JP5206760B2 - Organic electroluminescence element, lighting device and display device - Google Patents

Description

  The present invention relates to an organic electroluminescence element, an illuminating device, and a display device, and particularly relates to an organic electroluminescent element, an illuminating device, and a display device having the same that are excellent in light emission luminance, luminous efficiency, and durability.

  Conventionally, there is an electroluminescence display (ELD) as a light-emitting electronic display device. Examples of the constituent elements of ELD include inorganic electroluminescent elements and organic electroluminescent elements (hereinafter also referred to as organic EL elements).

  Inorganic electroluminescent elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements.

  On the other hand, an organic EL element has a structure in which a light emitting layer containing a compound that emits light is sandwiched between a cathode and an anode. By injecting electrons and holes into the light emitting layer and recombining them, excitons (exciton) are obtained. And emits light using the emission of light (fluorescence / phosphorescence) when the exciton is deactivated, and can emit light at a voltage of several volts to several tens of volts. Since it is a light-emitting type, it has a wide viewing angle, high visibility, and since it is a thin-film type complete solid-state device, it has attracted attention from the viewpoints of space saving and portability.

  For the development of organic EL elements for practical use in the future, organic EL elements that emit light efficiently and with high brightness with lower power consumption are desired. For example, stilbene derivatives, distyrylarylene derivatives, or tris A technique for doping a styrylarylene derivative with a trace amount of a phosphor to improve emission luminance and extending the lifetime of the device (see, for example, Patent Document 1), and using 8-hydroxyquinoline aluminum complex as a host compound. A device having an organic light-emitting layer doped with a phosphor (see, for example, Patent Document 2), a device having an organic light-emitting layer doped with a quinacridone dye as an 8-hydroxyquinoline aluminum complex as a host compound (for example, Patent Document 3) is known.

  In the technique disclosed in the above-mentioned patent document, when the emission from the excited singlet is used, the generation ratio of the singlet exciton and the triplet exciton is 1: 3. % And the light extraction efficiency is about 20%, so the limit of the external extraction quantum efficiency (ηext) is set to 5%.

  However, since Princeton University has reported on organic EL devices that use phosphorescence emission from excited triplets (see, for example, Non-Patent Document 1), research on materials that exhibit phosphorescence at room temperature has become active. (For example, see Non-Patent Document 2 and Patent Document 4).

  When excited triplets are used, the upper limit of internal quantum efficiency is 100%, so in principle the luminous efficiency is four times that of excited singlets, and the performance is almost the same as that of cold cathode tubes. It can be applied to and attracts attention.

  For example, many compounds have been studied focusing on heavy metal complexes such as iridium complexes (see, for example, Non-Patent Document 3).

  Further, studies using tris (2-phenylpyridine) iridium as a dopant have been made (for example, see Non-Patent Document 2).

In addition, L ₂ Ir (acac), for example, (ppy) ₂ Ir (acac) (see, for example, Non-Patent Document 4) is used as a dopant, and tris (2- (p-tolyl) pyridine) iridium (Ir ( ptpy) ₃ ), tris (benzo [h] quinoline) iridium (Ir (bzq) ₃ ), Ir (bzq) ₂ ClP (Bu) _3, etc. (for example, see Non-Patent Document 5) Yes. In addition, in order to obtain high luminous efficiency, a hole transporting compound is also used as a host of a phosphorescent compound (for example, see Non-Patent Document 6).

  Further, various electron transporting materials are used as phosphorescent compound hosts by doping them with a novel iridium complex (for example, see Non-Patent Document 4). Furthermore, high luminous efficiency is obtained by introducing a hole blocking layer (see, for example, Non-Patent Document 5).

  Currently, further improvement in light emission efficiency and long life of organic EL devices using phosphorescence is being studied.

  However, although the external extraction efficiency of 20%, which is the theoretical limit for green light emission, has been achieved, it is only in the low current region (low luminance region), and the theoretical limit is still in the high current region (high luminance region). Not achieved. Sufficient efficiencies have not yet been obtained for other luminescent colors, and improvements are required. In addition, organic EL elements that emit light efficiently and with high brightness with lower power consumption are expected to be put to practical use in the future. Development of devices is desired. Particularly, there is a demand for an element that emits light with high efficiency in an organic EL element that emits blue phosphorescence.

  As a phosphorescent organic EL device that solves these problems, Patent Document 5 describes an example in which a compound containing a boron atom in a molecule is used as a light emitting material or an electron transporting material. Was still inadequate. Patent Document 6 describes an organic EL element containing a boron complex of an 8-hydroxyquinoline derivative, but durability is a problem.

Japanese Patent No. 3093796 Japanese Unexamined Patent Publication No. 63-264692 JP-A-3-255190 US Pat. No. 6,097,147 JP 2003-234192 A JP 2000-150163 A

M.M. A. Baldo et al. , Nature, 395, 151-154 (1998) M.M. A. Baldo et al. , Nature, 403, 17, 750-753 (2000) S. Lamansky et al. , J .; Am. Chem. Soc. 123, 4304 (2001) M.M. E. Thompson et al. , The 10th International Workshop on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu) Moon-Jae Youn. 0 g, Tsutsuo Tsutsui et al. , The 10th International Workshop on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu) Ikai et al. , The 10th International Workshop on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu)

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an organic electroluminescent element material having high luminous efficiency and a long lifetime, and an organic electroluminescence device using the organic electroluminescent element material. It is providing a luminescence element, an illuminating device, and a display apparatus.

  The above object of the present invention has been achieved by the following constitution.

1. An organic electroluminescence device having a light emitting layer containing a phosphorescent light emitting material,
Following general formula organic electroluminescence device characterized by using the organic electroluminescence element material you express by (C).

(In the formula, A represents triethylamine, pyridine, or pyrrole, B represents a boron atom, and Ar ₁ , Ar ₂ , and Ar ₃ represent a substituted or unsubstituted aromatic group or heterocyclic group.)
2. Wherein Ar _1, Ar ₂ and Ar ₃ are organic electroluminescent element according to the 1, which is a group of atoms necessary for forming a 6-membered aromatic ring or a heterocyclic ring.

3. Wherein _Ar 1, Ar ₂ and Ar ₃ are organic electroluminescence element as described in 1 or 2, characterized in that a benzene ring.

4 . The organic electroluminescent device according to any one of the 1 to 3, characterized in that a hole blocking layer containing a pre Kieu machine electroluminescence element material.

5 . The organic electroluminescent device according to any one of the 1 to 3, wherein a light-emitting layer containing a pre Kieu machine electroluminescence element material.

6 . 6. The organic electroluminescence device according to any one of 1 to 5 , which emits blue light.

7 . 6. The organic electroluminescence device according to any one of 1 to 5 , which emits white light.

8 . 8. A display device comprising the organic electroluminescence element according to any one of 1 to 7 above.

9 . 8. An illuminating device comprising the organic electroluminescence element according to any one of 1 to 7 above.

10 . 10. A display device comprising the illumination device according to 9 and a liquid crystal element as display means.

  According to the present invention, it was possible to provide an organic electroluminescent element material having high luminous efficiency and a long lifetime, and an organic electroluminescent element, an illuminating device, and a display device using the organic electroluminescent element material.

An active matrix type full-color display device is shown. A schematic diagram of display part A of a full-color display device is shown. A schematic diagram of a pixel is shown. It is a schematic diagram of the display apparatus by a passive matrix system. It is the schematic of an illuminating device. It is sectional drawing of an illuminating device.

  As a result of intensive studies, the present inventors have found that the boron compound represented by the general formula (C) is a material for an organic EL device having high luminous efficiency and a long lifetime, and an organic EL device and an illumination using the same. It has been found that a device and a display device can be provided.

  It is presumed that the boron compound of the present invention is complexed with triethylamine, pyridine or pyrrole, so that the boron compound is stabilized, the luminous efficiency is high, and a long life can be achieved. In addition, the boron compound of the present invention can be made shorter than the boron complex of 8-hydroxyquinoline derivatives described in JP-A-2000-150163. High luminous efficiency was obtained when applied to an EL element.

  Hereinafter, the present invention will be described in detail.

<< Compound Represented by Formula (C) >>
In general formula (C), A represents triethylamine, pyridine or pyrrole.

In the general formula (C), Ar ₁ , Ar ₂ , and Ar ₃ are each independently represented by an aromatic group or a heterocyclic group. Ar ₁ , Ar ₂ and Ar ₃ are preferably an atomic group necessary to form a 6-membered aromatic ring or heterocyclic ring.

Examples of the aromatic group represented by Ar ₁ , Ar ₂ , Ar ₃ include benzene ring, naphthalene ring, anthracene ring, azulene ring, phenanthrene ring, triphenylene ring, pyrene ring, chrysene ring, naphthacene ring, perylene ring, Examples include a pentacene ring and a hexacene ring, which may have a substituent. Of these, a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable.

Examples of the heterocyclic group represented by Ar ₁ , Ar ₂ , Ar ₃ include carbazole ring, pyridine ring, pyrimidine ring, thiophene ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, triazole ring, oxazole ring, Examples include a thiazole ring, isoxazole, isothiazole ring, indole ring, phenanthroline ring, quinoline ring, isoquinoline ring, quinoline ring, and oxadiazole ring, and these may have a substituent. Among these, a carbazole ring, a pyridine ring, a pyrimidine ring, a triazole ring, and an oxadiazole ring are preferable, and a carbazole ring and a pyridine ring are more preferable.

  Examples of the substituent include aliphatic groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group). , Cyclopentyl group, cyclohexyl group, vinyl group, allyl group, ethynyl group, propargyl group, etc.), aromatic group (for example, phenyl group, naphthyl group, etc.), heterocyclic group (for example, furyl group, thienyl group, pyridyl group, etc.) Pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzimidazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.) Cycloalkoxy groups (eg, cyclopentyl) Xyl group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), acyl group (eg, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group) Group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon group (eg, Fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group and the like.

  Although the example of the boron compound represented by the said general formula (C) of this invention is shown with the example of a reference compound below, it is not limited to these.

  Hereinafter, synthesis examples of the compound synthesis represented by the general formula (C) according to the present invention will be shown.

Synthesis Example 1: Synthesis of Exemplified Compound 13 The compound was synthesized according to the following synthesis scheme.

After adding 1.68 g (10.8 mmol) of bromobenzene to a 200 ml three-head flask, the atmosphere was replaced with nitrogen. After adding 60 ml of diethyl ether and cooling to -78 ° C., 6.81 ml (10.8 mmol) of n-BuLi was added dropwise and stirred for 30 minutes. Thereafter, 0.45 ml (3.59 mmol) of BF ₃ .OEt ₂ was added, and the mixture was warmed to −78 ° C. for 1 hour, and then further stirred for 2 hours. Thereafter, 0.289 ml of pyridine was added dropwise at room temperature over 30 minutes while stirring the reaction solution. After the dropwise addition, the mixture was further stirred for 2 hours at room temperature and aged. After aging, this was transferred to a separatory funnel, 100 ml of ethyl acetate was added and washed with water three times. Thereafter, the organic solvent was removed under reduced pressure, and the residue was separated and purified by silica gel chromatography to obtain 0.90 g of Exemplified Compound 13. The structure of the compound was identified by ¹ H-NMR.

Synthesis Example 2: Synthesis of Exemplified Compound 14 p-Phenylbromobenzene (2.51 g, 10.8 mmol) was placed in a 200 ml three-headed flask and then purged with nitrogen. After adding 60 ml of diethyl ether and cooling to -78 ° C., 6.81 ml (10.8 mmol) of n-BuLi was added dropwise and stirred for 30 minutes. Thereafter, 0.45 ml (3.59 mmol) of BF ₃ .OEt ₂ was added, and the mixture was warmed to −78 ° C. for 1 hour, and then further stirred for 2 hours. Thereafter, 0.289 ml of pyridine was added dropwise at room temperature over 30 minutes while stirring the reaction solution. After the dropwise addition, the mixture was further stirred for 2 hours at room temperature and aged. After aging, this was transferred to a separatory funnel, 100 ml of ethyl acetate was added and washed with water three times. Thereafter, the organic solvent was removed under reduced pressure, and the residue was separated and purified by silica gel chromatography to obtain 1.31 g of Exemplified Compound 14. The structure of the compound was identified by ¹ H-NMR.

  Other compounds can be obtained by the same method.

<< Application of the compound represented by the general formula (C) to an organic EL device >>
When an organic EL element is produced using the compound represented by the general formula (C), it is preferably used for the hole blocking layer in the constituent layers (details will be described later) of the organic EL element.

  Although the preferable specific example of the layer structure of the organic EL element of this invention is shown below, this invention is not limited to these.

I: Anode / light emitting layer / cathode
II: Anode / light-emitting layer / electron transport layer / cathode
III: Anode / anode buffer layer / light emitting layer / cathode
IV: anode / anode buffer layer / light emitting layer / hole blocking layer / electron transport layer / cathode V: anode / hole transport layer / light emitting layer / electron transport layer / cathode
VI: Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode
VII: Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode
VIII: Anode / anode buffer layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode << light emitting layer >>
The light-emitting layer according to the present invention contains a light-emitting material, and is a layer that emits light by recombination of electrons and holes injected from an electrode, an electron transport layer, or a hole transport layer, and the light-emitting portion is a light-emitting layer The interface between the light emitting layer and the adjacent layer may be used.

  The color emitted by the present invention is measured with a spectral radiance meter CS-1000 (manufactured by Minolta) in FIG. 4.16 on page 108 of the “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). This is determined by the color when the result is applied to the CIE chromaticity coordinates.

