JP5699603B2 - Organic electroluminescence element, display device and lighting device - Google Patents

Description

The present invention relates to an organic electroluminescent device, it relates to a display device and an illumination equipment.

  Conventionally, as a light-emitting electronic display device, there is an electroluminescence display (hereinafter referred to as ELD). Examples of 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 device has a structure in which a light-emitting layer containing a light-emitting compound is sandwiched between a cathode and an anode, and excitons (excitons) are generated by injecting electrons and holes into the light-emitting layer and recombining them. The device emits light by utilizing 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. Therefore, it has a wide viewing angle, high visibility, and since it is a thin-film type completely solid element, it has attracted attention from the viewpoints of space saving and portability.

  However, in organic EL elements for practical use in the future, development of organic EL elements that emit light efficiently and with high luminance with lower power consumption is desired.

  In Japanese Patent No. 3093796, a small amount of a phosphor is doped into a stilbene derivative, a distyrylarylene derivative or a tristyrylarylene derivative to achieve an improvement in light emission luminance and a longer device lifetime.

  Further, an element having an organic light-emitting layer in which an 8-hydroxyquinoline aluminum complex is used as a host compound and a small amount of phosphor is doped thereto (for example, JP-A 63-264692), and an 8-hydroxyquinoline aluminum complex is used as a host compound. For example, an element having an organic light emitting layer doped with a quinacridone dye (for example, JP-A-3-255190) is known.

  As described above, when light emission from excited singlet is used, the generation ratio of singlet excitons and triplet excitons is 1: 3, and thus the generation probability of luminescent excited species is 25%. Since the efficiency is about 20%, the limit of the external extraction quantum efficiency (η) is set to 5%.

  However, since Princeton University reported on an organic EL device using phosphorescence emission from an excited triplet (MA Baldo et al., Nature, 395, 151-154 (1998)), Research on materials that exhibit phosphorescence has become active.

  For example, M.M. A. Baldo et al. , Nature, 403, 17, 750-753 (2000), US Pat. No. 6,097,147, and the like.

  When the excited triplet is used, the upper limit of the internal quantum efficiency is 100%. In principle, the luminous efficiency is four times that of the excited singlet. Therefore, it is attracting attention as a lighting application.

  For example, S.M. Lamansky et al. , J .; Am. Chem. Soc. , 123, 4304 (2001), etc., many compounds are being studied for synthesis centering on heavy metal complexes such as iridium complexes.

  In addition, the aforementioned M.I. A. Baldo et al. , Nature, 403, 17, 750-753 (2000), studies have been made using tris (2-phenylpyridine) iridium as a dopant.

In addition, M.M. E. Thompson et al. In The 10th International Works on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu) used L ₂ Ir (acac), for example, (ppy) ₂ Ir (acac), e 0 g, Tetsuo Tsutsui, etc., again The 10th International Workshop on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), the dopant as tris (2-(p-tolyl) pyridine) iridium (Ir _{(ptpy) 3),} tris ( Studies using benzo [h] quinoline) iridium (Ir (bzq) ₃ ) and the like are being conducted (note that these metal complexes are generally called ortho-metalated iridium complexes).

  In addition, the S. Lamansky et al. , J .; Am. Chem. Soc. , 123, 4304 (2001) and Japanese Patent Application Laid-Open No. 2001-247859, etc., attempts have been made to form devices using various iridium complexes.

  In order to obtain high luminous efficiency, in the 10th International Workshop on Inorganic and Organic Electroluminescence (EL'00, Hamamatsu), Ikai et al. Uses a hole transporting compound as a host of a phosphorescent compound. In addition, M.M. E. Thompson et al. Use various electron transporting materials as a host of phosphorescent compounds, doped with a novel iridium complex.

  Orthometalated complexes in which the central metal is platinum instead of iridium are also attracting attention. With respect to this type of complex, many examples are known in which ligands are characterized.

  In either case, the light emission brightness and light emission efficiency of the light emitting device are greatly improved compared to conventional devices because the emitted light is derived from phosphorescence. There was a problem that it was lower than the conventional element.

  As described above, it is difficult for phosphorescent high-efficiency light-emitting materials to shorten the light emission wavelength and improve the light-emission lifetime of the device, and have not been able to achieve practically sufficient performance.

  In addition, regarding wavelength shortening, introduction of an electron withdrawing group such as a fluorine atom, a trifluoromethyl group, a cyano group or the like into phenylpyridine as a substituent, and picolinic acid or a pyrazabole-based ligand as a ligand. It is known to introduce.

  However, with these ligands, the emission wavelength of the light-emitting material is shortened to achieve blue, and a high-efficiency device can be achieved. On the other hand, the light-emitting lifetime of the device is greatly deteriorated, so an improvement in the trade-off is required. It was.

  It is disclosed that a metal complex having phenylpyrazole as a ligand is a light emitting material having a short emission wavelength (for example, see Patent Documents 1 and 2). Furthermore, a metal complex formed from a ligand having a partial structure in which a 6-membered ring is condensed to a 5-membered ring of phenylpyrazole is disclosed (for example, see Patent Documents 3 and 4). There is a disclosure about a metal complex having a phenanthridine skeleton (see, for example, Patent Documents 5 and 6).

  However, the metal complexes described in the above-mentioned known documents do not improve the external extraction quantum efficiency and have not obtained a practically sufficient improvement effect on the light emission lifetime.

  Conventionally, a triarylamine compound is known as a good hole transport material, and a combination example of the compound having the phenanthridine skeleton and α-NPD is disclosed.

  However, the combined use with various phenanthridine compounds is still insufficient in terms of life and efficiency, and further improvement is required.

International Publication No. 04/085450 Pamphlet JP 2005-53912 A JP 2006-28101 A US Pat. No. 7,147,937 US Patent Application Publication No. 2007/190359 International Publication No. 07/095118 Pamphlet

The present invention has been made in view of the above problems, conditions, an object of the present invention specifically short wavelength emission is observed, it shows high luminous efficiency, and long have organic EL elements emission lifetime, lighting An apparatus and a display device are provided .

The above object of the present invention, Ru is achieved by the following means.

1. In an organic electroluminescence device having at least one light emitting layer sandwiched between an anode and a cathode,
The light emitting layer contains at least one compound having a structure represented by the following general formula (A) or general formula (B), and is represented by the following general formula (6) having a glass transition temperature of 100 ° C. or higher. An organic electroluminescent device comprising an organic layer containing at least one compound having a structure.

(In the formula, E1a represents a nitrogen atom and E1b represents a carbon atom. E1c to E1e each represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. The ring composed of E1a to E1e is an imidazole ring. Or E1f, E1h and E1k each represents a carbon atom or a nitrogen atom, E1g and E1i each represents a carbon atom, a nitrogen atom or a sulfur atom, and the ring composed of E1f to E1k represents pyrrole. ring, .R1a～R1f representing the pyrazole ring or imidazole ring, R1h～R1i each a hydrogen atom, a fluorine atom, a cyano group, an alkyl group, an acetyl group from 1 to 4 carbon atoms, a methoxycarbonyl group, a 3-pyridyl group , 2,5-dimethyl-pyrrolyl group or .R1g representing a phenyl group which may have a methyl group or vinyl group, is full E Group, mesityl group, tolyl group, xylyl group, naphthyl group, biphenylyl group, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group, thiazolyl group, benzothiazolyl group represents an isoxazolyl group, an isothiazolyl group or a thienyl group of these substituents may further be substituted with any of the substituents of the substituent group represented by each of the R1a~R1i X _1.. - L ₁ -X ₂ represents a monoanionic bidentate ligand of acetylacetone, picolinic acid, 4-dimethylaminopicolinic acid or 1-mesityl-2-phenyl-1H-imidazole, m1 represents 2 or 3 M2 represents 0 or 1, but m1 + m2 is 3.)

[0034]
[Chemical formula 2]
[0034]

_(Wherein, R 1 _{to R 20} are each a hydrogen atom, an alkyl group, an alkynyl group, or represents a fang aromatic hydrocarbon group or aromatic heterocyclic group. These _{substituents,} R 1 _{to R 20} is it may be further substituted by the substituents each represented. B is off Eniru group, a biphenyl group, a carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group, a fluorenyl group, linked composed pyrenyl group or an anthracenyl group Represents a group, and the molecular weight of the linking group is 180 or more, and these linking groups may be further substituted with the substituents represented by R _{1 to} R _{20, and} m and p each represent 1 to 2 Represents an integer.)

2 . Item 2. The general formula (6), wherein at least one of the substituents represented by R _{1 to} R ₁₀ or R _{1 to} R ₂₀ is a polymerizable substituent. Organic electroluminescence element.

3 . 3. The organic electroluminescent element according to item 1 or 2, wherein the light emitting layer is formed using a wet process.

