JP2011084746A - Light-emitting material comprising orthometalated iridium complex, light-emitting device, and novel iridium complex - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light-emitting device excellent in light-emitting properties, and a material for the same. <P>SOLUTION: The light-emitting material comprises a compound having a partial structure represented by formula (1) or a tautomer thereof. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a light-emitting element material and a light-emitting element that can emit light by converting electric energy into light, and includes a display element, a display, a backlight, an electrophotography, an illumination light source, a recording light source, an exposure light source, a reading light source, a sign, a signboard, The present invention relates to a light-emitting element that can be suitably used in the field of interior and the like. In addition, the present invention relates to a novel light emitting material expected to be applied in various fields.

  Today, research and development on various display elements are active. Among them, organic electroluminescence (EL) elements are attracting attention as promising display elements because they can emit light with high luminance at a low voltage. For example, a light-emitting element that forms an organic thin film by vapor deposition of an organic compound is known (Applied Physics Letters, 51, 913, 1987). The light-emitting element described in this document uses tris (8-hydroxyquinolinato) aluminum complex (Alq) as an electron transport material, and is laminated with a hole transport material (amine compound), thereby making it a conventional single-layer element. Compared to this, the emission characteristics are greatly improved.

  In recent years, application of organic EL elements to color displays has been actively studied, but in order to develop high-performance color displays, it is necessary to improve the characteristics of blue, green, and red light-emitting elements. .

As a means for improving the characteristics of the light emitting element, a green light emitting element utilizing light emission from an ortho-metalated iridium complex (Ir (ppy) ₃ : Tris-Ortho-Metalated Complex of Iridium (III) with 2-Phenylpyridine) has been reported. (Applied Physics Letters 75, 4 (1999).). This device has achieved an external quantum yield of 8%, which exceeds the external quantum yield of 5%, which was said to be the limit of the conventional device, but is limited to green light emission, so that it can be used as a display. There has been a demand for the development of light-emitting element materials that are narrow and emit light in other colors with high efficiency.

  On the other hand, organic light-emitting elements that achieve high-intensity light emission are elements in which organic substances are stacked by vacuum vapor deposition, but depending on the application method from the viewpoint of simplification of the manufacturing process, processability, large area, etc. Device fabrication is desirable. However, the device manufactured by the conventional coating method is inferior to the device manufactured by the vapor deposition method particularly in terms of luminous efficiency, and development of a new light emitting device material has been desired. In recent years, various fluorescent substances have been used in filter dyes, color conversion filters, photographic dyes, sensitizing dyes, pulp dyes, laser dyes, fluorescent materials for medical diagnosis, materials for organic light emitting devices, etc. The demand has been increasing, and a new light emitting material has been desired.

  An object of the present invention is to provide a light-emitting element having favorable light-emitting characteristics, a light-emitting element material that enables the light-emitting element, and a novel light-emitting material that can be used in various fields.

This object has been achieved by the following means.
1. A light emitting device material comprising a compound having a partial structure represented by the general formula (1) or a tautomer thereof.

  2. A light emitting device material comprising a compound having a partial structure represented by the general formula (2) or a tautomer thereof.

  3. A light emitting device material comprising a compound having a partial structure represented by the general formula (3) or a tautomer thereof.

In the formula, R ¹ and R ² each represent a substituent. q ¹ and q ² represent integers of 0 to 4, and q ¹ + q ² is 1 or more.

  4). A compound having a partial structure represented by the general formula (4) or a tautomer thereof.

In the formula, each of Z ¹¹ and Z ¹² represents a nonmetallic atomic group necessary for forming a 5-membered ring or a 6-membered ring with a carbon atom and / or a nitrogen atom, and this ring may have a substituent. Further, a condensed ring may be formed with another ring. Ln ¹ represents a divalent group. Y ¹ represents a nitrogen atom or a carbon atom, and b ¹ represents a single bond or a double bond.

  5. A light emitting material comprising the compound as described in 4 above.

  6). A light emitting material comprising a compound having a partial structure represented by the general formula (5).

  7. A light emitting material comprising a compound having a partial structure represented by the general formula (6).

  8). A light emitting material comprising a compound having a partial structure represented by the general formula (7) or a tautomer thereof.

In the formula, Z ²¹ and Z ²² each represent a nonmetallic atomic group necessary for forming a 5-membered ring or a 6-membered ring with a carbon atom and / or a nitrogen atom, and this ring may have a substituent. It may also form a condensed ring with another ring. Y ² represents a nitrogen atom or a carbon atom, and b ² represents a single bond or a double bond.

