a brightness of 100 cd/m.sup.2 was 9.87 cd/A and at this time, the voltage was 5.5 V.
(169) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound CP-5 and the phosphorescent light-emitting compound A were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 2.4% by weight of the above-described materials (in a weight ratio of polymer compound CP-5/phosphorescent light-emitting compound A=95/5). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer C8 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer C8 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device C8.
(170) When a voltage of until 20 V was applied to the light-emitting device C8, electroluminescence (EL) emitting blue color light was observed. However, the brightness could not reach 20 cd/m.sup.2, 50 cd/m.sup.2, and 100 cd/m.sup.2.
(171) TABLE-US-00002 TABLE 2 LIGHT-EMITTING LAYER PHOSPHO- ELEC- POLY- RESCENT TRON 20 cd/m.sup.2 50 cd/m.sup.2 100 cd/m.sup.2 MER LIGHT- TRANS- COMPO- LUMINOUS VOLT- LUMINOUS VOLT- LUMINOUS VOLT- COM- EMITTING PORT SITION EFFICIENCY AGE EFFICIENCY AGE EFFICIENCY AGE POUND COMPOUND MATERIAL RATIO (cd/A) (V) (cd/A) (V) (cd/A) (V) EXAMPLE 1 P-1 A ET-A 85/5/10 2.39 6.1 2.05 6.6 1.83 7.1 EXAMPLE 2 P-2 A 95/5/0 1.72 5.2 1.67 5.8 1.62 6.3 EXAMPLE 3 P-3 A 95/5/0 4.08 4.1 4.74 4.3 5.30 4.5 EXAMPLE 4 P-4 A 95/5/0 3.02 4.0 3.44 4.2 3.76 4.4 EXAMPLE 5 P-5 A 95/5/0 4.78 4.2 5.28 4.4 5.71 4.6 EXAMPLE 6 P-6 A 95/5/0 5.23 4.5 5.88 4.9 6.04 5.3 EXAMPLE 7 P-7 A 95/5/0 5.21 4.1 6.73 4.3 7.79 4.5 EXAMPLE 8 P-3 Ir-1 95/5/0 1.64 4.6 2.00 4.8 2.30 4.9 EXAMPLE 9 P-3 A 90/10/0 6.31 4.2 7.06 4.5 7.66 4.7 EXAMPLE 10 P-3 A 80/20/0 8.27 4.6 9.28 4.9 10.07 5.2 EXAMPLE 11 P-3 A 70/30/0 8.22 4.8 9.21 5.2 9.87 5.5 COMPARATIVE CP-1 A 95/5/0 0.01 18.8 EXAMPLE 1 COMPARATIVE CP-1 A ET-A 85/5/10 0.01 18.4 EXAMPLE 2 COMPARATIVE CP-2 A 95/5/0 0.01 13.1 EXAMPLE 3 COMPARATIVE CP-2 A ET-A 85/5/10 0.03 10.2 0.02 13.1 0.02 19.3 EXAMPLE 4 COMPARATIVE CP-3 A 95/5/0 EXAMPLE 5 COMPARATIVE CP-3 A ET-A 85/5/10 0.01 19.6 EXAMPLE 6 COMPARATIVE CP-4 A 95/5/0 0.04 15.2 0.03 18.4 EXAMPLE 7 COMPARATIVE CP-5 A 95/5/0 EXAMPLE 8
(172) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound P-3, The phosphorescent light-emitting compound A, the light-emitting material U, and the light-emitting material T were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 1.9% by weight of the above-described materials (in a weight ratio of polymer compound P-3/phosphorescent light-emitting compound A/light-emitting material U/light-emitting material T=77/20/2.0/1.0). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer 12 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer 12 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device 12.
(173) When a voltage of until 20 V was applied to the light-emitting device 12, electroluminescence (EL) emitting white color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 12.69 cd/A and at this time, the voltage was 4.7 V and the luminescent chromaticity was (0.50, 0.45). The luminous efficiency at a brightness of 50 cd/m.sup.2 was 14.25 cd/A and at this time, the voltage was 5.1 V and the luminescent chromaticity was (0.49, 0.45). The luminous efficiency at a brightness of 100 cd/m.sup.2 was 15.27 cd/A and at this time, the voltage was 5.5 V and the luminescent chromaticity was (0.48, 0.46).