4 . The organic layer contains at least one compound having the structure represented by the general formula (6), according to any one of the items 1 to 3, wherein, characterized by being formed using a wet process Organic electroluminescence element.

5 . 5. The organic electroluminescence device according to item 4 , wherein the organic layer containing at least one compound having the structure represented by the general formula (6) is a hole transport layer.

6 . 6. The organic electroluminescence device according to item 5, wherein the hole transport layer contains a polymer having a partial structure of a compound having a structure represented by the general formula (6).

7 . Said M is platinum or iridium, The organic electroluminescent element as described in any one of Claims 1-6 characterized by the above-mentioned.

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

9 . An illumination device comprising the organic electroluminescence element according to any one of Items 1 to 7 .

The present invention, specifically short wavelength emission is observed, shows high luminous efficiency and low drive voltage, Ru can provide long organic electroluminescent device of emission life. Further, as a result of the study by the present inventors, the present invention can greatly reduce the initial deterioration during device driving, and has succeeded in greatly reducing the dark spots of the light emitting device. Ru can provide EL element. The illumination device using the element, Ru can be provided a display device.

It is the schematic diagram which showed an example of the display apparatus comprised from an organic EL element. It is a schematic diagram of a display part. It is the schematic of an illuminating device. It is sectional drawing of an illuminating device.

Oite this onset Ming, high have shown the luminous efficiency and a long organic electroluminescent device emission lifetime, Ru can provide a lighting device and a display device using the element.

  In addition, the present inventors succeeded in molecular design of an organic EL element material useful for the organic electroluminescence element of the present invention. The organic electroluminescence device material of the present invention was observed to emit light with a specific short wave, and the lifetime of the organic electroluminescence device of the present invention could be remarkably improved.

  Hereinafter, details of each component according to the present invention will be sequentially described.

《Metal complex (also called metal complex compound)》
The metal complex according to the present invention will be described.

  The present inventors paid attention to the organic EL element material used for the light emitting layer of the organic EL element, and examined various metal complex compounds used as a light emitting dopant.

  The present inventors do not use a conventionally known approach of introducing a substituent into the basic skeleton of a metal complex to control the wavelength or improve the lifetime, but expanding the π-conjugated surface of the condensed ring can stabilize the compound. Various complexes were examined under the focus of increasing the properties. As a result, the improvement tendency of lifetime was found in several condensed ring structures. However, when a fused ring as known so far is introduced, the red shift of the emission wavelength is remarkable, resulting in green and red emission.

The present inventors have further studied, and compounds (metal complexes, metals) in which a condensed ring as shown in the partial structure represented by any one of the general formulas (1) to (4) according to the present invention is introduced. In the case where a complex compound) is applied to a light emitting material, a light emitting dopant having a small emission wavelength shift and a long lifetime at a desired emission wavelength has been successfully developed.

  Further investigation on this new basic skeleton has the disadvantage that the π-conjugated plane becomes larger and the planarity becomes higher, so that the association between metal complexes becomes a problem and the lifetime of the device is remarkably reduced. all right.

  As for the waveform, sub-emission is observed on the long wave side, and a decrease in color purity has become a problem. As a result of various investigations, by introducing at least one substituent into the ligand moiety, association between molecules can be prevented, side-light emission on the long wave side can be suppressed, and the stability of the metal complex (metal complex compound). It was found to improve.

  In addition, these metal complexes are characterized by significant oxidative degradation due to oxygen and light, and there has been concern over degradation over time during handling. As a result of various investigations, R1a in the transition metal complex compound containing at least one substituent in the ligand portion, particularly a partial structure represented by any one of the general formulas (1) to (4) according to the present invention. Alternatively, it has been found that by introducing a substituent into R1b, the oxidative degradation is greatly reduced and the stability of the compound is greatly improved.

  The metal complex compound containing the partial structure represented by any one of the general formulas (1) to (4) according to the present invention has a plurality of ligands depending on the valence of the transition metal element represented by M. However, the ligands may all be the same or may have ligands each having a different structure.

  Here, the part with a ligand remove | excluding the transition metal element M from the partial structure represented by either of General formula (1)-(4) is a ligand, respectively.

(Conventionally known ligand)
Moreover, as what is called a ligand, the said trader can use together a well-known ligand (it is also called a coordination compound) as a ligand as needed.

  From the viewpoint of preferably obtaining the effects described in the present invention, the type of ligand in the complex is preferably composed of 1 to 2 types, and more preferably 1 type.

  There are various known ligands used in conventionally known metal complexes. For example, “Photochemistry and Photophysics of Coordination Compounds” Springer-Verlag H. Published by Yersin, 1987, “Organometallic Chemistry-Fundamentals and Applications-” Liu Huabosha, Akio Yamamoto, published by 1982, etc. (for example, halogen ligands (preferably chlorine ligands), Nitrogen heterocyclic ligands (for example, bipyridyl, phenanthroline, etc.) and diketone ligands).

(Transition metal element of group 8-10 of the periodic table)
As a metal used for forming a compound (also referred to as a transition metal complex, a metal complex, or a metal complex compound) containing a partial structure represented by any one of the general formulas (1) to (4) according to the present invention, an element A transition metal element belonging to Group 8 to 10 in the periodic table (also simply referred to as a transition metal) is used, and among these, iridium and platinum are preferable transition metal elements.

(Contained layer of transition metal complex according to the present invention)
The containing layer of the metal complex compound including the partial structure represented by any one of the general formulas (1) to (4) according to the present invention is not particularly limited as long as it is a layer that transports charges (charge transport layer). However, a hole transport layer or a light emitting layer, a light emitting layer or an electron blocking layer is preferable, a light emitting layer or an electron blocking layer is more preferable, and a light emitting layer is particularly preferable.

  Moreover, when it contains in a light emitting layer, by using as a light emission dopant in a light emitting layer, the efficiency improvement (high brightness) of the external extraction quantum efficiency of the organic EL element of this invention and the lifetime improvement of a light emission lifetime are achieved. be able to. The constituent layers of the organic EL element of the present invention will be described in detail later.

<< Partial structure represented by any one of general formulas (1) to (4) >>
The partial structure represented by any one of the general formulas (1) to (4) according to the present invention will be described.

  In the partial structure represented by any one of the general formulas (1) to (4), the ring formed by E1a to E1e represents a 5-membered aromatic heterocyclic ring, such as an oxazole ring, a thiazole ring, or an oxadiazole. Examples include a ring, an oxatriazole ring, an isoxazole ring, a tetrazole ring, a thiadiazole ring, a thiatriazole ring, an isothiazole ring, a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a pyrazole ring, and a triazole ring. Among these, a pyrazole ring, an imidazole ring, an oxazole ring, and a thiazole ring are preferable, and a pyrazole ring and an imidazole ring are particularly preferable. Each of these rings may further have a substituent described later.

  In the partial structure represented by any one of the general formulas (1) to (4), the ring formed by E1f to E1k is a 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocycle Represents.

  Examples of the 6-membered aromatic hydrocarbon ring formed by E1f to E1k include a benzene ring. Furthermore, you may have the substituent mentioned later. Examples of the 5- or 6-membered aromatic heterocycle formed by E1f to E1k include a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine ring. Can be mentioned. Each of these rings may further have a substituent described later.

  In the partial structure represented by any one of the general formulas (1) to (4), the ring formed by E1l to E1q is a 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocycle These rings are each synonymous with a 6-membered aromatic hydrocarbon ring formed by E1f to E1k, or a 5-membered or 6-membered aromatic heterocycle.

  In the partial structure represented by any one of the general formulas (1) to (4), each of the substituents represented by R1a to R1i includes an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an 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 (for example, vinyl group, Allyl group), alkynyl group (for example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon ring group (aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group, mesityl group, Tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthate Group, indenyl group, pyrenyl group, biphenylyl group, etc.), aromatic heterocyclic group (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, , 1,2,4-triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, Thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group) One is replaced by a nitrogen atom), mushroom Linyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy) Group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.) Alkylthio groups (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio groups (eg, cyclopentylthio group, cyclohexylthio group, etc.), aryl Ruthio 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.), 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 Groups (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide groups (for example, methylcarbonylamino group, ethylcarbonylamino group, Dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, Octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group) Cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, Ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group 2-pyridylaminoureido 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 (eg methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group etc.), arylsulfonyl group or heteroarylsulfonyl group (eg , Phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group) Butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom), fluoride Hydrocarbon group (for example, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group) Group, triphenylsilyl group, phenyldiethylsilyl group, etc.), phosphono group and the like. These substituents may be further substituted with the above substituents.

  A plurality of these substituents may be bonded to each other to form a ring, and when a plurality of substituents are present, each substituent may be the same or different, and linked to each other to form a ring. It may be formed.