  9. A luminescent material comprising a compound having a partial structure represented by the general formula (8) or a tautomer thereof.

In the formula, X ²⁰¹ , X ²⁰² , X ²⁰³ and X ²⁰⁴ represent a nitrogen atom or C—R, and together with —C═N— form a nitrogen-containing heteroaryl 6-membered ring, and X ²⁰¹ , X ²⁰² , X ²⁰³ And at least one of X ²⁰⁴ represents a nitrogen atom. R represents a hydrogen atom or a substituent. Z ²⁰¹ represents an atomic group forming an aryl ring or a heteroaryl ring.
10. A light emitting material comprising a compound having a partial structure represented by the general formula (9) or a tautomer thereof.

In the formula, Z ²⁰¹ and Z ³⁰¹ represent an atomic group forming an aryl ring or a heteroaryl ring.
11. A light emitting material comprising a compound having a partial structure represented by the general formula (10) or a tautomer thereof.

In the formula, Z ²⁰¹ and Z ⁴⁰¹ each represents an atomic group forming an aryl ring or a heteroaryl ring.
12 A light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes, wherein the organic light-emitting element contains the light-emitting material according to any one of the above 1, 2, 3, 5 to 11 in at least one layer.
13. A light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes, has at least one layer made of a single light-emitting material described in 1, 2, 3, 5 to 11. An organic light emitting device.
14 In a light emitting device in which a light emitting layer or a plurality of organic compound thin layers including a light emitting layer is formed between a pair of electrodes, a coating process including a layer having an orthometalated iridium complex in at least one layer and containing an orthometalated iridium complex A light-emitting element formed by film formation.

  The compound of the present invention can be used as a material for organic EL, and high-efficiency and high-durability EL elements having various emission colors can be produced.

Hereinafter, the present invention will be described in detail. The compound of the present invention is a light emitting device material composed of orthometalated iridium complexes. Orthometalated metal complexes are, for example, “Organic Metal Chemistry-Fundamentals and Applications” p150, 232 Akio Yamamoto, 1982, “Photochemistry and Photophysics of Coordination Compounds”
p71-p77, p135-p146 Springer-Verlag is a general term for a group of compounds described in H. Yersin's 1987 publication.

  The valence of iridium in the orthometalated iridium complex is not particularly limited, but trivalent is preferable. The ligand of the orthometalated iridium complex is not particularly limited as long as it can form an orthometalated complex. For example, an aryl group-substituted nitrogen-containing heterocyclic derivative (the aryl group is substituted at a nitrogen-containing heterocyclic nitrogen) On the carbon adjacent to the atom, examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a pyrenyl group, and may further form a condensed ring with a carbocycle or a heterocycle. Examples of the heterocycle include pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, quinoxaline, phthalazine, quinazoline, naphtholidine, cinnoline, perimidine, phenanthroline, pyrrole, imidazole, pyrazole, oxazole, oxadiazole, triazole, thiadiazole, benzine. Imidazole, Nexoxazole, benzthiazole, phenanthridine and the like), heteroaryl group-substituted nitrogen-containing heterocyclic derivatives (the substitution position of the heteroaryl group is on the adjacent carbon of the nitrogen-containing heterocyclic nitrogen atom, For example, a group containing the above-mentioned nitrogen-containing heterocyclic derivative, thienyl group, furyl group, etc.), 7,8-benzoquinoline derivative, phosphinoaryl derivative, phosphinoheteroaryl derivative, phosphinoxyaryl derivative, phosphine Examples thereof include finoxyheteroaryl derivatives, aminomethylaryl derivatives, aminomethylheteroaryl derivatives, and the like. Preferred are aryl group-substituted nitrogen-containing aromatic heterocyclic derivatives, heteroaryl group-substituted nitrogen-containing aromatic heterocyclic derivatives, and 7,8-benzoquinoline derivatives. Phenylpyridine derivatives, thienylpyridine derivatives, 7,8-benzoquinoline derivatives, benzyl More preferred are pyridine derivatives, phenylpyrazole derivatives, phenylisoquinoline derivatives, phenyl substituted derivatives of azoles having two or more nitrogen atoms, thienylpyridine derivatives, 7,8-benzoquinoline derivatives, benzylpyridine derivatives, phenylpyrazole derivatives, phenylisoquinoline derivatives. Particularly preferred are phenyl-substituted derivatives of azoles having two or more nitrogen atoms.