  The light emitting layer can be formed by forming the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method. Although the film thickness as a light emitting layer does not have a restriction | limiting in particular, Usually, 5 nm-5 micrometers, Preferably it is chosen in the range of 5-200 nm. The light emitting layer may have a single layer structure in which these phosphorescent compounds and host compounds are composed of one or more kinds, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions. Good.

(Light emitting host and light emitting dopant)
The mixing ratio with the light emitting dopant to the light emitting host which is the host compound which is the main component in the light emitting layer (the phosphorescent compound according to the present invention, which will be described later, is a kind of light emitting dopant) is preferably 0.1. It is adjusting to the range of less than -30 mass%.

  A light-emitting host (also simply referred to as a host) means a compound having the largest mixing ratio (mass) in a light-emitting layer composed of two or more compounds. For other compounds, “dopant compound ( Simply referred to as a dopant). " For example, if the light emitting layer is composed of two types of compound A and compound B and the mixing ratio is A: B = 10: 90, compound A is a dopant compound and compound B is a host compound. Furthermore, if a light emitting layer is comprised from 3 types of compound A, compound B, and compound C, and the mixing ratio is A: B: C = 5: 10: 85, compound A and compound B are dopant compounds, Compound C is a host compound.

  In the present invention, a known host compound can be used as the host compound. As the known host compound, a compound having a hole transporting ability and an electron transporting ability, preventing the emission of light from being increased in wavelength, and having a high Tg (glass transition temperature) is preferable.

  Specific examples of known host compounds include compounds described in the following documents.

  JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, and the like.

  The light emitting layer according to the present invention preferably contains a dopant. Further, it is preferable to use a phosphorescent compound as the dopant compound. Thereby, high light emission luminance and light emission efficiency can be obtained. A phosphorescent compound is a compound in which light emission from an excited triplet is observed, is a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescence quantum yield of 0.01 or more at 25 ° C. It is. The phosphorescence quantum yield is preferably 0.1 or more.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence quantum yield used in the present invention only needs to achieve the above phosphorescence quantum yield in any solvent.

  There are two types of light emission of phosphorescent compounds in principle. One is the recombination of carriers on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is phosphorescent. An energy transfer type in which light emission from the phosphorescent compound is obtained by transferring to the compound, and the other is that the phosphorescent compound becomes a carrier trap, and carrier recombination occurs on the phosphorescent compound, and the phosphorescent compound In any case, the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.

  The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of the organic EL device.

  The phosphorescent compound used in the present invention is preferably a complex compound containing any one metal belonging to Group 8 to 10 in the periodic table, more preferably an iridium compound, an osmium compound, or Platinum compounds (platinum complex compounds) and rare earth complexes, and most preferred are iridium compounds.

  These compounds are described, for example, in Inorg. Chem. 40, 1704 to 1711, etc.

  In addition, for example, J. et al. Am. Chem. Soc. , 123, 4304-4312 (2001), International Publication No. 00/70655 pamphlet, No. 02/15645 pamphlet, JP-A No. 2001-247859, No. 2001-345183, No. 2002-117978. Gazette, 2002-170684 gazette, 2002-203678 gazette, 2002-235076 gazette, 2002-302671 gazette, 2002-324679 gazette, 2002-332291 gazette, 2002-332292 gazette. Iridium complexes mentioned in the general formula described in JP-A-2002-338588, etc., iridium complexes mentioned as specific examples, iridium complexes expressed in formula (IV) described in JP-A-2002-8860, etc. Is mentioned.

  The phosphorescent compound according to the present invention preferably has a phosphorescence quantum yield in solution of 0.001 or more at 25 ° C., more preferably 0.01 or more, and particularly preferably 0.1 or more. .

  The phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7.

  Although the specific example of the organometallic complex which shows phosphorescence is shown below, this invention is not limited to these.

  Moreover, each organometallic complex of said PL-1-PL-33 may be used independently, and may use it in combination of 2 or more types of compounds. These compounds are described in, for example, Inorg. Chem. , 40, 1704 to 1711, and the like.

  As the organometallic complex exhibiting phosphorescence emission in the present invention, the following blue light-emitting orthometal complex is preferably used as a so-called blue light-emitting dopant in which light emission from an excited triplet is blue.

《Blue Luminous Orthometal Complex》
The blue light-emitting ortho metal complex used in the present invention will be described.

  The blue light-emitting orthometal complex according to the present invention is an orthometal complex having a transition metal as a central metal having a light emission maximum wavelength in the range of 400 to 500 nm, and the shortest light emission maximum wavelength is 455 nm or less. It is preferable.

  As the blue light-emitting ortho metal complex according to the present invention, complexes classified into the following seven types are preferably used. Here, the seven modes are classified into (a) to (h), and each of the seven modes is specifically described.

  << Aspect (a) >> The blue light-emitting ortho metal complex is at least one of partial structures represented by the following general formulas (1) to (6), or a part represented by the general formulas (1) to (6) When having at least one tautomer of each structure as a partial structure.

(In the formula, Z11 represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. R ₁₁ , R ₁₂ and R ₁₃ each represents a hydrogen atom or a substituent. M ₁₁ Represents a group 8-10 metal in the periodic table.)

(In the formula, Z21 represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. R ₂₁ , R ₂₂ and R ₂₃ each represents a hydrogen atom or a substituent. M ₂₁ represents Represents a group 8-10 metal in the periodic table.)

(Wherein, Z31 _{is, .X 31, X 32, X} 33 represent the atoms necessary to form an aromatic hydrocarbon ring or aromatic heterocyclic ring, each carbon atom, -C _(R 3) - , A nitrogen atom or —N (R ₃ ) — (wherein R ₃ represents a hydrogen atom or a substituent), C ₃₁ represents a carbon atom, and M ₃₁ represents 8 to 10 in the periodic table. Represents a group metal, a bond between C ₃₁ and N, a bond between N and X ₃₃ , a bond between X ₃₂ and X ₃₃ , a bond between X ₃₁ and X ₃₂ , C ₃₁ And the bond between X ₃₁ represents a single bond or a double bond.)

(Wherein, Z41, at least one of _{.X 41, X 42} represent the atoms necessary to form an aromatic heterocyclic ring, a nitrogen atom or -N _(R 4) - (wherein, _{R 4} is _{.M 41} representing a representative.) a hydrogen atom or a _{substituent, .C 41, C 42, C} 43 representing the group 8-10 metals of the periodic table, the _{.M 41} each represent a carbon atom Represents a group 8-10 metal in the periodic table, a bond between C ₄₁ and C ₄₂ , a bond between C ₄₁ and X ₄₂ , a bond between X ₄₁ and X _42, and X ₄₁ and bond between C _43, bond between _{C 42} and _{C 43} represents a single bond or a double bond.)

(Wherein, Z51 is .X ₅₁ represent the atoms necessary to form an aromatic hydrocarbon ring or aromatic heterocyclic ring, .R _51, R ₅₂ representing an oxygen atom or a sulfur atom, a hydrogen atom Or M ₅₁ represents a group 8 to 10 metal in the periodic table.

(Wherein, Z61 _{is, .X 61, X 62, X} 63 represent the atoms necessary to form an aromatic hydrocarbon ring or aromatic heterocyclic ring are each carbon atoms, -C _(R 6) - , A nitrogen atom or —N (R ₆ ) — (wherein R ₆ represents a hydrogen atom or a substituent); M ₆₁ represents a group 8 to 10 metal in the periodic table.)
The light emitting layer and / or the hole blocking layer may be used as the metal complex-containing layer having the tautomers of the general formulas (1) to (6) or the general formulas (1) to (6) as a partial structure. In addition, when it is contained in the light emitting layer, it can be used as a light emitting dopant in the light emitting layer to increase the efficiency of external extraction quantum efficiency of the organic EL device of the present invention (higher brightness) and to extend the light emitting lifetime. Can be achieved.

<< General Formula (1) or Tautomer of General Formula (1) >>
In the tautomer of the general formula (1) or the general formula (1), examples of the aromatic hydrocarbon ring represented by Z ₁₁ include a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, Pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, Examples include perylene ring, pentaphen ring, picene ring, pyrene ring, pyranthrene ring, anthraanthrene ring.

Of these, a benzene ring is preferably used. Furthermore, the aromatic hydrocarbon ring may have a substituent represented by R ₁₁ , R ₁₂ , or R ₁₃ in the general formula (1) described later.

In the tautomer of the general formula (1) or the general formula (1), the aromatic heterocycle represented by Z ₁₁ includes a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine. Ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, Examples thereof include a carboline ring and a ring in which at least one carbon atom of a hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom.

Of these, a pyridine ring is preferred. Furthermore, the aromatic heterocyclic ring may have a substituent represented by each of R ₁₁ , R ₁₂ and R ₁₃ in the general formula (1) described later.

Examples of the substituents represented by R ₁₁ , R ₁₂ , and R ₁₃ in the tautomer of the general formula (1) or the general formula (1) include an alkyl group (for example, a methyl group, an ethyl group, and an isopropyl group). Hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), An aromatic hydrocarbon group (for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group, etc.), aromatic heterocyclic group (for example, furyl group, Thienyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, Zolyl group, thiazolyl group, quinazolinyl group, carbazolyl group, carbolynyl group, diazacarbazolyl group (diazacarbazolyl group is any one of the carbon atoms constituting the carboline ring of the carbolinyl group. Substituted).), Phthalazinyl group, etc.), alkoxyl group (eg, ethoxy group, isopropoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), cyano group, hydroxyl group Alkenyl group (for example, vinyl group), styryl group, halogen atom (for example, chlorine atom, bromine atom, iodine atom, fluorine atom). These groups may be further substituted.

Among these, in the present invention, at least one of the groups represented by R ₁₁ , R ₁₂ and R ₁₃ is preferably the aromatic hydrocarbon group or the aromatic heterocyclic group.

In the tautomer of the general formula (1) or the general formula (1), M ₁₁ represents a group 8 to 10 metal (a metal atom or an ion) in the periodic table, and is preferably used among them. Are platinum (Pt) and iridium (Ir). Further, in the metal complex having the general formula (1) or general formula互辺isomer of (1) as a partial structure, M ₁₁ may be a metal, or an ion.

In the present invention, a coordinate bond is formed between the tautomer of the above general formula (1) or the general formula (1) and the central metal represented by M ₁₁ (which may be a metal or an ion) (both complex formation). A metal complex is formed.

<< Tautomer of General Formula (2) or General Formula (2) >>
In the tautomer of the general formula (2) or the general formula (2), the aromatic hydrocarbon ring represented by Z ₂₁ is the Z tautomer of the general formula (1) or the general formula (1). It is synonymous with the aromatic hydrocarbon ring represented by ₁₁ .

In the tautomer of the general formula (2) or the general formula (2), the aromatic heterocycle represented by Z ₂₁ is Z ₁₁ in the tautomer of the general formula (1) or the general formula (1). It is synonymous with the aromatic heterocyclic ring represented by these.

In the tautomer of the general formula (2) or the general formula (2), the substituents represented by R ₂₁ , R ₂₂ and R ₂₃ are the tautomers of the general formula (1) or the general formula (1). It is synonymous with the substituent respectively represented by R < ₁₁ >, R < ₁₂ >, R < ₁₃ > in a sex body.

In the tautomer of the general formula (2) or the general formula (2), the group 8-10 metal (may be an ion) in the periodic table of elements represented by M ₂₁ is represented by the general formula (1) or the general formula. (1) in the tautomer of _the same meaning as metal 8-10 in the periodic table represented by _{M 11.}

<< General Formula (3) or Tautomer of General Formula (3) >>
In the tautomer of general formula (3) or general formula (3), the aromatic hydrocarbon ring represented by Z ₃₁ is the same as the tautomer of general formula (1) or general formula (1). It is synonymous with the aromatic hydrocarbon ring represented by ₁₁ .

In the tautomer of the general formula (3) or the general formula (3), the aromatic heterocycle represented by Z ₃₁ is Z ₁₁ in the tautomer of the general formula (1) or the general formula (1). It is synonymous with the aromatic heterocyclic ring represented by these.

In the tautomer of the general formula (3) or the general formula (3), the substituent represented by R ₃ of —N (R ₃ ) — represented by X ₃₁ , X ₃₂ , or X ₃₃ is In the tautomer of the formula (1) or the general formula (1), it is synonymous with the substituents represented by R ₁₁ , R ₁₂ and R ₁₃ .

In the tautomer of the general formula (3) or the general formula (3), the group 8-10 metal (may be an ion) in the periodic table of elements represented by M ₃₁ is represented by the general formula (1) or the general formula. (1) in the tautomers are _represented by _{M 11,} it is synonymous with 8-10 metals of the periodic table.

<< tautomer of general formula (4) or general formula (4) >>
In the tautomer of the general formula (4) or the general formula (4), the aromatic heterocycle represented by Z ₄₁ is the same as that of the tautomer of the general formula (1) or the general formula (1) in the Z ₁₁ It is synonymous with the aromatic heterocyclic ring represented by these.

In the tautomer of the general formula (4) or the general formula (4), the substituent represented by R ₄ of —N (R ₄ ) — represented by X ₄₁ or X ₄₂ is represented by the general formula (1). Or a substituent represented by R ₁₁ , R ₁₂ , or R ₁₃ in the tautomer of the general formula (1).