  In the partial structure represented by any one of the general formulas (1) to (4), the substituents represented by R1a to R1i are each a styryl group, an epoxy group, an oxetanyl group, an acrylic group in addition to the alkenyl group described above. , And may have a polymerizable group such as a tacryl group. Furthermore, the compound represented by the partial structure represented by any one of the general formulas (1) to (4) can react with the polymerizable groups or with other polymerizable monomers to form a polymer. .

  When a plurality of partial structures are present in the polymer, the partial structures represented by any one of the general formulas (1) to (4) may be the same or different.

  In the partial structure represented by the general formula (1), (2), (3) or (4), R1a or R1b is preferably an alkyl group, an aromatic hydrocarbon ring group or an aromatic heterocyclic group, A more preferred form of the aromatic hydrocarbon ring group and the aromatic heterocyclic group is a group represented by the general formula (1A), more preferably a group represented by the general formula (2A), and particularly preferred. Is a group represented by the general formula (3A).

Hereinafter, groups represented by general formula (1A) to general formula (3A) will be described.
In the formula, Z represents a 5- or 6-membered aromatic hydrocarbon group or aromatic heterocyclic group. A represents a nitrogen atom or a carbon atom. Ra represents a substituent having a steric parameter value (Es value) of −0.5 or less. Rb represents a hydrogen atom or a substituent. n represents an integer of 1 to 4.
In the formula, Ra represents a substituent having a steric parameter value (Es value) of −0.5 or less. Rb represents a hydrogen atom or a substituent. n represents an integer of 1 to 4.
In the formula, Ra and Rc each represent a substituent having a steric parameter value (Es value) of −0.5 or less. Rb represents a hydrogen atom or a substituent. n represents an integer of 1 to 4.

<< Group Represented by General Formula (1A) >>
In the general formula (1A), the atomic group necessary for forming a 6-membered aromatic hydrocarbon ring or a 5-membered to 6-membered aromatic heterocycle represented by Z is represented by the general formula (1) or In the partial structure represented by (2), each is synonymous with a 6-membered aromatic hydrocarbon ring formed by E1f to E1k, or a 5-membered or 6-membered aromatic heterocycle.

  In the general formula (1A), the substituent represented by Rb has the same definition as the substituent represented by R1a to R1i in the partial structure represented by the general formula (1) or (2).

  In the general formula (1A), a substituent having a steric parameter value (Es value) represented by Ra of −0.5 or less will be described in detail below. In addition, the substituent is preferably bonded to the atom adjacent to A constituting the 6-membered aromatic hydrocarbon ring or 5-membered to 6-membered aromatic heterocycle formed by the Z. Furthermore, this is preferably an electron donating group which will be described in detail below.

  Hereinafter, the three-dimensional parameter value (Es value) will be described.

(3D parameter value (Es value))
In the present invention, the Es value is a steric parameter derived from chemical reactivity. The smaller this value, the more sterically bulky substituent can be said.

  In general, in ester hydrolysis under acidic conditions, it is known that the influence of substituents on the progress of the reaction may only be considered as steric hindrance. The Es value is obtained by quantifying the steric hindrance.

The Es value of the substituent X is expressed by the following chemical reaction formula: X—CH ₂ COORX + H ₂ O → X—CH ₂ COOH + RXOH
A reaction rate constant k for hydrolysis of an α-monosubstituted acetate derived from α-monosubstituted acetic acid obtained by substituting one hydrogen atom of the methyl group of acetic acid represented by X and the following chemical reaction formula CH ₃ COORY + H ₂ O → CH ₃ COOH + RYOH
(RX is the same as RY), which is obtained from the reaction rate constant kH when the acetate corresponding to the α-monosubstituted acetate described above is hydrolyzed under acidic conditions.

Es = log (kX / kH)
The reaction rate decreases due to the steric hindrance of the substituent X, and as a result, kX <kH, so the Es value is usually negative. When the Es value is actually obtained, the above two reaction rate constants kX and kH are obtained and calculated by the above formula.

  Specific examples of Es values are given by Unger, S. et al. H. Hansch, C .; , Prog. Phys. Org. Chem. 12, 91 (1976). The specific numerical values are also described in “Structure-activity relationship of drugs” (Regional Chemistry Special Issue 122, Nankodo) and “American Chemical Society Reference Book, 'Exploring QSAR' p.81 Table 3-3”. There is. Next, a part is shown in Table 1.

  Here, it should be noted that the Es value as defined in this specification is not defined by defining that of a methyl group as 0, but by assuming that a hydrogen atom is 0, and an Es value where a methyl group is 0. Minus 1.24.

  The Es value according to the present invention is −0.5 or less. Preferably it is -7.0--0.6. Most preferably, it is -7.0 to -1.0.

  Here, in the present invention, when a steric parameter value (Es value) is -0.5 or less, for example, when a keto-enol tautomer may exist in Z, the keto moiety is an Esol isomer. The value is converted. Even when other tautomerism exists, the Es value is converted by the same conversion method. Furthermore, the substituent having an Es value of −0.5 or less is preferably an electron-donating substituent in terms of electronic effect.

(Electron donating group (electron donating substituent))
In the present invention, the electron-donating substituent is a substituent having a negative Hammett σp value as described below, and such a substituent has an electron on the bonding atom side compared to a hydrogen atom. Easy to give.

  Specific examples of the substituent exhibiting an electron donating property include a hydroxy group, a thiol group, an alkoxy group (for example, methoxy group), an alkylthio group, an arylthio group, an acetyloxy group, an amino group, a dimethylamino group, an acetylamino group, An alkyl group (for example, a methyl group, an ethyl group, a propyl group, a t-butyl group, etc.) and an aryl group (for example, a phenyl group, a mesityl group, etc.) are mentioned. For Hammett's σp value, for example, the following documents can be referred to.

  The Hammett σp value according to the present invention refers to Hammett's substituent constant σp. Hammett's σp value is a substituent constant determined by Hammett et al. From the electronic effect of the substituent on the hydrolysis of ethyl benzoate. “Structure-activity relationship of drugs” (Nanedo: 1979), “Substituent” The groups described in “Constants for Correlation Analysis in Chemistry and Biology” (C. Hansch and A. Leo, John Wiley & Sons, New York, 1979) can be cited.

  In the present invention, among the groups represented by the general formula (1A), the group represented by the general formula (2A) is preferable.

<< General formula (2A) >>
In the general formula (2A), the steric parameter value (Es value) represented by Ra has a steric parameter value (Es value) represented by Ra in the general formula (1A). It is synonymous with a substituent of −0.5 or less.

  In the general formula (2A), the substituent represented by Rb has the same meaning as the substituents represented by R1a to R1i in the partial structure represented by the general formula (1) or (2).

<< General formula (3A) >>
In the general formula (3A), the substituents each represented by Ra and Rc and having a steric parameter value (Es value) of −0.5 or less are the steric parameter values represented by Ra in the general formula (1A) ( (Es value) is synonymous with a substituent of -0.5 or less.

  In the general formula (3A), the substituent represented by Rb has the same meaning as the substituents represented by R1a to R1i in the partial structure represented by the general formula (1) or (2).

<Method for Polymerizing Partial Structure Represented by any of General Formulas (1) to (4)>
The polymer (polymer) of the partial structure represented by any one of the general formulas (1) to (4) is “Revised Polymer Synthesis Chemistry” Chemistry “Polymer Synthesis Experimental Method” Chemistry Dojin “4th Edition Experiment It can be synthesized using the method described in Chemistry Lecture 28 “Polymer Synthesis” Maruzen et al.

  Preferable polymerization methods include 1) polycondensation, 2) radical polymerization, 3) ionic polymerization, 4) polyaddition, addition condensation, and the like, which can be used depending on the type of polymerizable group.

  The polymer having a partial structure represented by any one of the general formulas (1) to (4) can be made into a homopolymer using the above method, or can be made into a copolymer in combination with a plurality of monomers. is there.

  Hereinafter, specific examples of the compound (also referred to as a metal complex or a metal complex compound) including a partial structure represented by any one of the general formulas (1) to (4) according to the present invention will be shown. It is not limited.

  In the above, the structures of acac, ppz, MPI, SBI, ppz, DPPD, 4Mesppz are shown below.

  In the above, the structure and substitution position of the substituents J1 to J30 are indicated by * below. The substitution position of Xylyl is also indicated by *. In the substituent J6J1, J1 is close to the mother nucleus.

  These metal complexes are described in, for example, Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, 3055-3066 (2002) , New Journal of Chemistry, 26, 1171 (2002), Organic Letter, vol8, No. 3, pages 415 to 418 (2006), and further by applying methods such as references described in these documents.

  Although the synthesis example of the metal complex based on this invention is shown below, this invention is not limited to these.