  The compound of the present invention may have other ligands in addition to the ligands necessary for forming the orthometalated complex. There are various known ligands as other ligands. For example, “Photochemistry and Photophysics of Coordination Compounds” published by Springer-Verlag H. Yersin in 1987, “Organic Metal Chemistry-Fundamentals and Applications” And the like. Preferred are halogen ligands (preferably chlorine ligands), nitrogen-containing heterocyclic ligands (for example, bipyridyl, phenanthroline, etc.). ), A diketone ligand, more preferably a chlorine ligand or a bipyridyl ligand.

  The type of the ligand of the compound of the present invention may be one type or a plurality of types. The number of ligands in the complex is preferably 1 to 3 types, particularly preferably 1 to 2, and more preferably 1 type.

  The number of carbon atoms of the compound of the present invention is preferably 5 to 100, more preferably 10 to 80, and still more preferably 14 to 50.

  Of the compounds having a partial structure represented by the general formulas (1) to (10) or tautomers thereof, represented by the general formulas (1), (2), (4) to (10) A compound having a partial structure or a tautomer thereof is more preferable.

  The compound having a partial structure represented by the general formula (1) or a tautomer thereof may have one iridium atom in the compound, or may be a so-called dinuclear complex having two or more. good. Other metal atoms may be contained at the same time. The same applies to compounds having a partial structure represented by the general formulas (2) to (10) or tautomers thereof.

In General formula (3), R < ¹ >, R < ² > represents a substituent. q ¹ and q ² represent integers of 0 to 4, and q ¹ + q ² is 1 or more. When q ¹ and q ² are 2 or more, the plurality of R ¹ and R ² may be the same or different from each other. Examples of R ¹ and R ² include an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, trifluoromethyl group, pentafluoroethyl group, etc.), alkenyl group (preferably having 2 to 30 carbon atoms, More preferably, it has 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, 3-pentenyl and the like, and an alkynyl group (preferably having 2 to 30 carbon atoms, More preferably, it has 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as propargyl, 3-pentynyl. And aryl groups (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, anthranyl, etc. An amino group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzyl) Amino, diphenylamino, ditolylamino, etc.), alkoxy groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy , 2-ethylhexyloxy, etc.), an aryloxy group (preferably having 6 to 30 carbon atoms). , More preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), heteroaryloxy groups (preferably carbon atoms). 1-30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy etc. are mentioned), an acyl group (preferably C1-C30). , More preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, pivaloyl, and the like, and an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably Has 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbo Le, such as ethoxycarbonyl. ), An aryloxycarbonyl group (preferably having a carbon number of 7 to 30, more preferably a carbon number of 7 to 20, particularly preferably a carbon number of 7 to 12, such as phenyloxycarbonyl), an acyloxy group (preferably Has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy.), An acylamino group (preferably 2 to 30 carbon atoms, More preferably, it has 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino, benzoylamino and the like, and an alkoxycarbonylamino group (preferably 2 to 30 carbon atoms, more preferably carbon atoms). 2 to 20, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino An aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino). A sulfonylamino group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino), a sulfamoyl group (Preferably has 0 to 30 carbon atoms, more preferably has 0 to 20 carbon atoms, and particularly preferably has 0 to 12 carbon atoms. Examples thereof include sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and phenylsulfamoyl. ), A carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably A prime number of 1-20, particularly preferably a carbon number of 1-12, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc., an alkylthio group (preferably having a carbon number of 1-30, more preferably a carbon number). 1 to 20, particularly preferably 1 to 12 carbon atoms, for example, methylthio, ethylthio, etc.), arylthio groups (preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably carbon atoms). And a heteroarylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms. Pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazoly Lucio etc. are mentioned. ), A sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl), a sulfinyl group (preferably carbon). 1 to 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl and benzenesulfinyl), ureido groups (preferably 1 to 30 carbon atoms, and more). Preferably it is C1-C20, Most preferably, it is C1-C12, for example, ureido, methylureido, phenylureido etc. are mentioned), phosphoric acid amide group (preferably C1-C30, more preferably It has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms. Examples thereof include diethyl phosphoric acid amide and phenyl phosphoric acid amide. Hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group Group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom, specifically, for example, imidazolyl, pyridyl and quinolyl. , Furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, etc.), a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably carbon number). 3 to 24, for example, trimethylsilyl, triphenylsilyl, etc. That.), And the like. These substituents may be further substituted. Further, R ¹ groups, R ² groups, or R ¹ groups and R ² groups may be bonded to form a condensed ring structure.