In the tautomer of the general formula (4) or the general formula (4), the group 8-10 metal (may be an ion) represented by M ₄₁ in the periodic table of the elements is represented by the general formula (1) or the general formula. (1) in the tautomers are _represented by _{M 11,} it is synonymous with 8-10 metals of the periodic table.

<< Tautomer of General Formula (5) or General Formula (5) >>
In the tautomer of the general formula (5) or the general formula (5), the aromatic hydrocarbon ring represented by Z ₅₁ is the same as in the tautomer of the general formula (1) or the general formula (1). It is synonymous with the aromatic hydrocarbon ring represented by ₁₁ .

In tautomer of the general formula (5) or the general formula (5), an aromatic heterocyclic ring represented by Z _51, in the tautomer of formula (1) or the general formula (1), Z ₁₁ It is synonymous with the aromatic heterocyclic ring represented by these.

In the tautomer of the general formula (5) or the general formula (5), each of the substituents represented by R ₅₁ and R ₅₂ is R in the tautomer of the general formula (1) or the general formula (1). It is synonymous with the substituent represented by each of ₁₁ , R ₁₂ and R ₁₃ .

In the tautomer of the general formula (5) or the general formula (5), the group 8-10 metal (may be an ion) in the periodic table of elements represented by M ₅₁ is represented by the general formula (1) or the general formula. (1) in the tautomers are _represented by _{M 11,} it is synonymous with 8-10 metals of the periodic table.

<< Tautomer of General Formula (6) or General Formula (6) >>
In the tautomer of the general formula (6) or the general formula (6), the aromatic hydrocarbon ring represented by Z ₆₁ is the same as that in the tautomer of the general formula (1) or the general formula (1). It is synonymous with the aromatic hydrocarbon ring represented by ₁₁ .

In tautomer of the general formula (6) or formula (6), an aromatic heterocyclic ring represented by Z _61, in the tautomer of formula (1) or the general formula (1), Z ₁₁ It is synonymous with the aromatic heterocyclic ring represented by these.

In the tautomer of the general formula (6) or the general formula (6), the group 8-10 metal (which may be an ion) in the periodic table of elements represented by M ₆₁ is represented by the general formula (1) or the general formula. (1) in the tautomers are _represented by _{M 11,} it is synonymous with 8-10 metals of the periodic table.

  Hereinafter, specific examples of the metal complex according to the present invention having a partial structure each of the tautomers of the general formulas (1) to (6) or the general formulas (1) to (6) will be described. The invention is not limited to these.

  << Aspect (b) >> The blue light-emitting orthometal complex is represented by a platinum complex represented by the following general formula (7).

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ represent a hydrogen atom or a substituent, at least one of which is necessarily a substituent. Ra represents a substituent. X ₁ represents an oxygen atom or a sulfur atom, Y ₁ -L ₁ -Y ₂ represents a bidentate ligand, and Y ₁ and Y ₂ each independently represent an oxygen atom, a nitrogen atom, a carbon atom or a sulfur atom. L ₁ represents an atomic group necessary to form a bidentate ligand together with Y ₁ and Y _2. )
<< Metal Complex Represented by General Formula (7) >>
The platinum complex represented by the general formula (7) will be described.

In the general formula (7), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are each represented by a hydrogen atom or a substituent, but at least one of them always represents a substituent. Even when two or more of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ are represented by a substituent, they are not bonded to each other to form a ring. Ra represents a substituent, and Xa represents an oxygen atom or a sulfur atom.

  In the general formula (7), the substituent represented by Ra is not particularly limited, but an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group), a cycloalkyl group (for example, Cyclohexyl group, cyclopentyl group, cyclopropyl group etc.), alkenyl group (eg vinyl group, allyl group, 2-butenyl group etc.), alkynyl group (eg ethynyl group, propynyl group etc.), aryl group (eg phenyl) Group, 2-naphthyl group, 2-pyridyl group, 2-thienyl group, 3-furyl group, etc.), heterocyclic group (N-morpholyl group, 2-tetrahydrofuranyl group, etc.) and the like.

  Among these, Ra is preferably an alkyl group having 1 to 30 carbon atoms, and Ra-Xa- is preferably an alkoxyl group or an alkylthio group.

In addition, examples of the substituent represented by R _{1 to} R ₇ include an alkyl group (for example, methyl group, isopropyl group, tert-butyl group), a cycloalkyl group (for example, cyclohexyl group, cyclopentyl group, cyclopropyl group). Etc.), alkenyl groups (eg vinyl group, allyl group, 2-butenyl group etc.), alkynyl groups (eg ethynyl group, propynyl group etc.), aryl groups (eg phenyl group, 2-naphthyl group, 9-phenanthryl) Group, 2-pyridyl group, mesityl group, carbazolyl group, fluorenyl group, 2-thienyl group, 3-furyl group, etc.), heterocyclic group (N-morpholyl group, 2-tetrahydrofuranyl group, etc.), amino group, alkylamino Group (eg, dimethylamino group, diphenylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, odor Atoms, iodine atoms, etc.), alkoxyl groups (eg, methoxy group, ethoxy group, isopropoxy group, etc.), aryloxy groups (eg, phenoxy group, perfluorophenoxy group, etc.), acylamino groups (eg, acetamido group, benzoylamide) Group), sulfonamide group (eg methanesulfonamide group, butanesulfonamide group, benzenesulfonamide group etc.), carboalkoxyl group (eg carboethoxy group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.) ), Acyloxy groups (eg, acetoxy group, benzoyloxy group, etc.), alkylthio groups (eg, methylthio group, etc.), arylthio groups (eg, phenylthio group, etc.), cyano groups, fluorinated hydrocarbon groups (eg, trifluoromethyl) Group, pentafluoro Eniru group).

In General Formula (7), Y ₁ -L ₂ -Y ₂ represents a bidentate ligand, and Y ₁ and Y ₂ each independently represent an oxygen atom, a nitrogen atom, a carbon atom, or a sulfur atom. , L ₁ represents an atomic group necessary for forming a bidentate ligand together with Y ₁ and Y ₂ .

Specific examples of the bidentate ligand represented by Y ₁ -L ₂ -Y ₂ include, but are not limited to, phenylpyridine, acetic acid, acetylacetone, thiocarbamic acid derivative which may have a substituent, Derivatives such as 2-acylphenol and picolinic acid are preferred.

In addition, the at least one substituent that is preferably introduced together with the alkoxyl group, the alkylthio group, and the like at positions 3p to 6p in the structure and not bonded to each other to form a ring is represented by the general formula (7). Groups represented by R ₁ , R ₂ , R ₃ and R ₄ , respectively, and at least one of the substituents represented by R _{1 to} R ₄ is an electron-donating substituent among the above-mentioned substituents. It is preferably a group. More preferably, at least two of the groups represented by R ₁ , R ₂ , R ₃ and R ₄ are electron donating substituents.

Most preferably, R ₂ and R ₄ in the general formula (7) are electron-donating substituents.

  As the electron-donating substituent, among the above groups, an alkyl group, an alkoxyl group, and an alkylamino group are most preferable.

  Next, preferred as these substituents are halogen atoms, especially fluorine atoms. Since the fluorine atom has a π-donor property, it may function as an electron donor, and it is considered that a favorable device performance can be imparted by the effect.

  Specific examples of the platinum complex represented by the general formula (7) used in the present invention will be given below, but the present invention is not limited thereto.

  << Aspect (c) >> The blue light-emitting orthometal complex is a platinum complex represented by the following general formulas (8) and (9), respectively.

(In the formula, A, B and C represent a hydrogen atom or a substituent, and at least two of them represent -Xa- (Ra) _na (Ra represents a substituent. Xa represents an oxygen atom, a sulfur atom or a nitrogen atom) .na representing the is represented by represents.) 1 or 2, is different which may be _{.R 1, R 2, R 3} , R 4, R 5 are identical to each other represent a hydrogen atom or a substituent .M ₁ Represents an element of Groups 8 to 10 in the periodic table.)

(In the formula, Rb, Rc and Rd represent a substituent, Xb, Xc and Xd represent an oxygen atom, a sulfur atom or a nitrogen atom. Nb, nc and nd represent 1 or 2. R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ each represent a hydrogen atom or a substituent, and M ₂ represents an element belonging to Groups 8 to 10 in the periodic table.
<< Metal Complex Represented by Formula (8) >>
The metal complex represented by the general formula (8) will be described.

  In the general formula (8), A, B, and C are represented by hydrogen atoms or substituents, but at least two of them are represented by the general formula (2) and may be different from each other. The substituent represented by A, B, or C is not particularly limited, but is preferably an alkyl group (for example, a methyl group, an isopropyl group, a tert-butyl group), a cycloalkyl group (for example, a cyclohexyl group, a cyclopentyl group). , Cyclopropyl group, etc.), alkenyl group (eg, vinyl group, allyl group, 2-butenyl group, etc.), alkynyl group (eg, ethynyl group, propynyl group, etc.), aryl group (eg, phenyl group, 2-naphthyl group, etc.) 9-phenanthryl group, 2-pyridyl group, 2-thienyl group, 3-furyl group, mesityl group, carbazolyl group, fluorenyl group, etc.), heterocyclic group (N-morpholyl group, 2-tetrahydrofuranyl group, etc.), amino Group (eg, dimethylamino group, diphenylamino group, etc.), halogen atom (eg, chlorine atom, bromine atom, iodine atom) ), Alkoxyl groups (for example, methoxy group, ethoxy group, isopropoxy group, etc.), aryloxy groups (for example, phenoxy group, perfluorophenoxy group, etc.), alkylthio groups (for example, methylthio group, ethylthio group, propylthio group, pentylthio group) Group, hexylthio group, octylthio group, dodecylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), cyano group, fluorinated hydrocarbon group (eg, trifluoromethyl group, pentafluorophenyl group, etc.), silyl Group (for example, triphenylsilyl group, trimethylsilyl group, etc.). Of these, amino groups, alkoxyl groups, aryloxy groups, alkylthio groups, arylthio groups, and aryl groups are particularly preferred. Most preferably, they are an amino group, an alkoxyl group, and an alkylthio group.

In General formula (8), R < ₁ >, R < ₂ >, R < ₃ >, R < ₄ >, R < ₅ > represents a hydrogen atom or a substituent. The substituents represented by R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ have the same meanings as those described as the substituents represented by A, B, and C.

In the general formula (8), _{M 1} represents a Group 8 to 10 of the elements in the periodic table. The group 8-10 elements are preferably ruthenium, rhodium, palladium, osmium, iridium and platinum, and most preferably iridium and platinum.

  In general formula (2), Ra represents a substituent. As a substituent represented by Ra, it is synonymous with what was demonstrated as a substituent represented by said A, B, and C. Of these, an alkyl group is particularly preferred.

  In General formula (8), Xa represents an oxygen atom, a sulfur atom, or a nitrogen atom. na represents 1 or 2.

  In General formula (8), the case where three of A, B, and C are represented by General formula (2) is the most preferable.

  In the general formula (8), when two of A, B, and C are represented by the general formula (2), most preferably, when the general formula (2) is substituted at the 4-position and the 6p-position, preferably the general formula This is a case where (2) is substituted at positions 4 and 4p.

<< Metal Complex Represented by Formula (9) >>
The metal complex represented by the general formula (9) will be described.

  In the general formula (9), Rb, Rc and Rd represent substituents, and examples of the substituent represented by Rb, Rc and Rd include the substituents represented by A, B and C in the general formula (8). It is synonymous with what was demonstrated as. The substituent for Rb, Rc and Rd is preferably an alkyl group.

  In General formula (9), Xb, Xc, and Xd represent an oxygen atom, a sulfur atom, or a nitrogen atom. The combination of Xb, Xc, and Xd atoms includes (1) Xd is a nitrogen atom, Xb and Xc are oxygen atoms, (2) Xd is a sulfur atom, Xb and Xc are oxygen atoms, or (3) Xb Xc and Xd are preferably oxygen atoms.

  In the general formula (9), nb, nc, and nd represent 1 or 2.

In General formula (9), R < ₆ >, R < ₇ >, R < ₈ >, R <_9> , R < ₁₀ > represents a hydrogen atom or a substituent. The substituents represented by R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ have the same meanings as those described as the substituents represented by A, B and C in the general formula (8).

In the general formula (9), _{M 2} represents a Group 8 to 10 of the elements in the periodic table. The group 8-10 elements are preferably ruthenium, rhodium, palladium, osmium, iridium and platinum, and most preferably iridium and platinum.

  Specific examples of the complex represented by the general formula (8) or (9) are given below, but the present invention is not limited to these.

  << Aspect (d) >> The blue light-emitting orthometal complex has a metal complex having a ligand represented by the following general formula (10) and a partial structure represented by the following general formula (11) or (12) When it is a metal complex or a metal complex having each tautomer of the partial structure represented by the general formula (11) or (12).

(In the formula, X ₁ , X ₂ , X ₃ and X ₄ each independently represent a carbon atom or a nitrogen atom, C ₁ and C ₂ represent a carbon atom, and Z ₁ represents C ₁ , X ₁ and X _3. together, Z2 is, C _2, together with _{X 2, X 4,} each .A ₁ represent the atoms necessary to form an aromatic hydrocarbon ring or aromatic heterocyclic ring represents a nitrogen atom or a boron atom, R ₁ represents a substituent: a bond between C ₁ and X ₁ , a bond between C ₂ and X ₂ , a bond between X ₁ and X ₃ , a bond between X ₂ and X ₄ Represents a single bond or a double bond.)