(174) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound P-3, the phosphorescent light-emitting compound A, the light-emitting material U, and the light-emitting material T were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 1.9% by weight of the above-described materials (in a weight ratio of polymer compound P-3/phosphorescent light-emitting compound A/light-emitting material U/light-emitting material T=78.5/20/1.0/0.5). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer 13 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer 13 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device 13.
(175) When a voltage of until 20 V was applied to the light-emitting device 13, electroluminescence (EL) emitting white color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 10.56 cd/A and at this time, the voltage was 4.8 V and the luminescent chromaticity was (0.48, 0.46). The luminous efficiency at a brightness of 50 cd/m.sup.2 was 12.27 cd/A and at this time, the voltage was 5.3 V and the luminescent chromaticity was (0.47, 0.47). The luminous efficiency at a brightness of 100 cd/m.sup.2 was 13.63 cd/A and at this time, the voltage was 5.7 V and the luminescent chromaticity was (0.46, 0.48).
(176) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co. Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound P-3, the phosphorescent light-emitting compound A, the light-emitting material U, and the light-emitting material T were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade) in a concentration of 1.9% by weight of the above-described materials (in a weight ratio of polymer compound P-3/phosphorescent light-emitting compound A/light-emitting material U/light-emitting material T=79.25/20/0.5/0.25). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer 14 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer 14 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device 14.
(177) When a voltage of until 20 V was applied to the light-emitting device 14, electroluminescence (EL) emitting white color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 13.77 cd/A and at this time, the voltage was 4.4 V and the luminescent chromaticity was (0.37, 0.50). The luminous efficiency at a brightness of 50 cd/m.sup.2 was 15.86 cd/A and at this time, the voltage was 4.8 V and the luminescent chromaticity as (0.3, 0.50). The luminous efficiency at a brightness of 100 cd/m.sup.2 was 17.29 cd/A and at this time, the voltage was 5.1 V and the luminescent chromaticity was (0.35, 0.51).
(178) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was placed and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have the resultant coating film has a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weigh, basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer compound P-3, the phosphorescent light-emitting compound A, the light-emitting material U, and the light-emitting material T were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade) in a concentration of 1.9% by weight of the above-described materials (in a weight ratio of polymer compound P-3/phosphorescent light-emitting compound A/light-emitting material U/light-emitting material T=79.4/20/0.5/0.1). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer 15 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1.010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer 15 in a thickness of about 5 nm and next, aluminum, was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device 15.
(179) When a voltage of until 20 V was applied to the light-emitting device 15, electroluminescence (EL) emitting white color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 14.77 cd/A and at this time, the voltage was 4.6 V and the luminescent chromaticity was (0.41, 0.49). The luminous efficiency at a brightness of 50 cd/m.sup.2 was 17.34 cd/A and at this time, the voltage was 5.0 V and the luminescent chromaticity was (0.40, 0.50). The luminous efficiency at a brightness of 100 cd/m.sup.2 was 19.07 cd/A and at this time, the voltage was 5.4 V and the luminescent chromaticity was (0.39, 0.51).