  Synthesis of exemplary compound A-97

Step 1: Synthesis of Complex C 2-methylimidazo [1,2-f] phenanthridine 0.9 g (0.003875 mol), 2-ethoxyethanol 13 ml, and water 3 ml were placed in a 100 ml four-necked flask, and nitrogen was blown into the flask. A tube, a thermometer and a condenser were attached and set on an oil bath stirrer. To this, 0.55 g (0.001560 mol) of IrCl ₃ 3H ₂ O and 0.16 g (0.001560 mol) of triethylamine were added, and the mixture was boiled and refluxed at an internal temperature of about 100 ° C. for 6 hours to complete the reaction. It was.

  After completion of the reaction, the reaction mixture was cooled to room temperature, methanol was added, and the precipitated solid was collected by filtration. The obtained solid was thoroughly washed with methanol and dried to obtain 1.05 g (98.1%) of Complex C.

Step 2: Synthesis of Complex D In a 50 ml four-necked flask, 1.0 g (0.0007244 mol) of Complex C, 0.29 g of acetylacetone, 1.0 g of sodium carbonate, and 24 ml of 2-ethoxyethanol were introduced, and nitrogen was blown into the flask. A tube, a thermometer and a condenser were attached and set on an oil bath stirrer. The mixture was heated and stirred for 1.5 hours at a nitrogen gas stream inner temperature of around 80 ° C.

  After completion of the reaction, the reaction solution was cooled to room temperature, methanol was added to the reaction solution, and the precipitated crystals were filtered. The crystals were washed with 30 ml of water and 10 ml of MeOH and dried to obtain 0.73 g of Complex D, 0.42 g (38.5%).

Step 3: Synthesis of Exemplified Compound A-97 In a 50 ml four-necked flask, 0.386 g (0.0005120 mol) of Complex D, 0.357 g of 2-methylimidazo [1,2-f] phenanthridine, glycerin 20 ml was added, and a nitrogen blowing tube, a thermometer, and an air cooling tube were attached and set on an oil bath stirrer. The reaction was completed by heating and stirring for 4.5 hours at an internal temperature of 150 ° C. under nitrogen flow. After completion of the reaction, the mixture was cooled to room temperature, methanol was added and dispersed, and the crystals were collected by filtration to obtain 0.38 g of crude crystals.

  The crystals were purified by column chromatography (developing solvent: toluene / ethyl acetate), and the obtained crystals were purified by suspension with heating in a mixed solvent of tetrahydrofuran and ethyl acetate, and 0.3 g (66.6%) of Exemplified Compound A-97 was obtained. )Obtained.

  The structure of Example Compound A-97 obtained was confirmed using 1H-NMR (nuclear magnetic resonance spectrum). Measurement conditions, chemical shift of each peak of the obtained spectrum, proton number, etc. are shown below.

1H-NMR (400 MHz, tetrahydrofuran-d8)
Measuring apparatus: JEOL JNM-AL400 (400 MHz): manufactured by JEOL Ltd. Spectrum attribution (chemical shift δ, proton number, peak shape)
8.48 (1H, d), 7.93 (1H, d), 7.75 (1H, s), 7.64 (1H, d), 7.54 (1H, t), 7.46 (1H) , T), 6.95 (1H, t), 6.83 (1H, d), 1.85 (3H, s). In addition, the emission wavelength in the solution of exemplary compound A-97 was 455 nm. (The emission wavelength is measured in 2-methyltetrahydrofuran.)
<< Compounds Represented by General Formulas (5) and (6) >>
The compounds represented by the general formulas (5) and (6) according to the present invention will be described.

In the general formula (5), R ₁ to R ₁₀ each represent a hydrogen atom or a substituent.

Examples of the substituent represented by R ₁ to R ₁₀ include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group). Group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), Aromatic hydrocarbon ring group (also called aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, Fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.) Group heterocyclic group (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1 , 2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl Group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (indicating that one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), quinoxalinyl group, pyridazinyl Group, triazinyl group, quinazolinyl group , Phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyl group) Oxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, 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 (for example, phenylthio group, naphthylthio group, etc.), a Coxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group) ), Sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl) Group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl 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) Group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentyl) Carbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, Benzylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group) 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido) Group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido 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 (for example, methyl Sulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (for example, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl) Group), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexyl group). Ruamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, diphenylamino group, phenylnaphthylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom), fluorinated hydrocarbon Group (for example, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, Triphenylsilyl group, phenyldiethylsilyl group, etc.), phosphono group and the like. These substituents may be further substituted with the above substituents.

  A plurality of these substituents may be bonded to each other to form a ring, and when a plurality of substituents are present, each substituent may be the same or different, and linked to each other to form a ring. It may be formed.

  In the general formula (5), A is an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, Pentadecyl group), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), aromatic hydrocarbon ring group (aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group, mesityl group , Tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.), aromatic heterocyclic group (for example, pyridyl group, pyrimidinyl group, Furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, pyrazoli Group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, Isoxazolyl, isothiazolyl, furazanyl, thienyl, quinolyl, benzofuryl, dibenzofuryl, benzothienyl, dibenzothienyl, indolyl, carbazolyl, carbolinyl, diazacarbazolyl One of the carbon atoms constituting the carboline ring is replaced by a nitrogen atom), quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl) Group, oxazolidyl group, etc.) . These groups may be further substituted with the above substituents.

  In General formula (5), m represents the integer of 1-4.

In the general formula (6), R ₁ to R ₂₀ each represent a hydrogen atom or a substituent, and examples of the substituent are the same as those in the general formula (5). In the general formula (6), B represents a linking group composed of an alkyl group, an aromatic hydrocarbon ring group, and an aromatic heterocyclic group. Examples of the alkyl group, the aromatic hydrocarbon ring group, and the aromatic heterocyclic group Is synonymous with the description in the general formula (5). These substituents may be further substituted with the above substituents.

  The linking group composed of an alkyl group, an aromatic hydrocarbon ring group, and an aromatic heterocyclic group each may have one substituent as a linking group, and may be a plurality of alkyl groups, aromatic hydrocarbon groups, aromatic groups. Group heterocyclic groups may be connected to each other. In addition, the connecting groups formed by connecting may be the same or different. The linking group may be substituted with a substituent in the general formula (5), and may be linked to each other to form a ring.

  The linking group represented by B in the general formula (6) is preferably a phenyl group, a biphenyl group, a terphenyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a fluorenyl group, a pyrenyl group, or an anthracenyl group.

  In the general formula (6), the molecular weight of the linking group represented by B is preferably 180 or more and 500 or less. More preferably, it is 180-300. Here, the molecular weight of the linking group is (molecular weight of the linking group itself− (m + p)). m and p represent an integer of 1 to 2.

  The glass transition temperature of the compound represented by the general formula (5) or (6) is preferably 100 ° C. or higher and lower than 400 ° C. More preferably, it is 100 degreeC or more and less than 350 degreeC. The glass transition temperature (also referred to as glass transition point) according to the present invention can be determined using a commercially available DSC (Differential Scanning Calorimetry) measuring device.

  The molecular weight of the compound represented by the general formula (5) or (6) is preferably 600 or more and less than 2000. However, when the compound represented by the general formula (5) or (6) forms a polymer, the molecular weight of the monomer is preferably 600 or more and less than 2000.

  More preferable forms in the general formula (5) or (6) are represented by the following general formulas (7) to (10).

In the general formula (7), R ₁ to R ₁₅ each represent a hydrogen atom or a substituent, and examples of the substituent are the same as those in the general formula (5). Each substituent may be the same or different. Moreover, each substituent may be further substituted with the substituent in General formula (5). Further, each adjacent substituent may be linked to each other to form a ring.

In the general formula (8), R ₁ to R ₂₀ each represent a hydrogen atom or a substituent, and examples of the substituent are the same as those in the general formula (5). Each substituent may be the same or different. Each substituent may be further substituted with a substituent in the general formula (5). Further, each adjacent substituent may be linked to each other to form a ring.

In the general formula (8), Ar ₁ and Ar ₂ represent an aromatic hydrocarbon ring group and an aromatic heterocyclic group, and examples of the aromatic hydrocarbon ring group and the aromatic heterocyclic group are explained in the general formula (5). It is synonymous with. Among the above aromatic hydrocarbon ring groups and aromatic heterocyclic groups, preferably a phenyl group, a biphenyl group, a terphenyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a fluorenyl group, a pyrenyl group, an anthracenyl group is there. The aromatic hydrocarbon ring group and aromatic heterocyclic group may be further substituted with a substituent described in the general formula (5).