(In the formula, C ₃ , C ₄ , C ₅ , C ₆ and C ₇ each represent a carbon atom, and Z ₃ forms an aromatic hydrocarbon ring or an aromatic heterocycle together with C ₃ , C ₄ and C _5. represents an atomic group necessary for, Z4 is, .A ₂ represent the atoms necessary to form an aromatic heterocyclic ring together with _{C 6,} C _{7, N} represents a nitrogen atom or a boron atom, R ₂ Represents a substituent, M ₁₁ represents an element belonging to Groups 8 to 10 in the periodic table, a bond between C ₃ and C ₄ , a bond between C ₄ and C ₅ , C ₆ and C The bond between ₇ and the bond between C ₇ and N represents a single bond or a double bond.)

(In the formula, A ₃ represents a nitrogen atom or a boron atom, R ₃ represents a substituent, R ₄ and R ₅ represent a substituent. N1 and n2 each represent an integer of 0 to 3. M ₁₂ Represents an element of Groups 8 to 10 in the periodic table.)
<< Metal Complex Having Ligand Represented by Formula (10) >>
The metal complex having the ligand represented by the general formula (10) will be described.

  First, the ligand represented by the general formula (10) will be described.

In the general formula (10), Z ₁ together with C ₁ , X ₁ , and X ₃ and Z ₂ together with C ₂ , X ₂ , and X ₄ include aromatic hydrocarbon rings such as benzene ring and biphenyl. Ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, Examples include a fluorene ring, a fluoranthrene ring, a naphthacene ring, a pentacene ring, a perylene ring, a pentaphen ring, a picene ring, a pyrene ring, a pyranthrene ring, and an anthraanthrene ring.

Of these, a benzene ring is preferably used. Furthermore, the aromatic hydrocarbon ring may have a substituent represented by R ₁ in the general formula (10) described later.

In the general formula (10), the aromatic heterocycle formed by Z ₁ together with C ₁ , X ₁ , X ₃ and Z ₂ together with C ₂ , X ₂ , X ₄ may be, for example, a furan ring or a thiophene ring. , Pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole Examples thereof include a ring, a quinoxaline ring, a quinazoline ring, a phthalazine ring, a carbazole ring, a carboline ring, a ring in which at least one carbon atom of a hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom.

Of these, a pyridine ring is preferred. Furthermore, the aromatic heterocyclic ring may have a substituent represented by R ₁ in the general formula (10) described later.

In the general formula (10), examples of the substituent represented by R ₁ include an alkyl group (for example, methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl). Group), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aromatic hydrocarbon group (eg, phenyl group, p-chlorophenyl group, mesityl). Group, tolyl group, xylyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group, etc.), aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group) , Imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, carbazolyl Group, phthalazinyl group, etc.), alkoxyl group (eg, methoxy group, ethoxy group, isopropoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), cyano group, hydroxyl group, alkenyl group (For example, vinyl group), styryl group, halogen atom (for example, chlorine atom, bromine atom, iodine atom, fluorine atom, etc.). These groups may be further substituted.

Among them, in the present invention, at least one of the groups represented by R ₁ is preferably the above aromatic hydrocarbon group or aromatic heterocyclic group.

  A coordination bond is formed (also referred to as complex formation) between the ligand represented by the general formula (10) and the central metal (which may be a metal or an ion) to form a metal complex.

Here, a coordination bond is formed between the ligand and a central metal (described later) among the atoms constituting the ligand represented by the general formula (10). It is preferable that a coordination bond or a covalent bond is formed between ₃ and / or X ₄ .

<< Metal Complex Having General Formula (11) or Its Tautomer as Partial Structure >>
A metal complex having the general formula (11) or a tautomer thereof as a partial structure will be described.

In the general formula (11), the aromatic hydrocarbon ring formed by Z ₃ together with C ₃ , C ₄ , and C _{5 is} formed by Z ₁ together with C ₁ , X ₁ , and X _{3 in the} general formula (10). Synonymous with aromatic hydrocarbon ring.

In the general formula (11), the aromatic heterocycle formed by Z ₃ together with C ₃ , C ₄ , and C ₅ is the aromatic formed by Z ₁ together with C ₁ , X ₁ , and X _{3 in the} general formula (10). Synonymous with family heterocycle.

In the general formula (11), the aromatic heterocycle formed by Z ₄ together with C ₆ , C ₇ and N is a pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzimidazole ring, oxadiazole ring, Triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, hydrocarbon ring constituting carboline ring And a ring in which at least one of the carbon atoms is further substituted with a nitrogen atom. Furthermore, the aromatic heterocyclic ring may have a substituent represented by R ₁ in the general formula (10).

In the general formula (11), the substituent represented by R ₂ has the same meaning as the substituent represented by R ₁ in the general formula (10).

In the general formula (11), the group 8 to 10 element in the periodic table represented by M ₁₁ is preferably platinum (Pt), iridium (Ir), or the like. In the general formula (11), M ₁₁ may be a metal or an ion.

<< Metal Complex Having General Formula (12) or its Tautomer as Partial Structure >>
A metal complex having the general formula (12) or a tautomer thereof as a partial structure will be described.

In the general formula (12), the substituent represented by R ₃ has the same meaning as the substituent represented by R ₁ in the general formula (10).

In the general formula (12), the substituents represented by R ₄ and R ₅ have the same meaning as the substituent represented by R ₁ in the general formula (10).

In the general formula _(12), represented by _{M 12,} as the 8-10 group element of the periodic table, platinum (Pt), iridium (Ir) or the like are preferable. In the general formula (12), M ₁₂ may be a metal or an ion.

  Below, a metal complex having a ligand represented by the general formula (10), a metal complex having a partial structure represented by the following general formula (11) or (12), or the general formula (11) or (12 Specific examples of metal complexes having tautomers of each of the partial structures represented by) are shown below, but the present invention is not limited to these.

  << Aspect (e) >> The blue light-emitting orthometal complex has a metal complex having a ligand represented by the following general formula (13), a metal complex having a partial structure represented by the following general formula (14), A metal complex having a partial structure represented by the general formula (15) or a tautomer thereof as a partial structure, a metal complex having a ligand represented by the following general formula (16), or a general formula (17) When it is a metal complex having a partial structure represented, or a metal complex having a partial structure represented by the following general formula (18).

(In the formula, X ₁ , X ₂ , X ₃ , and X ₄ each independently represent a carbon atom or a nitrogen atom, C ₁ and C ₂ each represent a carbon atom, and Z ₁ represents C ₁ , X ₁ , Along with X ₃ , Z ₂ represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with C ₂ , X ₂ , and X ₄ , and A ₁ represents a carbon atom or a silicon atom. , R ₁ and R ₂ each independently represents a hydrogen atom or a substituent, a bond between C ₁ and X ₁ , a bond between C ₂ and X _2, and a bond between X ₁ and X ₃ (The bond between X ₂ and X ₄ represents a single bond or a double bond, respectively.)

(In the formula, C ₃ , C ₄ , C ₅ , C ₆ and C ₇ represent a carbon atom, and Z ₃ forms an aromatic hydrocarbon ring or an aromatic heterocycle together with C ₅ , C ₃ and C _7. Z4 represents an atomic group necessary for forming an aromatic heterocyclic ring together with C ₆ , C ₄ , and N, A ₂ represents a carbon atom or a silicon atom, R ₃ , R ₄ each independently represents a hydrogen atom or a substituent, M ₁₁ represents an element of Groups 8 to 10 in the periodic table, a bond between C ₅ and C _3, and a bond between C ₃ and C ₇ . And the bond between C ₆ and C ₄ and the bond between C ₄ and N each represents a single bond or a double bond.)

(In the formula, A ₃ represents a carbon atom or a silicon atom, R ₅ and R ₆ each independently represent a hydrogen atom or a substituent, and R ₇ and R ₈ each independently represent a substituent. N1, n2 is _{.M 12} which each independently represent an integer of 0 to 3, represents a 8-10 element in the periodic table.)

(Wherein X ₃ , X ₄ , X ₅ and X ₆ each independently represent a carbon atom or a nitrogen atom, C _{8 to} C ₁₃ each represents a carbon atom, and Z 5 represents C ₈ , X ₃ , Along with X ₅ , Z 6 is together with C ₉ , X ₄ , X ₆ , Z 7 is along with C ₁₀ , C ₁₁ , Z 8 is together with C ₁₂ , C ₁₃ , each independently an aromatic hydrocarbon ring or aromatic heterocyclic ring A ₄ represents a carbon atom or a silicon atom, a bond between X ₃ and X ₅ , a bond between X ₄ and X ₆ , C ₈ and X ₃ coupling between the bond, the bond between _{C 9} and _{X 4,} the bond between _{C 10} and _{C 11,} and _{C 12} and _{C 13} between each represents a single bond or a double bond. )

(Wherein C _{14 to} C ₂₂ each represent a carbon atom, Z 9 together with C ₁₆ , C ₁₄ and C ₁₈ , Z 11 together with C ₁₉ and C ₂₀ , Z ₁₂ together with C ₂₁ and C ₂₂ , Each represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and Z10 represents an atomic group necessary for forming an aromatic heterocyclic ring together with C ₁₇ , C ₁₅ , and N. A ₅ represents a carbon atom or a silicon atom, M ₂₁ represents an element of Groups 8 to 10 in the periodic table, a bond between C ₁₈ and C _14, and a bond between C ₁₄ and C ₁₆ A bond between C ₁₇ and C ₁₅ , a bond between C ₁₅ and N, a bond between C ₁₉ and C ₂₀ , a bond between C ₂₁ and C ₂₂ is a single bond or Represents a double bond.)

(Wherein, _Z13, together with the C _{23, C 24, Z14,} together with the C _{25, C 26,} each represents an atomic group necessary for forming an aromatic hydrocarbon ring or aromatic heterocyclic ring, _{A 6} is R ₉ and R ₁₀ each independently represents a substituent, n 3 and n 4 each independently represent an integer of 0 to 3. M ₂₂ represents Groups 8 to 10 in the periodic table of elements. (The bond between C ₂₃ and C ₂₄ and the bond between C ₂₅ and C ₂₆ each represents a single bond or a double bond.)
<< Metal Complex Having Ligand Represented by General Formula (13) >>
The metal complex having a ligand represented by the general formula (13) will be described.

  First, the ligand represented by the general formula (13) will be described.

In the general formula (13), the aromatic hydrocarbon ring formed together with Z ₁ and C ₁ , X ₁ , X ₃ includes benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring , Chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring , Pentaphen ring, picene ring, pyrene ring, pyranthrene ring, anthraanthrene ring and the like.

Of these, a benzene ring is preferably used. Furthermore, the aromatic hydrocarbon ring may have a substituent represented by R ₁ or R ₂ in the general formula (13) described later.

In the general formula (13), the aromatic heterocycle formed together with Z ₁ and C ₁ , X ₁ , X ₃ includes a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, Benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring And a ring in which at least one of the carbon atoms of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom.

Of these, a pyridine ring is preferred. Furthermore, the aromatic heterocyclic ring may have a substituent represented by R ₁ or R ₂ in the general formula (13) described later.

In the general formula (13), examples of the substituent independently represented by R ₁ and R ₂ include an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a methoxymethyl group, a trifluoro group). Methyl group, t-butyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (for example, benzyl group, 2-phenethyl group, etc.), aromatic hydrocarbon group (for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group, etc.), aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group) , Pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolyl Group, carbazolyl group, phthalazinyl group, etc.), alkoxyl group (eg, ethoxy group, isopropoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), cyano group, hydroxyl group, alkenyl group (For example, vinyl group), styryl group, halogen atom (for example, chlorine atom, bromine atom, iodine atom, fluorine atom, etc.). These groups may be further substituted.

Among these, in the present invention, at least one of the groups represented by R ₁ and R ₂ is preferably the aromatic hydrocarbon group or the aromatic heterocyclic group.

  A coordination bond is formed (also referred to as complex formation) between the ligand represented by the general formula (13) and the central metal (which may be a metal or an ion) to form a metal complex.

Here, a coordination bond is formed between the ligand and a central metal (described later) among the atoms constituting the ligand represented by the general formula (13). It is preferable that a coordination bond or a covalent bond is formed between ₃ and / or X ₄ .

<< Metal Complex having Partial Structure Represented by General Formula (14) >>
The metal complex having a partial structure represented by the general formula (14) will be described.

In the general formula (14), the aromatic hydrocarbon ring formed by Z ₃ together with C ₅ , C ₃ , and C _{7 is} formed by Z ₁ together with C ₁ , X ₁ , and X _{3 in the} general formula (13). Synonymous with aromatic hydrocarbon ring.

In the general formula (14), the aromatic heterocycle formed by Z ₃ together with C ₅ , C ₃ and C ₇ is the fragrance formed together with Z ₁ and C ₁ , X ₁ and X _{3 in the} general formula (13). Synonymous with family heterocycle.

In the general formula (14), the aromatic heterocycle formed by Z ₄ together with C ₆ , C ₄ , and N includes a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a benzimidazole ring, and an oxadiazole. Carbon, constituting the ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, carboline ring Examples include a ring in which at least one carbon atom of the hydrogen ring is further substituted with a nitrogen atom. Furthermore, the aromatic heterocyclic ring may have a substituent represented by each of R ₁ and R ₂ in the general formula (13).

In the general formula (14), the substituents independently represented by R ₃ and R ₄ have the same meanings as the substituents independently represented by R ₁ and R ₂ in the general formula (13). .

In the general formula _{(14), M 11} represents an 8-10 Group VIII of the in the periodic table, among them preferably used is a platinum (Pt) and iridium (Ir). In the general formula (14), M ₁₁ may be a metal or an ion.