R ¹ and R ² are preferably an alkyl group, an aryl group, an alkoxy group, an amino group, a cyano group, or a group that combines to form a condensed ring structure, and an alkyl group or a group that combines to form an aromatic condensed ring structure. More preferred. q ¹ and q ² are preferably 0, ¹ , ² and more preferably q ¹ + q ² = 1 or 2.

In the general formula (4), Z ¹¹ and Z ¹² each represent a nonmetallic atomic group necessary for forming a 5-membered ring or a 6-membered ring, and this ring may have a substituent, and further And a condensed ring may be formed. Examples of the substituent include a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, cyano, nitro, —OR ¹⁰¹ , —SR ¹⁰² , —CO ₂ R ¹⁰³ , —OCOR ¹⁰⁴ , —NR ¹⁰⁵ R ¹⁰⁶ , —CONR ^{107. _{R 108, -SO 2 R 109,}} -SO 2 NR 110 R 111, -NR 112 CONR 113 R 114, -NR 115 CO 2 R 116, -COR 117, -NR 118 COR 119 , or -NR ¹²⁰ SO ₂ R ¹²¹ Is mentioned. Here, R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ , R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹² , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ , R ¹¹⁸ , R ¹¹⁹ , R ¹²⁰ and R ¹²¹ are each independently a hydrogen atom, an aliphatic group or an aryl group.

The substituent halogen atom in the aliphatic group, an aryl ^{group, -OR 101, -SR 102, -NR} 105 R 106, -SO 2 R 109, -NR 112 CONR 113 R 114, -NR 115 CO 2 R ¹¹⁶ , —NR ¹¹⁸ COR ¹¹⁹ or —NR ¹²⁰ SO ₂ R ¹²¹ is preferable, and halogen atom, aliphatic group, aryl group, —OR ¹⁰¹ , —SR ¹⁰² , —NR ¹⁰⁵ R ¹⁰⁶ or —SO ₂ R ¹⁰⁹ is more preferable, and a halogen atom, an alkyl group, an aryl group, an alkoxy group, a phenoxy group, and a dialkylamino group are more preferable, and a halogen atom, an alkyl group having 1 to 10 carbon atoms, and a carbon number of 6 Are more preferably an aryl group having 10 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms, and most preferably a halogen atom and an alkyl group having 1 to 4 carbon atoms.

  Here, the aliphatic group means an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group.

As the 5-membered ring and 6-membered ring formed by Z ¹¹ and Z ¹² , an aromatic ring or a heteroaromatic ring is preferable. For example, a furan ring, a thiophene ring, an imidazole ring, a thiazole ring, an oxazole ring, a pyrrole ring, a pyrazole ring, There are 1,2,3-triazole rings, 1,2,4-triazole rings, selenazole rings, oxadiazole rings, thiadiazole rings, benzene rings, pyridine rings, pyrimidine rings, pyrazine rings and pyridazine rings. Among these, Z ¹¹ is preferably a thiophene ring, an imidazole ring, a thiazole ring, an oxazole ring, a pyrrole ring, a pyrazole ring, a benzene ring and a pyridine ring, more preferably a thiazole ring, a pyrrole ring, a benzene ring and a pyridine ring, A benzene ring is most preferred. Z ¹² is preferably an imidazole ring, a thiazole ring, an oxazole ring, a pyrrole ring, a pyrazole ring, a 1,2,3-triazole ring, a 1,2,4-triazole ring, a pyridine ring or a pyrimidine ring, and an imidazole ring or a thiazole ring. , A pyrrole ring, a pyrazole ring, a pyridine ring and a pyrimidine ring are more preferable, and a pyrazole ring and a pyridine ring are more preferable. Z ¹¹ and Z ¹² each preferably has 3 to 40 carbon atoms, more preferably 3 to 30, and particularly preferably 3 to 20.