In the general formula (8), J ₁ represents a linking group, specifically, an alkylene group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, —O—, —NRa—, —S—, —Se—. , -P (= O)-, -PRb-, -SiRc-, -CRdRe-, and the like. Here, Ra, Rb, Rc, Re, and Re represent a hydrogen atom or a substituent, and description of the substituent is synonymous with the description in General formula (5). In the general formula (8), q represents an integer of 0 to 3, and when q is 0, J ₁ -Ar ₂ represents a bond.

In the general formula (9), R ₁ to R ₂₈ each represent a hydrogen atom or a substituent, and examples of the substituent are the same as those in the general formula (5). Each substituent may be the same or different. Each substituent may be further substituted with a substituent in the general formula (5). Further, each adjacent substituent may be linked to each other to form a ring. R ₂₂ and R ₂₅ and / or R ₂₄ and R ₂₇ may be linked to each other to form a ring.

In the general formula (10), R ₁ to R ₃₂ each represent a hydrogen atom or a substituent, and examples of the substituent are the same as those in the general formula (5). Each substituent may be the same or different. Each substituent may be further substituted with a substituent in the general formula (5). Further, each adjacent substituent may be linked to each other to form a ring. R ₂₆ and R ₂₉ , and / or R ₂₈ and R ₃₁ may be connected to each other to form a ring.

  In General formula (10), X and Y represent an oxygen atom, a sulfur atom, a selenium atom, and —NRf—, and Rf represents a hydrogen atom or an alkyl group, an aromatic hydrocarbon ring group, and an aromatic heterocyclic group. The description of the alkyl group, aromatic hydrocarbon ring group, and aromatic heterocyclic group in Rf has the same meaning as in General Formula (5). Each alkyl group, aromatic hydrocarbon ring group, and aromatic heterocyclic group may be further substituted with a substituent in the general formula (5).

  The compounds represented by the general formulas (5) to (10) may have a polymerizable group such as a styryl group, an epoxy group, an oxetanyl group, an acrylic group, and a methacryl group in addition to the alkenyl group described above. . Furthermore, the compounds represented by the general formulas (5) to (10) can react with the polymerizable groups or with other polymerizable monomers to form a polymer.

  When a plurality of partial structures are present in the polymer, the partial structures represented by any one of the general formulas (5) to (10) may be the same or different.

<Method for Polymerizing Compounds Represented by General Formulas (5) to (10)>
The polymer (polymer) of the compound represented by the general formulas (5) to (10) can be synthesized according to the polymerization method of the partial structure represented by any one of the general formulas (1) to (4). it can. The polymer (polymer) of the compounds represented by the general formulas (5) to (10) can be made into a homopolymer using the above-described method, or can be made into a copolymer combined with a plurality of monomers. .

  Although the specific example of a compound represented by either of General formula (5)-(10) below is shown, this invention is not limited to these.

These compounds can be synthesized using known methods. For example, synthesis is performed using the methods described in JP-A-4-126790, JP-A-9-194441, JP-A-2004-26732, JP-A-2006-22089, JP-A-2007-91719, and the like. << Constitutional layer of organic EL element >>
The constituent layers of the organic EL element of the present invention will be described. In this invention, although the preferable specific example of the layer structure of an organic EL element is shown below, this invention is not limited to these.

(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) Anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode (vi) Anode / hole transport layer / electron block layer / light emitting layer / hole block layer / electron transport layer / cathode In the organic EL device of the present invention, blue light emission The light emission maximum wavelength of the layer is preferably 430 to 480 nm, the green light emission layer is preferably a monochromatic light emitting layer having a light emission maximum wavelength of 510 to 550 nm, and the red light emitting layer is a light emission maximum wavelength of 600 to 640 nm. A display device using these is preferable. Alternatively, a white light emitting layer may be formed by laminating at least three light emitting layers. Further, a non-light emitting intermediate layer may be provided between the light emitting layers. The organic EL element of the present invention is preferably a white light emitting layer, and is preferably a lighting device using these.

  Each layer which comprises the organic EL element of this invention is demonstrated.

<Light emitting layer>
The light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.

  The total film thickness of the light emitting layer is not particularly limited, but it is 2 nm to from the viewpoint of preventing the application of a high voltage unnecessary for the film homogeneity and light emission and improving the stability of the emission color with respect to the drive current. It is preferable to adjust to the range of 5 micrometers, More preferably, it adjusts to the range of 2-200 nm, Most preferably, it is the range of 10-20 nm.

  For the production of the light-emitting layer, a light-emitting dopant or a host compound, which will be described later, is formed 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. it can.

  The light emitting layer of the organic EL device of the present invention preferably contains a light emitting host compound and a light emitting dopant (phosphorescent dopant (also referred to as phosphorescent dopant), fluorescent dopant, etc.).

(Host compound (also called luminescent host))
The host compound used in the present invention will be described.

  Here, the host compound in the present invention is a phosphorescent quantum yield of phosphorescence emission at a room temperature (25 ° C.) having a mass ratio of 20% or more in the compound contained in the light emitting layer. Is defined as a compound of less than 0.1. The phosphorescence quantum yield is preferably less than 0.01. Moreover, it is preferable that the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.

  As the host compound, known host compounds may be used alone or in combination of two or more. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the efficiency of the organic EL element can be increased. Moreover, it becomes possible to mix different light emission by using multiple types of light emission dopants mentioned later, and, thereby, arbitrary luminescent colors can be obtained.

  In addition, the light emitting host used in the present invention may be a conventionally known low molecular compound or a high molecular compound having a repeating unit, and a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (deposition polymerization property). Light emitting host).

  Although the specific example of the host compound preferably used for this invention below is shown, this invention is not limited to these.

  As a known host compound that may be used in combination, a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from being increased in wavelength, and has 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.

(Luminescent dopant)
The luminescent dopant according to the present invention will be described.

  As the light-emitting dopant according to the present invention, a fluorescent dopant (also referred to as a fluorescent compound) or a phosphorescent dopant (also referred to as a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like) can be used. From the viewpoint of obtaining an organic EL device with high luminous efficiency, the above-mentioned host compound is used as a light emitting dopant (sometimes simply referred to as a light emitting material) used in the light emitting layer or light emitting unit of the organic EL device of the present invention. It is preferable to contain a phosphorescence dopant simultaneously with containing.

(Phosphorescent dopant)
The phosphorescent dopant according to the present invention will be described.

  The phosphorescent dopant according to the present invention is a compound in which light emission from an excited triplet is observed. Specifically, the phosphorescent dopant is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 25 ° C. Although defined as 0.01 or more compounds, the preferred phosphorescence quantum yield is 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 dopant according to the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. That's fine.

  There are two types of light emission of phosphorescent dopants 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 transferred to the phosphorescent dopant. Energy transfer type to obtain light emission from the phosphorescent dopant, another is that the phosphorescent dopant becomes a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant is obtained In any case, the excited state energy of the phosphorescent dopant is required to be lower than the excited state energy of the host compound.

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

  The phosphorescent dopant according to the present invention is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex compound), Rare earth complexes, most preferably iridium compounds.

  The compound used as the phosphorescent dopant according to the present invention is preferably a transition metal complex compound including a partial structure represented by any one of the general formulas (1) to (4) according to the present invention.

  Moreover, you may use together a conventionally well-known light emission dopant as shown below.

(Fluorescent dopant (also called fluorescent compound))
As fluorescent dopants, coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes , Polythiophene dyes, or rare earth complex phosphors.

  Next, an injection layer, a blocking layer, a hole transport layer, an electron transport layer, and the like used as a constituent layer of the organic EL element of the present invention will be described.

<< Injection layer: electron injection layer, hole injection layer >>
The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, it exists between the anode and the light emitting layer or the hole transport layer and between the cathode and the light emitting layer or the electron transport layer. May be.

  An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (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 preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm although it depends on the material.

<Blocking layer: hole blocking layer, electron blocking layer>
The blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

  The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed. The hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.

  In the hole blocking layer, the carbazole derivative, carboline derivative, diazacarbazole derivative (shown by replacing one of the carbon atoms constituting the carboline ring of the carboline derivative with a nitrogen atom) as the host compound described above. It is preferable to contain.

  Further, in the present invention, when a plurality of light emitting layers having different light emission colors are provided, it is preferable that the light emitting layer whose emission maximum wavelength is the shortest is the closest to the anode among all the light emitting layers. In this case, it is preferable that a hole blocking layer is additionally provided between the shortest wave layer and the light emitting layer next to the anode next to the shortest wave layer. Furthermore, it is preferable that 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.

  The ionization potential is defined by the energy required to emit electrons at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level, and can be determined by, for example, the following method.

  (1) Gaussian 98 (Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.), a molecular orbital calculation software manufactured by Gaussian, USA, is used as a keyword. By performing structural optimization using B3LYP / 6-31G *, the ionization potential can be obtained as a value obtained by rounding off the second decimal place of the calculated value (eV unit converted value). This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.