<< Metal Complex Having General Formula (15) or its Tautomer as Partial Structure >>
A metal complex having the general formula (15) or a tautomer thereof as a partial structure will be described.

In the general formula (15), the substituents independently represented by R ₅ and R ₆ and the substituents independently represented by R ₇ and R ₈ are the same as those represented by R ₁ , R 6 in the general formula (13). ₂ is synonymous with the substituents each independently represented.

In the general formula (15), at least one of R ₅ and R ₆ is preferably an aromatic hydrocarbon group or an aromatic heterocyclic group.

In the general formula _(15), 8-10 element in the periodic table represented by _{M 12,} in the general formula _{(14), M 11} is 8-10 element as defined in the periodic table is there.

<< Metal complex having a ligand represented by the general formula (16) >>
The metal complex having a ligand represented by the general formula (16) will be described.

In the general formula (16), Z ₅ is together with C ₈ , X ₃ and X ₅ , Z ₆ is together with C ₉ , X ₄ and X ₆ , Z ₇ is together with C ₁₀ and C ₁₁ , Z ₈ is The aromatic hydrocarbon ring independently formed together with C ₁₂ and C _{13 is the same} as the aromatic hydrocarbon ring formed with Z ₁ together with C ₁ , X ₁ and X ₃ in the general formula (13). .

In the general formula (16), Z ₅ is together with C ₈ , X ₃ and X ₅ , Z ₆ is together with C ₉ , X ₄ and X ₆ , Z ₇ is together with C ₁₀ and C ₁₁ , Z ₈ is The aromatic heterocyclic ring independently formed together with C ₁₂ and C ₁₃ has the same meaning as the aromatic heterocyclic ring formed with Z ₁ together with C ₁ , X ₁ and X ₃ in the general formula (13).

<< Metal Complex having Partial Structure Represented by General Formula (17) >>
The metal complex having the partial structure represented by the general formula (17) will be described.

In the general formula (17), Z ₉ is together with C ₁₆ , C ₁₄ , C ₁₈ , Z ₁₁ is together with C ₁₉ , C ₂₀ , and Z ₁₂ is independently formed with C ₂₁ , C _22. hydrocarbon ring, in the general formula (13) is synonymous with an aromatic hydrocarbon ring formed _{by Z 1} with _{C 1, X 1, X 3} .

In the general formula (17), Z ₉ is together with C ₁₆ , C ₁₄ , C ₁₈ , Z ₁₁ is together with C ₁₉ , C ₂₀ , and Z ₁₂ is independently formed with C ₂₁ , C _22. heterocycle, in the general formula (13), is synonymous with the aromatic heterocyclic ring formed _{by Z 1} with _{C 1, X 1, X 3} .

In the general formula (17), an aromatic heterocycle formed by Z ₁₀ together with C ₁₇ , C ₁₅ and N is an aromatic heterocycle formed by Z ₄ together with C ₆ , C ₄ and N in the general formula (14). Synonymous with family heterocycle.

In the general formula _(17), represented by _{M 21,} is 8-10 element in the periodic table, in the general formula _{(14), M 11} is 8-10 element as defined in the periodic table It is.

<< Metal Complex having Partial Structure Represented by General Formula (18) >>
The metal complex having a partial structure represented by the general formula (18) will be described.

In the general formula _{(18), Z 13,} together with the _{C 23,} C _{24, Z 14,} together with the C _{25, C 26,} an aromatic hydrocarbon ring to each form, in the general formula (13), _{Z 1} is C _{1, X 1, X 3} is synonymous with an aromatic hydrocarbon ring formed together.

In the general formula (18), Z ₁₃ together with C ₂₃ and C ₂₄ , Z ₁₄ together with C ₂₅ and C ₂₆ , the aromatic heterocycle formed respectively in Z ₁ and C ₁ , X ₁ and X ₃ are synonymous with the aromatic heterocyclic ring formed.

In General Formula (18), the substituents independently represented by R ₉ and R ₁₀ have the same meanings as the substituents independently represented by R ₁ and R ₂ in General Formula (13).

In the general formula _(18), represented by _{M 22,} is 8-10 element in the periodic table, in the general formula _{(14), M 11} is 8-10 element as defined in the periodic table It is.

  Hereinafter, a metal complex having a ligand represented by the general formula (13), a metal complex having a partial structure represented by the general formula (14), a partial structure represented by the general formula (15), or a combination thereof. Metal complex having mutant as partial structure, metal complex having ligand represented by general formula (16), metal complex having partial structure represented by general formula (17), or general formula (18) Although the specific example of the metal complex which has the partial structure represented by this is shown, this invention is not limited to these.

  << Aspect (f) >> The case where at least one platinum complex selected from the group consisting of the following general formulas (19) to (27) is used as the blue light-emitting orthometal complex.

(In the formula, R ₁ and R ₂ each represent a hydrogen atom or a substituent. However, at least one of R ₁ and R ₂ is the substituent. X ₁ and X ₂ are a carbon atom and nitrogen, respectively. Represents an atom, an oxygen atom, or a sulfur atom, and Z ₁ and Z ₂ each represents an atomic group necessary to form an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and n1 is an integer of 1 or 2 And when n1 is 1, L1 represents a bidentate ligand, and p1 and q1 each represent an integer of 0 to 4.)

(Wherein R ₃ and R ₄ each represent a hydrogen atom or a substituent, provided that at least one of R ₃ and R ₄ is the substituent. N2 is an integer of 1 or 2, and n2 When L is 1, L2 represents a bidentate ligand, and p2 and q2 each represent an integer of 0 to 4.)

(Wherein R ₅ and R ₆ each represent a hydrogen atom or a substituent. Z ₃ represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. N3 is 1 or And when n3 is 1, L3 represents a bidentate ligand, p3 represents an integer of 0 to 3, and q3 represents an integer of 0 to 4.)

(Wherein R ₇ and R ₈ each represent a hydrogen atom or a substituent. R _{9 to} R ₁₃ each represent a hydrogen atom or a substituent. N4 is an integer of 1 or 2, and n4 is 1) L4 represents a bidentate ligand, p4 represents an integer of 0 to 3, and q4 represents an integer of 0 to 4.)

(Wherein R ₁₄ and R ₁₅ each represent a hydrogen atom or a substituent. Z ₄ represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. N5 is 1 or And when n5 is 1, L5 represents a bidentate ligand, p5 represents an integer of 0 to 4, and q5 represents an integer of 0 to 3.)

(Wherein R ₁₆ and R ₁₇ each represent a hydrogen atom or a substituent. R _{18 to} R ₂₂ each represent a hydrogen atom or a substituent. N6 is an integer of 1 or 2, and n6 is 1) L6 represents a bidentate ligand, p6 represents an integer of 0 to 3, and p7 represents an integer of 0 to 4.)

(Wherein R ₂₃ and R ₂₄ each represent a hydrogen atom or a substituent. Z ₅ represents an atomic group necessary for forming an aromatic heterocyclic ring together with a nitrogen atom. N7 is 1 or 2) When n7 is 1, L7 represents a bidentate ligand, p8 represents an integer of 0 to 3, and q6 represents an integer of 0 to 4.)

(In the formula, R ₂₅ and R ₂₆ each represent a hydrogen atom or a substituent. Z ₆ represents an atomic group necessary for forming an aromatic heterocyclic ring together with a nitrogen atom. N8 is 1 or 2) When n8 is 1, L8 represents a bidentate ligand, p9 represents an integer of 0 to 3, and q7 represents an integer of 0 to 4.)

(In the formula, R ₂₇ and R ₂₈ each represent a hydrogen atom or a substituent. At least one of R ₂₇ and R ₂₈ is the substituent. L 0 represents a divalent linking group. X ₃ , X ₄ represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, respectively, Z ₇ and Z ₈ each represents an atomic group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and n9. (It is an integer of 1 or 2, and when n9 is 1, L9 represents a bidentate ligand. P10 and q8 each represent an integer of 0 to 4.)
<< Platinum Complex Represented by General Formula (19) >>
The platinum complex represented by the general formula (19) will be described. In this invention, what is represented by the tautomer of the said General formula (19) shall also be included.

In the general formula (19), examples of the substituent represented by R ₁ and R ₂ include an alkyl group (for example, methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl). Group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, p-chlorophenyl group). Mesityl group, tolyl group, xylyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group, etc.), aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, Triazinyl, imidazolyl, pyrazolyl, thiazolyl, quinazolinyl, Basolyl group, phthalazinyl group, etc.), alkoxyl group (eg, ethoxy group, isopropoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), cyano group, hydroxyl group, alkenyl group (eg, Vinyl group, etc.), styryl group, halogen atom (for example, chlorine atom, bromine atom, iodine atom, fluorine atom, etc.). These groups may be further substituted.

In the general formula (19), examples of the aromatic hydrocarbon ring or aromatic heterocyclic ring formed by Z ₁ include a benzene ring, naphthalene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, and furan ring. Thiophene ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring and the like. Of these, a benzene ring is preferred.

In the general formula (19), examples of the aromatic hydrocarbon ring or aromatic heterocycle formed by Z ₂ include a pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzimidazole ring, benzothiazole ring, Examples thereof include a benzoxazole ring, a quinazoline ring, and a phthalazine ring. Of these, a pyridine ring is preferred.

  In the general formula (19), n1 is an integer of 1 or 2, and when n1 is 1, L1 represents a bidentate ligand. Examples of the bidentate ligand represented by L1 include oxycarboxylic acid, oxyaldehyde and derivatives thereof (for example, salicylaldehyde, oxyacetophenonate, etc.), dioxy compounds (for example, biphenolate, etc.), diketones (for example, Acetylacetonato, dibenzoylmethanato, diethylmalonate, ethylacetoacetate, etc.), oxyquinones (eg, pyromeconato, oxynaphthoquinato, oxyanthraquinato, etc.), tropolones (eg, troponato, hinokitiolato, etc.), N-oxide compounds, aminocarboxylic acids and similar compounds (for example, glycinato, alaninato, anthranilate, picolinato, etc.), hydroxylamines (for example, aminophenolato, ethanolaminato, mercaptoethylaminato, etc.), oxines (for example, 8-oxyquinolinato, etc.), aldimines (eg, salicylaldiminato, etc.), oximes (eg, benzoin oximato, salicylaldoximato, etc.), oxyazo compounds (eg, oxyazobenzonate, phenylazonaphtholato, etc.) , Nitrosonaphthols (for example, β-nitroso-α-naphtholate, etc.), triazenes (for example, diazoaminobenzenato, etc.), biurets (for example, biuretate, polypeptide group, etc.), formasenes and dithizones (for example, Diphenylcarbazonate, diphenylthiocarbazonate and the like), piguanides (for example, piguanidate and the like), glyoximes (for example, dimethylglyoximato and the like) and the like.

  Although the general formula and specific example of a bidentate ligand which are preferably used in the present invention are listed below, the present invention is not limited thereto.

  In the general formula of the above bidentate ligand, Ra to Rv are each an alkyl group (for example, methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc. Or a halogenated alkyl group (for example, those in which at least one hydrogen atom of the alkyl group is substituted by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or the like).

  In the general formula of the above bidentate ligand, Ara to Arc are aryl groups (for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group). Etc.) or an aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, carbazolyl group, carbolinyl group, A diazacarbazolyl group (here, a diazacarbazolyl group is one in which any one of the carbon atoms constituting the carboline ring of the carbolinyl group is substituted with a nitrogen atom), a phthalazinyl group, etc. ).

<< Platinum Complex Represented by Formula (20) >>
The platinum complex represented by the general formula (2) according to the present invention will be described.

In the general formula (20), the substituents represented by R ₃ and R ₄ have the same meanings as the substituents represented by R ₁ and R ₂ in the general formula (19).

  In the general formula (20), the bidentate ligand represented by L2 has the same meaning as the bidentate ligand represented by L1 in the general formula (19).

<< Platinum Complex Represented by Formula (21) >>
The platinum complex represented by the general formula (21) according to the present invention will be described.

In the general formula (21), the substituents represented by R ₅ and R ₆ have the same meanings as the substituents represented by R ₁ and R ₂ in the general formula (19).

  In the general formula (21), the bidentate ligand represented by L3 has the same meaning as the bidentate ligand represented by L1 in the general formula (19).

In the general formula (21), the aromatic hydrocarbon ring formed by Z ₃ and C (carbon atom) includes benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene Ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen And a ring, a picene ring, a pyrene ring, a pyranthrene ring, and an anthraanthrene ring. Furthermore, the aromatic hydrocarbon ring may have a substituent represented by each of R ₁ and R ₂ in the general formula (19).

In the general formula (21), the aromatic heterocycle formed by Z ₃ and C (carbon atom) includes a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, and a benzimidazole. Ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, carboline Examples include a ring in which at least one carbon atom of the hydrocarbon ring constituting the ring is further substituted with a nitrogen atom. Furthermore, the aromatic heterocycle may have a substituent represented by each of R ₁ and R ₂ in the general formula (19).

<< Platinum Complex Represented by Formula (22) >>
The platinum complex represented by the general formula (22) according to the present invention will be described.

In the general formula (22), the substituents represented by R _{7 to} R ₁₃ have the same meanings as the substituents represented by R ₁ and R ₂ in the general formula (19).

  In the general formula (22), the bidentate ligand represented by L4 has the same meaning as the bidentate ligand represented by L1 in the general formula (19).