Ln ¹ represents a divalent group. Examples of the divalent group include —C (R ¹³¹ ) (R ¹³² ) —, —N (R ¹³³ ) —, —O—, —P (R ¹³⁴ ) —, or —S—. Here, R ¹³¹ and R ¹³² are each independently a hydrogen atom, halogen atom, aliphatic group, aryl group, heterocyclic group, cyano, —OR ¹⁴¹ , —SR ¹⁴² , —CO ₂ R ¹⁴³ , —OCOR ¹⁴⁴ , —NR ¹⁴⁵ R ¹⁴⁶ , -CONR ¹⁴⁷ R ¹⁴⁸ , -SO ₂ R ¹⁴⁹ , -SO ₂ NR ¹⁵⁰ R ¹⁵¹ , -NR ¹⁵² CONR ¹⁵³ R ¹⁵⁴ , -NR ¹⁵⁵ CO ₂ R ¹⁵⁶ , -COR ¹⁵⁷ , -NR ¹⁵⁸ COR ¹⁵⁹ or -NR ¹⁶⁰ SO ₂ R ¹⁶¹ , R ¹⁴¹ , R ¹⁴² , R ¹⁴³ , R ¹⁴⁴ , R ¹⁴⁵ , R ¹⁴⁶ , R ¹⁴⁷ , R ¹⁴⁸ , R ¹⁴⁹ , R ¹⁵⁰ , R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ , R ¹⁵⁶ , R ¹⁵⁷ , R ¹⁵⁸ , R ¹⁵⁹ , R ¹⁶⁰ and R ¹⁶¹ are each independently a hydrogen atom, an aliphatic group or an aryl group. R ¹³³ represents an aliphatic group, an aryl group, or a heterocyclic group, and R ¹³⁴ represents an aliphatic group, an aryl group, a heterocyclic group, and —OR ¹⁷¹ , and R ¹⁷¹ represents a hydrogen atom, an aliphatic group, or an aryl group. is there.

Ln ¹ is preferably —C (R ¹³¹ ) (R ¹³² ) —, —O— or —S—, more preferably —C (R ¹³¹ ) (R ¹³² ) —, wherein R ¹³¹ and R ¹³² are hydrogen atoms. , An aliphatic group or an aryl group, more preferably —C (R ¹³¹ ) (R ¹³² ) —, wherein R ¹³¹ and R ¹³² are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The number of carbon atoms of Ln ¹ is preferably 0-20, more preferably 0-15, and particularly preferably 0-10.

Y ¹ represents a nitrogen atom or a carbon atom. When Y ¹ is a nitrogen atom, b ¹ represents a single bond, and when Y ¹ is a carbon atom, b ¹ represents a double bond.

In the general formula (7), Z ²¹ and Z ²² represent a nonmetallic atomic group necessary for forming a 5-membered ring or a 6-membered ring, and this ring may have a substituent, A ring and a condensed ring may be formed. Examples of the substituent include a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, cyano, nitro, —OR ²⁰¹ , —SR ²⁰² , —CO ₂ R ²⁰³ , —OCOR ²⁰⁴ , —NR ²⁰⁵ R ²⁰⁶ , —CONR ²⁰⁷ R ²⁰⁸ , —SO ₂ R ²⁰⁹ , —SO ₂ NR ²¹⁰ R ²¹¹ , —NR ²¹² CONR ²¹³ R ²¹⁴ , —NR ²¹⁵ CO ₂ R ²¹⁶ , —COR ²¹⁷ , —NR ²¹⁸ COR ²¹⁹ or —NR ²²⁰ SO ₂ R ²²¹ . Wherein ^{R 201, R 202, R 203} , R 204, R 205, R 206, R 207, R 208, R 209, R 210, R 211, R 212, R 213, R 214, R 215, R 216, R ²¹⁷ , R ²¹⁸ , R ²¹⁹ , R ²²⁰ and R ²²¹ are each independently a hydrogen atom, an aliphatic group or an aryl group.

The preferred substituents for Z ²¹ and Z ²² are exactly the same as those for Z ¹¹ and Z ¹² .

As the 5-membered ring and 6-membered ring formed by Z ²¹ , furan ring, thiophene ring, imidazole ring, thiazole ring, oxazole ring, pyrrole ring, pyrazole ring, 1,2,3-triazole ring, 1,2,4- There are triazole ring, selenazole ring, oxadiazole ring, thiadiazole ring, benzene ring, pyridine ring, pyrimidine ring, pyrazine ring and pyridazine ring. Of these, thiophene ring, imidazole ring, thiazole ring, oxazole ring, pyrrole ring, pyrazole ring, benzene ring and pyridine ring are preferable, thiazole ring, pyrrole ring, benzene ring and pyridine ring are more preferable, and benzene ring is most preferable. . Z ²² includes pyrazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring and pyridazine ring, and pyrazole ring is most preferable. Z ¹¹ and Z ¹² each preferably has 3 to 40 carbon atoms, more preferably 3 to 30, and particularly preferably 3 to 20.