  (2) The ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy. For example, a method known as ultraviolet photoelectron spectroscopy can be suitably used using a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki.

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

  Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed. In that case, it is also possible to use the aromatic tertiary amine compound according to any one of the general formulas (5) to (10) according to the present invention as an electron blocking layer, separately from the hole transport layer described later. . The film thickness of the hole blocking layer and the electron transporting layer according to the present invention is preferably 3 to 100 nm, and more preferably 5 to 30 nm.

《Hole transport layer》
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

  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, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  The above-mentioned materials can be used as the hole transport material, but any of the porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds, particularly any one of the general formulas (5) to (10) according to the present invention. The aromatic tertiary amine compounds described are preferably used. 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.

  JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material as described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, these materials are preferably used because a light-emitting element with higher efficiency can be obtained.

  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. The hole transport layer may have a single layer structure composed of one or more of the above materials.

  Alternatively, a hole transport layer having a high p property doped with impurities can be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.

  In the present invention, it is preferable to use a hole transport layer having such a high p property because a device with lower power consumption can be produced.

《Electron transport layer》
The electron transport layer is made of a material having a function of transporting electrons. In a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers.

  Conventionally, in the case of a single electron transport layer and a plurality of layers, an electron transport material (also serving as a hole blocking material) used for an electron transport layer adjacent to the light emitting layer on the cathode side is injected from the cathode. As long as it has a function of transferring electrons to the light-emitting layer, any material can be selected and used from among conventionally known compounds. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives Thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like.

  Furthermore, in the above 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.

  In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), 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, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material. In addition, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and the hole transport layer. Can also be used as an electron transporting material.

  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.

  Further, an electron transport layer having a high n property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

  In the present invention, it is preferable to use an electron transport layer having such a high n property because an element with lower power consumption can be produced.

"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 electrode materials include metals such as Au, and conductive transparent materials such as 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, these electrode materials may be formed into a thin film 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 pattern accuracy is not so high (about 100 μm or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.

  Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be 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, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / 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 the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

  In addition, a transparent or semi-transparent cathode can be produced by producing the conductive transparent material mentioned in the description of the anode on the cathode after producing the metal with a thickness of 1 to 20 nm on the cathode. By applying the above, it is possible to manufacture a device in which both the anode and the cathode are transparent.

《Support substrate》
As a support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention, there is no particular limitation on the type of glass, plastic, etc., and it is transparent. May be opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.

  Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Polyetherimide, polyether ketone imide, polyamide, fluorine resin, nylon, polymethyl methacrylate, acrylic or polyarylates, and cycloolefin resins such as ARTON (manufactured by JSR) or APEL (manufactured by Mitsui Chemicals).

On the surface of the resin film, an inorganic film, an organic film, or a hybrid film of both may be formed. Water vapor permeability (25 ± 0.5 ° C.) measured by a method according to JIS K 7129-1992. , Relative humidity (90 ± 2)% RH) is preferably 0.01 g / (m ² · 24 h) or less, and more preferably oxygen permeability measured by a method according to JIS K 7126-1987. A high barrier property film having a degree of 10 ⁻³ ml / (m ² · 24 h · atm) or less and a water vapor permeability of 10 ⁻⁵ g / (m ² · 24 h) or less is preferable.

  As a material for forming the barrier film, any material may be used as long as it has a function of suppressing entry of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and organic material layers. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

  The method for forming the barrier film is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma polymerization A plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.

  Examples of the opaque support substrate include metal plates such as aluminum and stainless steel, films, opaque resin substrates, and ceramic substrates.

  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. 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.

<Sealing>
As a sealing means used for this invention, the method of adhere | attaching a sealing member, an electrode, and a support substrate with an adhesive agent can be mentioned, for example.

  As a sealing member, it should just be arrange | positioned so that the display area | region of an organic EL element may be covered, and concave plate shape or flat plate shape may be sufficient. Further, transparency and electrical insulation are not particularly limited.

  Specific examples include a glass plate, a polymer plate / film, and a metal plate / film. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.

In the present invention, a polymer film and a metal film can be preferably used because the element can be thinned. Furthermore, the polymer film has an oxygen permeability of 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less measured by a method according to JIS K 7126-1987, and a method according to JIS K 7129-1992. It is preferable that the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured in (1) is 1 × 10 ⁻³ g / (m ² · 24 h) or less.

  For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.

  Specific examples of the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to. Moreover, heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.

  In addition, since an organic EL element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable. A desiccant may be dispersed in the adhesive.

  Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.

  In addition, it is also preferable to form an inorganic or organic layer on the outer side of the electrode on the side facing the support substrate with the organic layer interposed therebetween, and form an inorganic or organic layer in contact with the support substrate to form a sealing film. it can. In this case, the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can. Further, in order to improve the brittleness of the film, it is preferable to have a laminated structure of these inorganic layers and layers made of organic materials. There are no particular limitations on the method of forming these films. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

  In the gap between the sealing member and the display area of the organic EL element, an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase. preferable. A vacuum can also be used. Moreover, a hygroscopic compound can also be enclosed inside.

  Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate). Etc.), metal halides (eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.), perchloric acids (eg perchloric acid) Barium, magnesium perchlorate, and the like), and anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.

《Protective film, protective plate》
In order to increase the mechanical strength of the element, a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the support substrate with the organic layer interposed therebetween or on the sealing film. In particular, when the sealing is performed by the sealing film, the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate. As a material that can be used for this, the same glass plate, polymer plate / film, metal plate / film, and the like used for the sealing can be used, but the polymer film is light and thin. Is preferably used.

《Light extraction》
The organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1) and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said. This is because light incident on the interface (interface between the transparent substrate and air) at an angle θ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the element side surface.

  As a method for improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435), A method of improving efficiency by providing a light collecting property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on a side surface of an element (Japanese Patent Laid-Open No. 1-220394), and light emission from a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the bodies (Japanese Patent Laid-Open No. 62-172691), a flat having a lower refractive index between the substrate and the light emitter than the substrate A method of introducing a layer (Japanese Patent Laid-Open No. 2001-202827), a method of forming a diffraction grating between any one of a substrate, a transparent electrode layer and a light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 11-283951) Gazette).

  In the present invention, these methods can be used in combination with the organic EL device of the present invention. However, a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, transparent A method of forming a diffraction grating between any layers of the electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.

  In the present invention, by combining these means, it is possible to obtain an element having higher luminance or durability.

  When a medium having a low refractive index is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.

  Examples of the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.

  The thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate.

  The method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency. This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction. Of these, light that cannot be emitted due to total reflection between layers, etc. is diffracted by introducing a diffraction grating into any layer or medium (inside a transparent substrate or transparent electrode), and the light is removed. I want to take it out.

  The introduced diffraction grating desirably has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much.

  However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.

  As described above, the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or in the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.

  At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium. The arrangement of the diffraction grating is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.

<Condenser sheet>
The organic EL device of the present invention is processed on the light extraction side of the substrate so as to provide, for example, a microlens array structure, or combined with a so-called condensing sheet, for example, with respect to a specific direction, for example, the device light emitting surface. By condensing in the front direction, the luminance in a specific direction can be increased.

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

  As the condensing sheet, for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used. As such a sheet, for example, Sumitomo 3M brightness enhancement film (BEF) can be used. As the shape of the prism sheet, for example, the base material may be formed by forming a △ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 μm, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.

  Moreover, in order to control the light emission angle from a light emitting element, you may use together a light diffusing plate and a film with a condensing sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

<< 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 / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode will be described.

  First, a desired electrode material, for example, a thin film made of a material for an anode 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. .

  Next, organic compound thin films such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer, which are organic EL element materials, are formed thereon.

  As a method for forming each of these layers, there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method) and the like as described above, but it is easy to obtain a homogeneous film and it is difficult to generate pinholes. In view of the above, film formation by a coating method such as a spin coating method, an ink jet method, or a printing method is preferable in the present invention.

  Examples of the liquid medium for dissolving or dispersing the organic EL material according to the present invention include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, and mesitylene. Aromatic hydrocarbons such as cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as DMF and DMSO can be used. Moreover, as a dispersion method, it can disperse | distribute by dispersion methods, such as an ultrasonic wave, high shear force dispersion | distribution, and media dispersion | distribution.

  After these layers are formed, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 50 to 200 nm, and a cathode is provided. Thus, a desired organic EL element can be obtained.

  In addition, it is possible to reverse the production order and produce the cathode, the electron transport layer, the hole blocking layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. 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.

<Application>
The organic EL element of the present invention can be used as a display device, a display, and various light emission sources. For example, lighting devices (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 Although the light source of a sensor etc. are mentioned, It is not limited to this, Especially, it can use effectively for the use as a backlight of a liquid crystal display device, and a light source for illumination.