<< Platinum Complex Represented by Formula (23) >>
The platinum complex represented by the general formula (23) according to the present invention will be described.

In the general formula (23), the substituents represented by R ₁₄ and R ₁₅ have the same meanings as the substituents represented by R ₁ and R ₂ in the general formula (19).

  In the general formula (23), the bidentate ligand represented by L5 has the same meaning as the bidentate ligand represented by L1 in the general formula (19).

In the general formula (23), the aromatic hydrocarbon ring formed by Z ₄ and C (carbon atom) is the same as the aromatic carbon ring formed by Z ₃ and C (carbon atom) in the general formula (21). Synonymous with hydrogen ring.

In the general formula (23), the aromatic heterocycle formed by Z ₄ and C (carbon atom) is the same as the aromatic heterocycle formed by Z ₃ and C (carbon atom) in the general formula (21). It is synonymous with.

<< Platinum Complex Represented by Formula (24) >>
The platinum complex represented by the general formula (24) according to the present invention will be described.

In the general formula (24), the substituents represented by R _{16 to} R ₂₂ are synonymous with the substituents represented by R ₁ and R ₂ in the general formula (19).

  In the general formula (24), the bidentate ligand represented by L6 has the same meaning as the bidentate ligand represented by L1 in the general formula (19).

<< Platinum Complex Represented by Formula (25) >>
The platinum complex represented by the general formula (25) according to the present invention will be described.

In the general formula (25), the substituents represented by R ₂₃ and R ₂₄ have the same meanings as the substituents represented by R ₁ and R ₂ in the general formula (19).

  In the general formula (25), the bidentate ligand represented by L7 has the same meaning as the bidentate ligand represented by L1 in the general formula (19).

In the general formula (25), the aromatic heterocycle formed by Z ₅ and N (nitrogen atom) includes a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a benzimidazole ring, and an oxadiazole ring. , Triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, carboline ring Examples include rings in which at least one of the ring carbon atoms is further substituted with a nitrogen atom. Furthermore, the aromatic heterocycle may have a substituent represented by each of R ₁ and R ₂ in the general formula (19).

<< Platinum Complex Represented by Formula (26) >>
The platinum complex represented by the general formula (26) according to the present invention will be described.

In the general formula (26), the substituents represented by R ₂₅ and R ₂₆ have the same meanings as the substituents represented by R ₁ and R ₂ in the general formula (19).

  In the general formula (26), the bidentate ligand represented by L8 has the same meaning as the bidentate ligand represented by L1 in the general formula (19).

In the general formula (26), examples of the aromatic heterocycle formed by Z ₆ and N (nitrogen atom) include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a benzimidazole ring, and an oxadiazole ring. , Triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, carboline ring, carboline ring Examples include rings in which at least one of the ring carbon atoms is further substituted with a nitrogen atom. Furthermore, the aromatic heterocycle may have a substituent represented by each of R ₁ and R ₂ in the general formula (19).

<< Platinum Complex Represented by Formula (27) >>
The platinum complex represented by the general formula (27) according to the present invention will be described.

In the general formula (27), the substituents represented by R ₂₇ and R ₂₈ have the same meanings as the substituents represented by R ₁ and R ₂ in the general formula (19).

  In the general formula (27), the bidentate ligand represented by L9 has the same meaning as the bidentate ligand represented by L1 in the general formula (19).

In the general formula (27), the 5-membered or 6-membered ring formed by Z ₇ has the same meaning as the 5-membered or 6-membered ring formed by Z ₁ in the general formula (19).

In the general formula (27), the 5-membered or 6-membered ring formed by Z ₈ has the same meaning as the 5-membered or 6-membered ring formed by Z ₂ in the general formula (19).

In the general formula (27), as the divalent linking group represented by L0, an alkylene group (for example, ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, pentamethylene group, hexamethylene group, 2,2,4-trimethylhexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, cyclohexylene group (for example, 1,6-cyclohexanediyl group, etc.), Cyclopentylene group (for example, 1,5-cyclopentanediyl group, etc.), alkenylene group (for example, vinylene group, propenylene group, etc.), alkynylene group (for example, ethynylene group, 3-pentynylene group, etc.), arylene group In addition to hydrocarbon groups such as, a group containing a hetero atom (for example, -O-, -S Divalent group containing a chalcogen atom etc., -N (R) - group, where, R represents a hydrogen atom or an alkyl group, the alkyl group in the general formula _(19), R 1, R Or an alkyl group described in the substituent represented by ₂ ).

  Although the specific example of the platinum complex compound used as the organic EL element material of this invention is shown below, this invention is not limited to these. In the specific examples shown below, the periphery of an aryl group that cannot rotate freely or an aromatic heterocyclic group that cannot rotate freely is indicated by a dotted line.

《Aryl group that cannot rotate freely, Aromatic heterocyclic group that cannot rotate freely》
In the present invention, “an aryl group that cannot be freely rotated and an aromatic heterocyclic group that cannot be freely rotated” represents a substituent that cannot freely rotate a bond due to steric hindrance.

  However, as a state where the free rotation is not possible, when the aryl group and the aromatic heterocyclic group are close to other substituents arranged in the vicinity, it is physically impossible to rotate freely. As a matter of course, an aryl which cannot rotate freely even in the presence of a bond rotation barrier derived from the conformational energy with the bond axis of the aryl group or the substituent formed through the bond axis of the aromatic heterocyclic group Group, an aromatic heterocyclic group that cannot rotate freely.

  Here, the conformational energy for generating the bond rotation barrier is preferably 25 kcal / mol or more.

  In the present invention, an aryl group and an aromatic heterocyclic group, each of which is physically incapable of free rotation, are preferred.

  Examples of the aryl group that can be used as an aryl group that cannot freely rotate include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

  Examples of the aromatic heterocyclic group that can be used as an aromatic heterocyclic group that cannot rotate freely include, for example, a furyl group, a thienyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, an imidazolyl group, and a pyrazolyl group. , Thiazolyl group, quinazolinyl group, phthalazinyl group and the like.

  << Aspect g >> The case where the blue light-emitting orthometal complex includes at least one partial structure selected from the group consisting of the following general formulas (28) to (32) or a tautomer of the partial structure.

(In the formula, C represents a carbon atom, N represents a nitrogen atom, Z ₁₁ represents an atomic group necessary for forming an aromatic heterocyclic ring together with the carbon atom and the nitrogen atom, and Z ₁₂ represents a non-aromatic group together with the carbon atom. Represents an atomic group necessary for forming a ring, and M represents a metal.)

(In the formula, C represents a carbon atom, N represents a nitrogen atom, Z ₂₁ and Z ₂₂ represent an atomic group necessary for forming an aromatic ring together with the carbon atom and the nitrogen atom, respectively, and M represents a metal. )

(In the formula, C represents a carbon atom, N represents a nitrogen atom, Z ₃₁ represents an atomic group necessary for forming an aromatic heterocyclic ring together with the carbon atom and the nitrogen atom, and Z ₃₂ represents a 5-membered or (This represents an atomic group composed of carbon atoms, nitrogen atoms, or oxygen atoms necessary to form a 6-membered aromatic heterocyclic ring, and M represents a metal.)

(In the formula, C represents a carbon atom, N represents a nitrogen atom, Z ₄₁ represents a group of atoms necessary to form a ring together with the carbon atom and the nitrogen atom, and Z ₄₂ represents a ring together with the carbon atom. Represents a necessary atomic group, and M represents a metal.)

(In the formula, C represents a carbon atom, N represents a nitrogen atom, Z ₅₁ represents an atomic group necessary for forming an aromatic heterocyclic ring together with the carbon atom and the nitrogen atom, and Z ₅₂ represents an azulene ring together with the carbon atom. Represents an atomic group to be formed, and M represents a metal.)
The metal complex compound having a specific structure represented by each of the general formulas (28) to (32) will be described.

In the general formula (28), Z ₁₁ represents an atomic group necessary for forming an aromatic heterocyclic ring together with a carbon atom and a nitrogen atom, and Z ₁₂ is necessary for forming a non-aromatic ring together with the carbon atom. Represents an atomic group, and M represents a metal. Examples of the aromatic heterocycle formed by Z ₁₁ include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a benzimidazole ring, a benzothiazole ring, a benzoxazole ring, a quinazoline ring, and a phthalazine ring. It is done. Examples of the non-aromatic ring formed by Z ₁₂ include the rings described below.

In the general formula (28), preferably non-aromatic ring represented by _{Z 12} is an R-2 or R-6.

  Next, general formula (29) will be described.

In the general formula (29), Z ₂₁ and Z ₂₂ each represent an atomic group necessary for forming an aromatic heterocyclic ring together with a carbon atom and a nitrogen atom, and M represents a metal. The aromatic ring formed by Z ₂₁ includes the same aromatic heterocycle as Z ₁₁ described above, and examples of the aromatic heterocycle formed by Z ₂₂ include a pyrrole ring, a pyrazole ring, an imidazole ring, and a triazole ring. , Indole ring, benzimidazole ring and the like. Preferred is a pyrrole ring or a triazole ring.

  Next, general formula (30) will be described.

In the general formula (30), Z ₃₁ represents an atomic group necessary for forming an aromatic heterocyclic ring together with a carbon atom and a nitrogen atom, and Z ₃₂ is necessary for forming an aromatic 5-membered ring together with the carbon atom. Represents an atomic group composed of carbon, nitrogen or oxygen atoms, and M represents a metal. The aromatic heterocyclic ring formed by Z ₃₁ include similar aromatic heterocyclic and the Z _11, the aromatic 5-membered ring formed by Z _32, for example, a pyrrole ring, a furan ring, an imidazole ring , Pyrazole ring, oxazole ring, oxadiazole ring, and the like, preferably a nitrogen-containing aromatic heterocyclic ring, more preferably a nitrogen-containing aromatic heterocyclic ring containing a plurality of nitrogen or oxygen atoms.

  Next, general formula (31) will be described.

In the general formula (31), Z ₄₁ represents an atomic group necessary for forming an aromatic heterocyclic ring together with a carbon atom and a nitrogen atom, and Z ₄₂ represents an atomic group necessary for forming a ring together with the carbon atom. , M represents a metal. Aromatic heterocyclic ring formed by Z _41, the include similar aromatic heterocyclic and Z _11, the ring formed by Z ₄₂ is may be a non-aromatic ring in the aromatic ring, preferably a non-aromatic It is a ring.

  Next, general formula (32) will be described.

In the general formula (32), Z ₅₁ represents an atomic group necessary for forming an aromatic heterocyclic ring together with a carbon atom and a nitrogen atom, and Z ₅₂ represents an atomic group necessary for forming an azulene ring together with the carbon atom. M represents metal. Aromatic heterocyclic ring formed by Z ₅₁ may include the same aromatic heterocyclic and Z _11.

In the general formulas (28) to (32) described above, the ring formed by Z ₁₁ , Z ₁₂ , Z ₂₁ , Z ₂₂ , Z ₃₁ , Z ₃₂ , Z ₄₁ , Z ₄₂ , Z ₅₁ and Z ₅₂ is Furthermore, you may have a substituent and substituents may couple | bond together and you may form a ring further. In the general formulas (28) to (32), M is preferably a group 8-10 metal in the periodic table, more preferably M is iridium, osmium or platinum, and most preferably M is iridium. It is.

  Although the specific example of a compound represented by either of general formula (28)-(32) below is given, this invention is not limited to these.

  << Aspect h >> The case where the blue light-emitting orthometal complex is represented by a platinum complex having a partial structure represented by the following general formula (A) or (B).

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ each represents a hydrogen atom or a substituent, but at least one of R ₁ , R ₂ , R ₃ , R ₄ ) One is an electron donating group, and Ra and Rb each represents a substituent.)

(Wherein R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ each represents a hydrogen atom or a substituent, but at least one of R ₁₁ , R ₁₃ is an electron withdrawing group. Rc and Rd represent a substituent.)
At least one platinum complex represented by the general formula (A) or (B) will be described.

<< Platinum Complex Having Partial Structure Represented by General Formula (A) >>
The platinum complex having the partial structure represented by the general formula (A) will be described.

In the general formula (A), examples of the substituent represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ include an alkyl group (for example, a methyl group, an ethyl group). Propyl group, isopropyl group, (t) butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group etc.), Alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, propargyl group, etc.), aryl group (eg, phenyl group, tolyl group, xylyl group, naphthyl group, biphenylyl group, anthryl group, phenanthryl group, mesityl group) Group, fluorenyl group, etc.), heterocyclic group (for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group) , Furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, carbazolyl group, etc.), alkoxyl group (for example, methoxy group, ethoxy group, propyloxy group) , Pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxyl group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), Alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group, etc.) Arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (Eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octyl) Aminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), Id group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), acyl group (for example, Acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group ( For example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amino Group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group) Group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylamino) Carbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarb Nyl group, 2-pyridylaminocarbonyl group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group etc.), alkylsulfonyl group or arylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl) Group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentyl) Amino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), nitro group, cyano group, silyl group (trimethylsilyl group, t-butyldimethylsilyl group, dimethylphenylsilyl group) , Triphenylsilyl group, etc.).

In the present invention, at least one of the groups represented by R ₁ , R ₂ , R ₃ , and R ₄ is preferably an electron donating group, and more preferably, the R ₁ , R ₂ , R ₃ , R _At least two of the groups represented by ₄ are electron donating groups, and at least one σp of the electron donating group is -0.20 or less, most preferably The electron donating group is introduced into R ₂ or R ₄ of the general formula (A).