(180) Onto a glass substrate coated with an ITO film by a sputtering method in a thickness of 45 nm, a suspension of CLEVIOS P was place and was made to a coating film by a spin coating method so as to have a thickness of about 50 nm, and the resultant coating film was dried on a hot plate at 200 C. for 10 minutes. Next, the polymer compound HP-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 0.7% by weight, and the resultant xylene solution was placed onto the film of CLEVIOS P and was made to a coating film by a spin coating method so as to have a thickness of about 20 nm. The resultant coating film was dried in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis) at 180 C. for 60 minutes, thus obtaining a thermally treated film. Next, the polymer Compound P-3, the phosphorescent light-emitting compound A, the light-emitting material U, and the light-emitting material T were dissolved in xylene (manufactured by Kanto Chemical Co., Ltd.; for the electronic industries (EL grade)) in a concentration of 1.9% by weight of the above-described materials (in a weight ratio of polymer compound P-3/phosphorescent light-emitting compound A/light-emitting material U/light-emitting material T=79/20/0.5/0.5). The resultant xylene solution was placed onto the thermally treated film of the polymer compound HP-1 and was made to a coating film as a light-emitting layer 16 by a spin coating method so as to have a thickness of about 60 nm. Then, in a nitrogen atmosphere having an oxygen concentration and a water concentration of each 10 ppm or less (on a weight basis), the resultant coating film was dried at 130 C. for 10 minutes. The pressure of the atmosphere was reduced to 1010.sup.4 Pa or less and as the cathode, barium was vapor-deposited on the film of the light-emitting layer 16 in a thickness of about 5 nm and next, aluminum was vapor-deposited on the barium layer in a thickness of about 60 nm. After the vapor-deposition, the sealing was performed using a glass substrate, thus manufacturing a light-emitting device 16.
(181) When a voltage of until 20 V was applied to the light-emitting device 16, electroluminescence (EL) emitting white color light was observed. The luminous efficiency at a brightness of 20 cd/m.sup.2 was 17.41 cd/A and at this time, the voltage was 4.5 V and the luminescent chromaticity was (0.33, 0.55). The luminous efficiency at a brightness of 50 cd/m.sup.2 was 20.47 cd/A and at this time, the voltage was 4.9 V and the luminescent chromaticity was (0.32, 0.55). The luminous efficiency at a brightness of 100 cd/m.sup.2 was 22.64 cd/A and at this time, the voltage was 5.2 V and the luminescent chromaticity was (0.31, 0.55).
(182) TABLE-US-00003 TABLE 3 LIGHT-EMITTING LAYER PHOSPHO- RESCENT LIGHT- ELEC- EMITTING TRON POLY- COMPOUND TRANS- 20 cd/m.sup.2 MER OR LIGHT- PORT LUMINOUS VOLT- LUMINES- COM- EMITING MATE- COMPOSITION EFFICIENCY AGE CENT CHRO- POUND MATERIAL RIAL RATIO (cd/A) (V) MATICITY EXAMPLE 12 P-3 A/U/T 77/20/2/1/0 12.69 4.7 (0.50, 0.45) EXAMPLE 13 P-3 A/U/T 78.5/20/1/0.5/0 10.56 4.8 (0.48, 0.46) EXAMPLE 14 P-3 A/U/T 79.25/20/0.5/0.25/0 13.77 4.4 (0.37, 0.50) EXAMPLE 15 P-3 A/U/T 79.4/20/0.5/0.1/0 14.77 4.6 (0.41, 0.49) EXAMPLE 16 P-3 A/U/T 79/20/0.5/0.5/0 17.41 4.5 (0.33, 0.55) EXAMPLE 3 P-3 A 95/5/0 4.08 4.1 (0.16, 0.31) 50 cd/m.sup.2 100 cd/m.sup.2 LUMINOUS VOLT- LUMINES- LUMINOUS VOLT- LUMINES- EFFICIENCY AGE CENT CHRO- EFFICIENCY AGE CENT CHRO- (cd/A) (V) MATICITY (cd/A) (V) MATICITY EXAMPLE 12 14.25 5.1 (0.49, 0.45) 15.27 5.5 (0.48, 0.46) EXAMPLE 13 12.27 5.3 (0.47, 0.47) 13.63 5.7 (0.46, 0.48) EXAMPLE 14 15.86 4.8 (0.35, 0.50) 17.29 5.1 (0.35, 0.51) EXAMPLE 15 17.34 5.0 (0.40, 0.50) 19.07 5.4 (0.39, 0.51) EXAMPLE 16 20.47 4.9 (0.32, 0.55) 22.64 5.2 (0.31, 0.55) EXAMPLE 3 4.74 4.3 (0.16, 0.30) 5.30 4.5 (0.15, 0.30)