  In the organic EL element of the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned, and a conventionally known method may be used in the fabrication of the element. it can.

  The light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with the total CS-1000 (manufactured by Konica Minolta Sensing) is applied to the CIE chromaticity coordinates.

When the organic EL element of the present invention is a white element, white means that the chromaticity in the CIE 1931 color system at 1000 cd / m ² is X = It is in the region of 0.33 ± 0.07, Y = 0.33 ± 0.1.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

Example 1
<< Production of Organic EL Element 1-1 >>
A transparent support substrate provided with this ITO transparent electrode after patterning a substrate (NH45 made of NH technoglass) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode Was subjected to ultrasonic cleaning with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.

This transparent support substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of α-NPD was put in a molybdenum resistance heating boat, and 200 mg of H-1 as a host compound was put in another molybdenum resistance heating boat, 200 mg of BAlq was put into another resistance heating boat made of molybdenum, 100 mg of FIr (pic) was put into another resistance heating boat made of molybdenum, and 200 mg of Alq ₃ was put into another resistance heating boat made of molybdenum, and attached to the vacuum deposition apparatus. .

Next, after reducing the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD was heated by heating, 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 H-1 and FIr (pic) is energized and heated, and co-deposited on the hole transport layer at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively, A light emitting layer having a thickness of 40 nm was provided. In addition, the substrate temperature at the time of vapor deposition was room temperature.

  Further, the heating boat containing BAlq was energized and heated, and deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a 10 nm thick hole blocking layer.

Further, the heating boat containing Alq ₃ was further energized and heated, and was deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further provide an electron transport 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.

<< Production of Organic EL Elements 1-2 to 1-21 >>
In the production of the organic EL device 1-1, except that H-1 as the host compound of the light emitting layer, FIr (pic) as the dopant compound, and the hole transport material were replaced with the compounds shown in Table 1, Organic EL elements 1-2 to 1-21 were produced.

<< Evaluation of organic EL elements >>
When evaluating the obtained organic EL elements 1-1 to 1-21, the non-light-emitting surface of each organic EL element after production was covered with a glass case, and a glass substrate having a thickness of 300 μm was used as a sealing substrate. An epoxy photo-curing adhesive (Luxe Track LC0629B manufactured by Toagosei Co., Ltd.) is applied as a sealant around the periphery, and this is placed on the cathode so as to be in close contact with the transparent support substrate and irradiated with UV light from the glass substrate side. Then, it was cured and sealed, and an illumination device as shown in FIGS. 3 and 4 was formed and evaluated.

  FIG. 3 is a schematic diagram of the lighting device, and the organic EL element 101 is covered with a glass cover 102 (in addition, the sealing operation with the glass cover is performed in a nitrogen atmosphere without bringing the organic EL element 101 into contact with the atmosphere. (In a high purity nitrogen gas atmosphere with a purity of 99.999% or more).

  4 shows a cross-sectional view of the lighting device. In FIG. 4, reference numeral 105 denotes a cathode, 106 denotes an organic EL layer, and 107 denotes a glass substrate with a transparent electrode. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

(External quantum efficiency)
By lighting the organic EL element under a constant current condition of room temperature (about 23 to 25 ° C.) and ^2.5 mA / cm ² , and measuring the light emission luminance (L) [cd / m ² ] immediately after the start of lighting, The external extraction quantum efficiency (η) was calculated. Here, CS-1000 (manufactured by Konica Minolta Sensing) was used for measurement of light emission luminance. The external extraction quantum efficiency was expressed as a relative value with the organic EL element 1-1 as 100.

(Half life)
The half-life was evaluated according to the measurement method shown below. Each organic EL device driven with a constant current at a current giving an initial luminance 1000 cd / ^{m 2,} obtains the time to be 1/2 (500cd / ^{m 2)} of the initial luminance, which was used as a measure of the half-life. The half life was expressed as a relative value when the comparative organic EL element 1-1 was set to 100.

(Initial deterioration)
The initial deterioration was evaluated according to the following measurement method. The time for the luminance to reach 90% during the half-life measurement was measured, and this was used as a measure of initial deterioration. The initial deterioration was 100 for the comparative organic EL element 1-1. The initial deterioration was calculated based on the following formula.

Initial deterioration = (luminance 90% arrival time of organic EL element 1-1) / (luminance 90% arrival time of each element) × 100
That is, the smaller the initial deterioration value, the smaller the initial deterioration.

(Dark spot)
The light emitting surface when each organic EL element was continuously lit under a constant current condition of ^2.5 mA / cm ² at room temperature was visually evaluated. For each element after 10 hours of continuous lighting by visual evaluation by 10 randomly extracted people, the following was set.

×: When the number of confirmed dark spots is 5 or more Δ: When the number of confirmed dark spots is 1 to 4 ○: When the number of confirmed dark spots is 0

(Storage element voltage rise)
Each organic EL element was stored for 1 week under conditions of 50 ° C. and humidity 80%, and then the voltage when driven under a constant current condition of ^2.5 mA / cm ² was measured and compared with the driving voltage before storage. Voltage rise after storage = (drive voltage after storage of each element / drive voltage before storage of each element)
Note that the closer the value is to 1, the smaller the increase in drive voltage before and after storage.

  From Table 2, it can be seen that the organic EL device of the present invention has higher external extraction quantum efficiency and less initial luminance deterioration, and has a longer lifetime as compared with the comparative device. It can also be seen that the generation of dark spots is suppressed. Furthermore, it has been found that the organic EL device of the present invention can greatly suppress an increase in drive voltage after storage.

Example 2
<< Production of Organic EL Elements 2-1 to 2-9 >>
In the production of the organic EL element 1-1, FIr (pic), which is a dopant compound, is changed to A-97 and F-40, and the hole transport material is represented by B in the general formula (6) and the glass transition temperature shown in Table 2. Organic EL elements 2-1 to 2-9 were produced in the same manner except that the exemplified compound having the molecular weight of the represented linking group was used.

<< Evaluation of organic EL elements >>
Evaluation of the obtained organic EL elements 2-1 to 2-9 was performed in the same manner as in Example 1 with respect to external extraction efficiency, half life, initial deterioration, and dark spots. Comparative organic EL element 1-1 was set to 100 for external extraction efficiency, half life, and initial deterioration. The results are shown in Table 2.

  From Table 3, compared with the comparative device, the organic EL device of the present invention has a high external extraction quantum efficiency depending on the glass transition temperature of the hole transport material and the molecular weight of the linking group, and the initial luminance degradation is low. It can be seen that there is little and a long life. It can also be seen that the generation of dark spots is suppressed.

Example 3
<Production of full-color display device>
(Production of blue light emitting element)
The organic EL element 2-4 of Example 2 was used as a blue light emitting element.

(Production of green light emitting element)
In the organic EL element 1-1 of Example 1, a green light emitting element was produced in the same manner except that the comparison 1 was changed to Ir-1, and this was used as the green light emitting element.

(Production of red light emitting element)
In the organic EL device 1-1 of Example 1, a red light emitting device was produced in the same manner except that the comparison 1 was changed to Ir-9, and this was used as a red light emitting device.

  The red, green, and blue light-emitting organic EL elements produced above were juxtaposed on the same substrate to produce an active matrix type full-color display device having a configuration as shown in FIG. In FIG. 2, only the schematic diagram of the display part A of the produced display device is shown.

  That is, a plurality of pixels 3 (light emission color is a red region pixel, a green region pixel, a blue region pixel, etc.) juxtaposed with a wiring portion including a plurality of scanning lines 5 and data lines 6 on the same substrate. 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 lattice shape and are connected to the pixels 3 at the orthogonal positions (for details, see FIG. 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. The image data signal is received from the data line 6 and light is emitted according to the received image data. In this way, a full color display device was manufactured by appropriately juxtaposing red, green, and blue pixels.

  It has been found that when this full-color display device is driven, a high-brightness, high durability, and clear full-color moving image display can be obtained.

Example 4
<< Preparation of white light emitting element and white lighting device >>
The electrode of the transparent electrode substrate of Example 1 was patterned to 20 mm × 20 mm, and an exemplary compound 187 was formed thereon with a thickness of 25 nm as a hole injecting / transporting layer in the same manner as in Example 1; The heated boat containing 1 and the boat containing Exemplified Compound A-97 and the boat containing Ir-9 are energized independently, and CBP as a luminescent host and Illustrative Compound A-97 and Ir as a luminescent dopant are supplied. The vapor deposition rate of −9 was adjusted to be 100: 5: 0.6, vapor deposition was performed so as to have a thickness of 30 nm, and a light emitting layer was provided.

Next, 10 nm of BAlq was deposited to provide a hole blocking layer. Furthermore, it was deposited Alq ₃ at 40nm an electron transporting layer.