<< Electron-donating group with σp of -0.20 or less >>
Here, as the electron donating group having σp of −0.20 or less, for example, cyclopropyl group (−0.21), cyclohexyl group (−0.22), tert-butyl group (−0.20) , —CH ₂ Si (CH ₃ ) ₃ (−0.21), amino group (−0.66), hydroxylamino group (−0.34), —NHNH ₂ (−0.55), —NHCONH ₂ ( _{-0.24), - NHCH 3 (-0.84} ), - NHC 2 H 5 (-0.61), - NHCONHC 2 H 5 (-0.26), - NHC 4 H 9 (-0.51 ), —NHC ₆ H ₅ (−0.40), —N═CHC ₆ H ₅ (−0.55), —OH (−0.37), —OCH ₃ (−0.27), —OCH ₂ COOH (−0.33), —OC ₂ H ₅ (−0.24), —OC ₃ H ₇ (−0. 25), —OCH (CH ₃ ) ₂ (−0.45), —OC ₅ H ₁₁ (−0.34), —OCH ₂ C ₆ H ₅ (−0.42) and the like. Is not limited to these.

In the general formula (A), the substituents represented by Ra and Rb are respectively R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ in the general formula (A). Although it is synonymous with the substituent represented, Preferably, Ra and Rb are the cases where both are alkyl groups.

<< Platinum Complex Having Ligand Represented by Formula (B) >>
The platinum complex having the partial structure represented by the general formula (B) will be described.

In the general formula (B), R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , and R ₁₇ are each a substituent represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ have the same meanings as the substituents respectively represented. Provided _that at least one of R _{11, R 13} is an electron withdrawing _group, preferably R _{11, R 13} are both electron-withdrawing group, more preferably, .sigma.p of the electron withdrawing group is 0. 10 or more.

<< Electron withdrawing group with σp of 0.10 or more >>
Here, as an electron withdrawing group having σp of 0.10 or more, for example, —B (OH) ₂ (0.12), bromine atom (0.23), chlorine atom (0.23), iodine atom ( _{0.18), - CBr 3 (-0.29} ), - CCl 3 (0.33), - CCF 3 (0.54), - CN (0.66), - CHO (0.42), - _{COOH (0.45), CONH 2 (} 0.36), - CH 2 SO 2 CF 3 (0.31), - COCH 3 (0.45), 3- Bareniru group (0.19), - CF ( _{CF 3) 2 (0.53),} - CO 2 C 2 H 5 (0.45), - CF 2 CF 2 CF 2 CF 3 (0.52), - C 6 F 5 (0.41), 2 - benzoxazolyl group (0.33), 2-benzothiadiazolyl no doubt Lil group _{(0.29), - C = O} (C 6 H 5) (0.43) _{, -OCF 3 (0.35), -} OSO 2 CH 3 (0.36), - SO 2 (NH 2) (0.57), - SO 2 CH 3 (0.72), - COCH 2 CH 3 (0.48), —COCH (CH ₃ ) ₂ (0.47), —COC (CH ₃ ) ₃ (0.32) and the like can be mentioned, but the present invention is not limited thereto.

In the general formula (B), the substituents represented by Rc and Rd are, in the general formula (1), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , respectively. Although it is synonymous with the substituent represented, Preferably, Rc and Rd are both a case where it is an alkyl group.

  Although the specific example of the platinum complex which has the partial structure represented by general formula (A) or (B) based on this invention below is shown, this invention is not limited to these.

<Blocking layer: hole blocking layer, electron blocking layer>
The hole blocking layer is an electron transport layer in a broad sense, and is made of a material that has a function of transporting electrons and has a very small ability to transport holes. By blocking holes while transporting electrons, And the recombination probability of holes can be improved.

  The hole blocking layer has a role of blocking the holes moving from the hole transport layer from reaching the cathode and a compound that can efficiently transport the electrons injected from the cathode toward the light emitting layer. It is formed. The physical properties required of the material constituting the hole blocking layer are higher than the ionization potential of the light emitting layer in order to have high electron mobility and low hole mobility and to efficiently confine holes in the light emitting layer. It is preferable to have a value of ionization potential or a band gap larger than that of the light emitting layer.

  It is preferable to use the compound represented by the general formula (C) of the present invention as a hole blocking material. In addition, as a known hole blocking material, it is effective to obtain at least one of a styryl compound, a triazole derivative, a phenanthroline derivative, an oxadiazole derivative, and a boron derivative for obtaining the effects of the present invention.

  Examples of other compounds include exemplified compounds described in JP-A Nos. 2003-31367, 2003-31368, and Japanese Patent No. 2721441.

  On the other hand, the electron blocking layer is a hole transport layer in a broad sense, made of a material that has a function of transporting holes and has a very small ability to transport electrons, and blocks electrons while transporting holes. Thus, the probability of recombination of electrons and holes can be improved.

  The hole blocking layer and the electron blocking layer can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, an ink jet method, or an LB method. .

  The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic.

  For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Conventionally known materials such as stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers, may be used.

  As the hole transport material, those described above can be used, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and two more described in US Pat. No. 5,061,569 Having a condensed aromatic ring of, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  The hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. This hole transport layer may have a single layer structure composed of one or more of the above materials.

《Electron transport layer》
The electron transport layer according to the present invention is only required to have a function of transmitting electrons injected from the cathode to the light emitting layer, and as the material thereof, any one of conventionally known compounds can be selected and used. Can do.

  Examples of materials used for this electron transport layer (hereinafter referred to as electron transport materials) include heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, carbodiimides, Examples include fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, and oxadiazole derivatives. Furthermore, in the oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as an electron transport material. .

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

Or metal complexes of 8-quinolinol derivatives, such as tris (8-quinolinol) aluminum (Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material.

  In addition, metal-free or metal phthalocyanine, and those having the terminal substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material. Alternatively, the distyrylpyrazine derivative exemplified as the material for the light-emitting layer can also be used as an electron transport material, and, like the hole injection layer and the hole transport layer, inorganic such as n-type-Si and n-type-SiC A semiconductor can also be used as an electron transport material.

  The electron transport layer can be formed by forming the above compound by a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method.

  The electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

"anode"
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such an electrode substance include conductive transparent materials such as metals such as Au, CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, a thin film may be formed by depositing these electrode materials by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when the pattern accuracy is not required (100 μm or more) Degree), a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. When light emission is extracted from the anode, it is desirable that the transmittance is greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

"cathode"
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, such as a magnesium / silver mixture, magnesium, from the viewpoint of electron injectability and durability against oxidation, etc. / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.

  The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the emission luminance is advantageously improved.

  Moreover, after producing the said metal with a film thickness of 1-20 nm on a cathode, a transparent or semi-transparent cathode can be produced by producing the electroconductive transparent material quoted by description of the anode on it, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

<< Buffer layer: anode buffer layer, cathode buffer layer >>
The injection layer is provided as necessary, and has a cathode buffer layer (electron injection layer) and an anode buffer layer (hole injection layer). As described above, between the anode and the light emitting layer or the hole transport layer, and the cathode and the light emission. You may exist between a layer or an electron carrying layer.

  The buffer layer is a layer provided between the electrode and the organic layer in order to lower the driving voltage and improve the light emission luminance. “The organic EL element and the forefront of its industrialization (published by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes an anode buffer layer and a cathode buffer layer.

  The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. Examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. . The buffer layer (injection layer) is desirably a very thin film, and although it depends on the material, the film thickness is preferably in the range of 0.1 nm to 5 μm.

<< Substrate (also referred to as substrate, substrate, support, etc.) >>
The organic EL device of the present invention is preferably formed on a substrate.

  There are no particular limitations on the type of substrate, such as glass or plastic, and there is no particular limitation as long as it is transparent, but examples of substrates that are preferably used include glass, quartz, and light-transmitting resin films. Can do. A particularly preferable substrate is a resin film that can give flexibility to the organic EL element.

  Examples of the resin film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), and cellulose triacetate. Examples thereof include films having (TAC), cellulose acetate propionate (CAP) and the like. In addition, an inorganic or organic film or a hybrid film of both may be formed on the surface of the resin film.

  The external extraction quantum efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more. Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

  In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination. In the case of using a color conversion filter, the λmax of light emission of the organic EL element is preferably 480 nm or less.

<< Method for producing organic EL element >>
As an example of the method for producing the organic EL device of the present invention, a method for producing an organic EL device comprising an anode / anode buffer layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode. explain.

  First, a thin film made of a desired electrode material, for example, an anode material ITO, is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 to 200 nm. Make it. Next, an organic compound thin film of an anode buffer layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and a cathode buffer layer, which are organic EL element materials, is formed thereon.

As a method of thinning the organic compound thin film, there are the above-described vapor deposition method, wet process (spin coating method, casting method, ink jet method, printing method), etc., but it is easy to obtain a uniform film, and there is a pinhole. From the viewpoint of difficulty in formation, vacuum deposition, spin coating, ink jet, and printing are preferable. Further, different film forming methods may be applied for each layer. When a vapor deposition method is employed for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a degree of vacuum of 10 ⁻⁶ to 10 ⁻² Pa, and a vapor deposition rate of 0.01. It is desirable to select appropriately within a range of ˜50 nm / second, a substrate temperature of −50 to 300 ° C., and a film thickness of 0.1 nm to 5 μm, preferably 5 to 200 nm.

  After these layers are formed, a cathode material, for example, a thin film made of Al is formed thereon by a method such as vapor deposition or sputtering so as to have a thickness of 1 μm or less, preferably in the range of 50 to 200 nm. By providing, a desired organic EL element can be obtained. The organic EL element is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

  The multicolor display device of the present invention is provided with a shadow mask only when the light emitting layer is formed, and the other layers are common, so that patterning of the shadow mask or the like is unnecessary, and the evaporation method, the casting method, the spin coating method, the ink jet method on one side. A film can be formed by a method or a printing method.

  When patterning is performed only on the light-emitting layer, the method is not limited, but a vapor deposition method, an inkjet method, and a printing method are preferable. In the case of using a vapor deposition method, patterning using a shadow mask is preferable.

  Moreover, it is also possible to produce the cathode, the cathode buffer layer, the electron transport layer, the hole transport layer, the light emitting layer, the hole transport layer, the anode buffer layer, and the anode in this order by reversing the order of production. When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

  The display device of the present invention can be used as a display device, a display, and various light emission sources. In a display device or display, full-color display is possible by using three types of organic EL elements of blue, red, and green light emission.

  Examples of the display device and the display include a television, a personal computer, a mobile device, an AV device, a character broadcast display, and an information display in a car. In particular, it may be used as a display device for reproducing still images and moving images, and the driving method when used as a display device for reproducing moving images may be either a simple matrix (passive matrix) method or an active matrix method.

  The lighting device of the present invention includes home lighting, interior lighting, clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light sensors Although a light source etc. are mentioned, it is not limited to this.

  Further, the organic EL element according to the present invention may be used as an organic EL element having a resonator structure.

  Examples of the purpose of use of the organic EL element having such a resonator structure include a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processing machine, and a light source of an optical sensor. It is not limited. Moreover, you may use for the said use by making a laser oscillation.

<Display device>
The organic EL element of the present invention may be used as one kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a display for directly viewing a still image or a moving image. It may be used as a device (display). When used as a display device for reproducing moving images, the driving method may be either a simple matrix (passive matrix) method or an active matrix method. Alternatively, a full-color display device can be manufactured by using three or more organic EL elements of the present invention having different emission colors. Alternatively, it is possible to make a single color emission color, for example, white emission, into BGR using a color filter to achieve full color. Further, it is possible to convert the emission color of the organic EL to another color by using a color conversion filter, and in this case, λmax of the organic EL emission is preferably 480 nm or less.

  An example of a display device having the organic EL element of the present invention as a configuration will be described with reference to the drawings.

  FIG. 1 is a schematic diagram illustrating an example of a display device including organic EL elements. It is a schematic diagram of a display such as a mobile phone that displays image information by light emission of an organic EL element.

  The display 1 includes a display unit A having a plurality of pixels, a control unit B that performs image scanning of the display unit A based on image information, and the like.

  The control unit B is electrically connected to the display unit A, and sends a scanning signal and an image data signal to each of the plurality of pixels based on image information from the outside. The pixels for each scanning line are converted into image data signals by the scanning signal. In response to this, light is sequentially emitted and image scanning is performed to display image information on the display unit A.

  FIG. 2 is a schematic diagram of the display unit A.

  The display unit A includes a wiring unit including a plurality of scanning lines 5 and data lines 6, a plurality of pixels 3 and the like on a substrate. The main members of the display unit A will be described below. FIG. 2 shows a case where the light emitted from the pixel 3 is extracted in the direction of the white arrow (downward).

  The scanning lines 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern and are connected to the pixels 3 at orthogonal positions (details are shown in FIG. Not shown).

  When a scanning signal is applied from the scanning line 5, the pixel 3 receives an image data signal from the data line 6 and emits light according to the received image data. Full color display is possible by appropriately arranging pixels in the red region, the green region, and the blue region that emit light on the same substrate.

  Next, the light emission process of the pixel will be described.

  FIG. 3 shows a schematic diagram of a pixel.

  The pixel includes an organic EL element 10, a switching transistor 11, a driving transistor 12, a capacitor 13, and the like. A full color display can be performed by using red, green, and blue light emitting organic EL elements as the organic EL elements 10 in a plurality of pixels, and juxtaposing them on the same substrate.