  Next, as in Example 1, a square perforated mask having the same shape as the transparent electrode made of stainless steel was placed on the electron transport layer, and lithium fluoride 0.5 nm as the cathode buffer layer and aluminum 150 nm as the cathode. Vapor deposition and film formation were performed.

  This element was provided with a sealing can having the same method and the same structure as in Example 1, and a flat lamp as shown in FIGS. 3 and 4 was produced. When this flat lamp was energized, almost white light was obtained, and it was found that it could be used as a lighting device.

Example 5
<< Production of White Light Emitting Element and White Lighting Device-2 >>
A transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) obtained by forming a 100 nm film of ITO (indium tin oxide) on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode. The supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.

  On this transparent support substrate, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water 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 first hole transport layer having a thickness of 30 nm.

  The substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg of the exemplary compound 131 dissolved in 10 ml of toluene was formed on the first hole transport layer by spin coating at 1000 rpm for 30 seconds. After irradiating with ultraviolet light for 180 seconds to perform photopolymerization and crosslinking, vacuum drying was performed at 60 ° C. for 1 hour to obtain a second hole transport layer.

  Next, using a solution obtained by dissolving Compound D (60 mg), Ir-14 (3.0 mg), and F-9 (3.0 mg) in 6 ml of toluene, a film is formed by spin coating under conditions of 1000 rpm and 30 seconds. did. Irradiated with ultraviolet light for 15 seconds to cause photopolymerization and crosslinking, and further heated in vacuum at 150 ° C. for 1 hour to obtain a light emitting layer.

  Furthermore, using a solution obtained by dissolving Compound E (20 mg) in 6 ml of toluene, a film was formed by spin coating under conditions of 1000 rpm and 30 seconds. It was irradiated with ultraviolet light for 15 seconds to cause photopolymerization and crosslinking, and further heated in vacuum at 80 ° C. for 1 hour to form a hole blocking layer.

Subsequently, this substrate was fixed to a substrate holder of a vacuum vapor deposition apparatus, and 200 mg of Alq ₃ was put into a molybdenum resistance heating boat and attached to the vacuum vapor deposition apparatus. After depressurizing the vacuum chamber to 4 × 10 ⁻⁴ Pa, energizing and heating the heating boat containing Alq ₃ , depositing on the hole blocking layer at a deposition rate of 0.1 nm / second, An electron transport layer having a thickness of 40 nm was provided.

  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 white light emitting organic EL element was produced.

  When this element was energized, almost white light was obtained, indicating that it could be used as a lighting device.

Example 6
<< Production of Organic EL Element 6-1 >>
A transparent substrate provided with this ITO transparent electrode after patterning was performed on a substrate (NH-Technoglass NA-45) obtained by forming a 100 nm film of ITO (indium tin oxide) on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode. The supporting substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.

  On this transparent support substrate, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water 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 first hole transport layer having a thickness of 30 nm.

  This substrate was transferred to a nitrogen atmosphere, and a solution of 50 mg α-NPD dissolved in 10 ml of toluene was formed on the first hole transport layer by spin coating at 1000 rpm for 30 seconds.

  The film was vacuum-dried at 60 ° C. for 1 hour to form a second hole transport layer.

  In the case where the second hole transport material has a polymerizable group, after irradiation with ultraviolet light for 180 seconds, photopolymerization and crosslinking, vacuum drying is performed at 60 ° C. for 1 hour, did.

  Next, using a solution of H-5 (60 mg) and A-97 (3.0 mg) dissolved in 6 ml of toluene, a film was formed by spin coating under conditions of 1000 rpm and 30 seconds to form a light emitting layer.

  Subsequently, this substrate was fixed to a substrate holder of a vacuum deposition apparatus, 200 mg of BAlq was put into a molybdenum resistance heating boat, and attached to the vacuum deposition apparatus.

The vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then heated by energizing the heating boat containing BAlq, and deposited on the light emitting layer at a deposition rate of 0.1 nm / sec. The electron transport layer was provided.

  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 white light emitting organic EL element was produced.

<< Production of Organic EL Elements 6-2 to 6-9 >>
In the production of the organic EL element 6-1, the organic EL elements 6-2 to 6-6 were similarly performed except that α-NPD as the hole transport material and A-97 as the dopant compound were replaced with the compounds shown in Table 3. -9 was produced.

<< Evaluation of organic EL elements >>
The obtained organic EL elements 6-1 to 6-9 were evaluated in the same manner as the organic EL elements 1-1 to 1-21 in Example 1. The external extraction quantum efficiency, half-life, and initial degradation were expressed as relative values with the comparative organic EL element 1-1 of Example 1 as 100, respectively. The evaluation results are shown in Table 4.

  From Table 4, it can be considered that the device of the comparative example has α-NPD dissolved at the time of application of the light emitting layer and diffused to the light emitting layer, thereby significantly reducing the device performance. It can be seen that the hole transport material does not diffuse to other layers, the external extraction quantum efficiency is high, the initial luminance degradation is small, and the lifetime is accordingly increased. It can also be seen that the generation of dark spots is suppressed.

DESCRIPTION OF SYMBOLS 1 Display 3 Pixel 5 Scan line 6 Data line A Display part B Control part 101 Organic EL element 107 Glass substrate with a transparent electrode 106 Organic EL layer 105 Cathode 102 Glass cover 108 Nitrogen gas 109 Water catching agent

Claims (9)

In an organic electroluminescence device having at least one light emitting layer sandwiched between an anode and a cathode,
The light emitting layer contains at least one compound having a structure represented by the following general formula (A) or general formula (B), and is represented by the following general formula (6) having a glass transition temperature of 100 ° C. or higher. An organic electroluminescent device comprising an organic layer containing at least one compound having a structure.
(In the formula, E1a represents a nitrogen atom and E1b represents a carbon atom. E1c to E1e each represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. The ring composed of E1a to E1e is an imidazole ring. Or E1f, E1h and E1k each represents a carbon atom or a nitrogen atom, E1g and E1i each represents a carbon atom, a nitrogen atom or a sulfur atom, and the ring composed of E1f to E1k represents pyrrole. ring, .R1a～R1f representing the pyrazole ring or imidazole ring, R1h～R1i each a hydrogen atom, a fluorine atom, a cyano group, an alkyl group, an acetyl group from 1 to 4 carbon atoms, a methoxycarbonyl group, a 3-pyridyl group , 2,5-dimethyl-pyrrolyl group or .R1g representing a phenyl group which may have a methyl group or vinyl group, is full E Group, mesityl group, tolyl group, xylyl group, naphthyl group, biphenylyl group, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group, thiazolyl group, benzothiazolyl group represents an isoxazolyl group, an isothiazolyl group or a thienyl group of these substituents may further be substituted with any of the substituents of the substituent group represented by each of the R1a~R1i X _1.. - L ₁ -X ₂ represents a monoanionic bidentate ligand of acetylacetone, picolinic acid, 4-dimethylaminopicolinic acid or 1-mesityl-2-phenyl-1H-imidazole, m1 represents 2 or 3 M2 represents 0 or 1, but m1 + m2 is 3.)
_(Wherein, R 1 _{to R 20} are each a hydrogen atom, an alkyl group, an alkynyl group, or represents a fang aromatic hydrocarbon group or aromatic heterocyclic group. These _{substituents,} R 1 _{to R 20} is it may be further substituted by the substituents each represented. B is off Eniru group, a biphenyl group, a carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group, a fluorenyl group, linked composed pyrenyl group or an anthracenyl group Represents a group, and the molecular weight of the linking group is 180 or more, and these linking groups may be further substituted with the substituents represented by R _{1 to} R _{20, and} m and p each represent 1 to 2 Represents an integer.) 2. The substituent according to claim 1 , wherein at least one of the substituents represented by R _{1 to} R ₁₀ or R _{1 to} R ₂₀ in the general formula (6) is a polymerizable substituent. Organic electroluminescence element. The organic electroluminescent device according to claim 1 or 2, wherein the light emitting layer is formed using a wet process. The organic layer according to any one of claims 1 to 3 , wherein an organic layer containing at least one compound having a structure represented by the general formula (6) is formed using a wet process. Electroluminescence element. The organic electroluminescence device according to claim 4 , wherein the organic layer containing at least one compound having a structure represented by the general formula (6) is a hole transport layer. 6. The organic electroluminescence device according to claim 5 , wherein the hole transport layer contains a polymer having a partial structure of a compound having a structure represented by the general formula (6). Wherein M is an organic electroluminescent device according to any one of claims 1 to 6, characterized in that a platinum or iridium. Display apparatus comprising the organic electroluminescent device according to any one of claims 1-7. An illuminating device comprising the organic electroluminescence element according to any one of claims 1 to 7 .