  In FIG. 3, an image data signal is applied from the control unit B to the drain of the switching transistor 11 through the data line 6. When a scanning signal is applied from the control unit B to the gate of the switching transistor 11 via the scanning line 5, the driving of the switching transistor 11 is turned on, and the image data signal applied to the drain is supplied to the capacitor 13 and the driving transistor 12. Is transmitted to the gate.

  By transmitting the image data signal, the capacitor 13 is charged according to the potential of the image data signal, and the drive of the drive transistor 12 is turned on. The drive transistor 12 has a drain connected to the power supply line 7 and a source connected to the electrode of the organic EL element 10, and the power supply line 7 connects to the organic EL element 10 according to the potential of the image data signal applied to the gate. Current is supplied.

  When the scanning signal is moved to the next scanning line 5 by the sequential scanning of the control unit B, the driving of the switching transistor 11 is turned off. However, even if the driving of the switching transistor 11 is turned off, the capacitor 13 maintains the potential of the charged image data signal, so that the driving of the driving transistor 12 is kept on and the next scanning signal is applied. Until then, the light emission of the organic EL element 10 continues. When the scanning signal is next applied by sequential scanning, the driving transistor 12 is driven according to the potential of the next image data signal synchronized with the scanning signal, and the organic EL element 10 emits light.

  That is, the organic EL element 10 emits light by the switching transistor 11 and the drive transistor 12 that are active elements for the organic EL element 10 of each of the plurality of pixels, and the light emission of the organic EL element 10 of each of the plurality of pixels 3. It is carried out. Such a light emitting method is called an active matrix method.

  Here, the light emission of the organic EL element 10 may be light emission of a plurality of gradations by a multi-value image data signal having a plurality of gradation potentials, or on / off of a predetermined light emission amount by a binary image data signal. But you can.

  The potential of the capacitor 13 may be held continuously until the next scanning signal is applied, or may be discharged immediately before the next scanning signal is applied.

  In the present invention, not only the active matrix method described above, but also a passive matrix light emission drive in which the organic EL element emits light according to the data signal only when the scanning signal is scanned.

  FIG. 4 is a schematic view of a passive matrix display device. In FIG. 4, a plurality of scanning lines 5 and a plurality of image data lines 6 are provided in a lattice shape so as to face each other with the pixel 3 interposed therebetween.

  When the scanning signal of the scanning line 5 is applied by sequential scanning, the pixels 3 connected to the applied scanning line 5 emit light according to the image data signal. In the passive matrix system, the pixel 3 has no active element, and the manufacturing cost can be reduced.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, the embodiment of this invention is not limited to these.

Example 1
(Production of organic EL element)
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass) made of ITO (indium tin oxide) with a thickness of 100 nm on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. A solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water on this transparent support substrate at 3000 rpm for 30 seconds. After film formation by a spin coating method, the film was dried at 200 ° C. for 1 hour to provide a 30-nm first hole transport layer. The transparent support substrate provided with the first hole transport layer was fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of α-NPD was placed as a second hole transport layer in a molybdenum resistance heating boat, 200 mg of compound 1 as a host compound is put in another molybdenum resistance heating boat, 100 mg of Ir-12 is put in another resistance heating boat made of molybdenum, and 200 mg of BAlq is put in another resistance heating boat made of molybdenum. 200 mg of Alq ₃ was put into a resistance heating boat and attached to a vacuum deposition apparatus.

Next, after reducing the vacuum chamber to 4 × 10 ⁻⁴ Pa, the second heating plate was heated by energizing the heating boat containing α-NPD and deposited on the transparent support substrate at a deposition rate of 0.1 nm / sec. The hole transport layer was provided. Further, the heating boat containing the compound 1 and Ir-12 was energized and heated, and co-deposited on the hole transport layer at a deposition rate of 0.2 nm / sec and 0.012 nm / sec, respectively, to a film thickness of 30 nm. The light emitting layer was provided. In addition, the substrate temperature at the time of vapor deposition was room temperature. In addition, an electron transport layer that also serves as a hole blocking function with a film thickness of 10 nm is provided by energizing and heating the heating boat containing BAlq and depositing on the light emitting layer at a deposition rate of 0.1 nm / sec. It was. Furthermore, the heating boat containing Alq ₃ was further energized and heated, and was deposited on the electron transport layer at a deposition rate of 0.1 nm / sec to provide an electron injection layer having a thickness of 40 nm. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Then, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited, the cathode was formed, and the organic EL element 1-1 was produced.

  In the production of the organic EL element 1-1, the organic EL elements 1-2 to 1- 1 were the same as the organic EL element 1-1 except that the compound 1 used as the host compound of the light emitting layer was replaced with the compounds shown in Table 1. 13 was produced. The structure of each compound used above is shown below.

(Evaluation of organic EL elements)
The produced organic EL elements 1-1 to 1-13 were evaluated as follows, and the results are shown in Table 1.

<External extraction quantum efficiency>
With respect to the organic EL element, the external extraction quantum efficiency (%) was measured when a 10 mA / cm ² constant current was applied at 23 ° C. in a dry nitrogen gas atmosphere. A spectral radiance meter CS-1000 (manufactured by Konica Minolta) was used for the measurement.

  The measurement results of the external extraction quantum efficiency in Table 1 are expressed as relative values when the measured value of the organic EL element 1-12 is 100.

  From Table 1, it was found that the organic EL device of the present invention was very excellent in external extraction quantum efficiency.

Example 2
(Production of organic EL element)
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass) made of ITO (indium tin oxide) with a thickness of 100 nm on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. A solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water on this transparent support substrate at 3000 rpm for 30 seconds. After film formation by a spin coating method, the film was dried at 200 ° C. for 1 hour to provide a 30-nm first hole transport layer. The transparent support substrate provided with the first hole transport layer was fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of α-NPD was placed as a second hole transport layer in a molybdenum resistance heating boat, In another molybdenum resistance heating boat, 200 mg of CBP was added, in another molybdenum resistance heating boat, 100 mg of Ir-1 was added, and in another molybdenum resistance heating boat, 200 mg of Compound 1 was added as a hole blocking material. 200 mg of Alq ₃ was placed in a molybdenum resistance heating boat and attached to a vacuum deposition apparatus.

Next, after the pressure in the vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD was energized and heated, and deposited on the transparent support substrate at a deposition rate of 0.1 nm / sec. The first hole transport layer was provided. Further, the heating boat containing CBP and Ir-1 was energized and heated, and co-deposited on the hole transport layer at a deposition rate of 0.2 nm / sec and 0.012 nm / sec, respectively, to have a film thickness of 30 nm. A light emitting layer was provided. In addition, the substrate temperature at the time of vapor deposition was room temperature. Further, an electron transport layer that also serves as a hole blocking layer having a film thickness of 10 nm by being heated by energizing the heating boat containing the compound 1 and being deposited on the light emitting layer at a deposition rate of 0.1 nm / sec. Was provided. Furthermore, the heating boat containing Alq ₃ was further energized and heated, and was deposited on the electron transport layer at a deposition rate of 0.1 nm / sec to provide an electron injection layer having a thickness of 40 nm. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Subsequently, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited to form a cathode, and an organic EL element 2-1 was produced.

  In the production of the organic EL element 2-1, the organic EL elements 2-1 to 2-13 were prepared in the same manner as the organic EL element 2-1, except that the compound 1 used as the hole blocking material was replaced with the compounds shown in Table 2. Was made. The structure of the compound used above is shown below.

(Evaluation of organic EL elements)
In the same manner as in Example 1, the external extraction quantum efficiency of the organic EL elements 2-1 to 2-13 was evaluated. Furthermore, the lifetime was evaluated according to the measurement method shown below.

(lifespan)
When driving at a constant current of 10 mA / cm ² , the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance) is measured, and this is used as the half-life time (τ 0.5). It was used as an index. A spectral radiance meter CS-1000 (manufactured by Konica Minolta) was used for the measurement.

  The measurement results of external extraction quantum efficiency and lifetime in Table 2 are expressed as relative values when the organic EL element 2-12 is set to 100.

  From Table 2, it was found that the organic EL device of the present invention achieved a long lifetime.

Example 3
The organic EL element 1-4 of the present invention produced in Example 1, the organic EL element 2-5 of the present invention produced in Example 2, and the phosphorescent compound of the organic EL element 2-5 of the present invention are shown below. A red light-emitting organic EL element produced in the same manner except that Btp ₂ Ir (acac) was replaced was juxtaposed on the same substrate to produce an active matrix type full-color display device shown in FIG. FIG. 2 shows only a schematic diagram of the display portion A of the produced full-color display device. That is, a wiring portion including a plurality of scanning lines 5 and data lines 6 and a plurality of juxtaposed pixels 3 (light emission color is a red region pixel, a green region pixel, a blue region pixel, etc.) on the same substrate. Each of the scanning lines 5 and the plurality of data lines 6 in the wiring portion is made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a lattice shape and are connected to the pixels 3 at the orthogonal positions (details). Is not shown). The plurality of pixels 3 are driven by an active matrix system provided with an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor, and a scanning signal is applied from a scanning line 5. Then, an image data signal is received from the data line 6 and light is emitted according to the received image data. In this way, full-color display is possible by appropriately juxtaposing the red, green, and blue pixels.

  By driving the full-color display device, a clear full-color moving image display with high external extraction quantum efficiency and good durability was obtained.

Example 4
The electrode of the transparent electrode substrate of Example 1 was patterned to 20 mm × 20 mm, and then poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / Plate) as a hole injection / transport layer in the same manner as in Example 1. PSS, manufactured by Bayer, Baytron P Al 4083) and α-NPD were formed to a thickness of 50 nm, and the heated boat containing Compound 1 and the boat containing Ir-12 and Btp ₂ Ir (acac) The entrained boats were energized independently to adjust the deposition rate of PVK as the light emitting host and Ir-12 and Btp ₂ Ir (acac) as the light emitting dopants to 100: 5: 0.6, 30 nm The light emitting layer was provided by vapor deposition so as to have a thickness of 1 mm.

Next, the compound 13 of the present invention was formed to a thickness of 10 nm to provide an electron transport layer. Further, Alq ₃ was deposited at 40 nm to provide an electron injection layer.

  Next, the vacuum chamber is opened, and a square perforated mask having the same shape as the transparent electrode made of stainless steel is placed on the electron injection layer, and 0.5 nm of lithium fluoride is deposited as a cathode buffer layer and 110 nm of aluminum is deposited as a cathode. A film was formed.

  Finally, using a glass substrate having a thickness of 300 μm as a sealing substrate, an epoxy photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealing material around the glass substrate, and this is overlaid on the cathode. The flat support substrate shown in FIGS. 5 and 6 was produced by closely contacting the transparent support substrate, irradiating UV light from the glass substrate side, curing, and sealing. FIG. 5 is a schematic view of the lighting device, and FIG. 6 is a cross-sectional view of the lighting device. The organic EL element 100 is covered with a glass cover 102, the glass substrate 101 with a transparent electrode and the glass cover 102 are sealed with a sealant 107, and a power line (anode) 103 and a power line (cathode) 104 are connected. Has been. 105 is a cathode and 106 is an organic EL layer. The glass cover 102 is filled with nitrogen gas 108 and a water replenisher 109 is provided.

  When this flat lamp was energized, almost white light was obtained, and it was found that it could be used as a lighting device. It has been found that white light emission can be obtained in the same manner even when the light emitting host is replaced with another compound of the present invention.

Example 5
A flat lamp was prepared in the same manner as in Example 4 except that Compound 1 in Example 4 was replaced with CBP and BAlq was replaced with Compound 14 of the present invention. As in Example 4, almost white light was obtained and used as a lighting device. I understood that I could do it. It has been found that white light emission can be obtained in the same manner even when the light emitting host is replaced with another compound of the present invention.

DESCRIPTION OF SYMBOLS 1 Display 3 Pixel 5 Scan line 6 Data line A Display part B Control part 100 Organic EL element 101 Glass substrate with a transparent electrode 102 Glass cover 103 Power supply line (anode)
104 Power line (cathode)
105 Cathode 106 Organic EL layer 107 Sealant 108 Nitrogen gas 109 Water trapping agent

Claims (10)

An organic electroluminescence device having a light emitting layer containing a phosphorescent light emitting material,
Following general formula organic electroluminescence device characterized by using the organic electroluminescence element material you express by (C).

(In the formula, A represents triethylamine, pyridine, or pyrrole, B represents a boron atom, and Ar ₁ , Ar ₂ , and Ar ₃ represent a substituted or unsubstituted aromatic group or heterocyclic group.) Wherein Ar _1, Ar ₂ and Ar ₃ are organic electroluminescence element according to claim 1, characterized in that the atomic group necessary for forming a 6-membered aromatic ring or a heterocyclic ring. Wherein _Ar 1, Ar ₂ and Ar ₃ are organic electroluminescence element according to claim 1 or 2, characterized in that a benzene ring. The organic electroluminescence device according to claim 1, further comprising a hole blocking layer containing the material for the organic electroluminescence device. It has a light emitting layer containing the said organic electroluminescent element material, The organic electroluminescent element of any one of Claims 1-3 characterized by the above-mentioned. The organic electroluminescent element according to claim 1 , which emits blue light. The organic electroluminescent element according to claim 1 , which emits white light. Display device characterized by having an organic electroluminescent element of any one of claims 1 to 7. It has an organic electroluminescent element of any one of Claims 1-7 , The illuminating device characterized by the above-mentioned. A display device comprising: the lighting device according to claim 9; and a liquid crystal element as display means.

Images