Y ² represents a nitrogen atom or a carbon atom. When Y ² is a nitrogen atom, b ² represents a single bond, and when it is a carbon atom, b ² represents a double bond.

In the general formula (8), X ²⁰¹ , X ²⁰² , X ²⁰³ and X ²⁰⁴ represent a nitrogen atom or C—R, and together with —C═N— form a nitrogen-containing heteroaryl 6-membered ring, ^At least one of ²⁰¹ , X ²⁰² , X ²⁰³ and X ²⁰⁴ represents a nitrogen atom. ^{X 201, X 202, X 203} , X 204 is -C = heteroaryl 6-membered ring nitrogen-containing to form together with the N- may form a condensed ring. R represents a hydrogen atom or a substituent, and the substituent has the same meaning as described for R ¹ and R ² . Pyrazine, pyrimidine, pyridazine, triazine, quinoxaline, quinazoline, phthalazine, cinnoline, purine, pteridine and the like are preferable, and pyrazine, pyrimidine, pyridazine, quinoxaline, quinazoline, phthalazine and cinnoline are more preferable. Z ²⁰¹ represents an atomic group forming an aryl ring or a heteroaryl ring. Aryl ring Z ²⁰¹ is formed, preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl group, naphthyl group, anthryl group, phenanthryl group, A pyrenyl group etc. are mentioned, Furthermore, you may form a carbocyclic ring, a heterocyclic ring, and a condensed ring. Heteroaryl ring preferably a carbon atom to which Z ²⁰¹ represents a nitrogen atom, an oxygen atom, a heteroaryl ring comprising a sulfur atom, more preferably 5 to represent a heteroaryl ring 6 membered, further form a condensed ring Preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, quinoxaline, phthalazine, quinazoline, Examples include naphtholidine, cinnoline, perimidine, phenanthroline, pyrrole, imidazole, pyrazole, oxazole, oxadiazole, triazole, thiadiazole, benzimidazole, benzoxazole, benzthiazole, phenanthridine, thienyl group, and furyl group. Ring Z ²⁰¹ forms an aryl ring.

In the general formula (9), Z ²⁰¹ has the same meaning as in the general formula (8), Z ³⁰¹ represents an atomic group forming an aryl ring or a heteroaryl ring condensed to a pyridine ring, and the aryl ring or heteroaryl to be formed The ring is the same as the aryl ring and heteroaryl ring formed by Z ^{201 in} formula (8). The ring formed by Z ³⁰¹ is preferably an aryl ring.

In the general formula (10), Z ²⁰¹ has the same meaning as in the general formula (8), Z ⁴⁰¹ represents an atomic group forming an aryl ring or a heteroaryl ring condensed to a pyridine ring, and the aryl ring or heteroaryl to be formed The ring is the same as the aryl ring and heteroaryl ring formed by Z ^{201 in} formula (8). The ring formed by Z ⁴⁰¹ is preferably an aryl ring.

  A more preferable form of the compound of the present invention is a compound represented by the general formula (11) to the general formula (20). The compounds represented by general formulas (11) to (12) and the compounds represented by general formulas (14) to (20) are particularly preferable.

The general formula (11) will be described. R ¹¹ and R ¹² represent a substituent, and examples of the substituent include the substituents described in the above R ¹ .

R ¹¹ and R ¹² are preferably an alkyl group or an aryl group, and more preferably an alkyl group.

q ¹¹ represents an integer of 0 to 2, 0, 1 are preferred, more preferably 0. q ¹² represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0. When q ¹¹ and q ¹² are 2 or more, the plurality of R ¹¹ and R ¹² may be the same or different from each other, and may be connected to form a condensed ring.

L ¹ represents a ligand. Examples of the ligand include the ligands necessary for forming the orthometalated iridium complex and the ligands described in the other ligands. L ¹ is preferably a ligand, a nitrogen-containing heterocyclic ligand, a diketone ligand, or a halogen ligand necessary for forming an orthometalated iridium complex, and more preferably for forming an orthometalated iridium complex. Necessary ligand, bipyridyl ligand.

n ¹ represents 0 to 5, and 0 is preferable. m ¹ represents ¹ , 2, 3 and is preferably 3. The combination of the numbers of n ¹ and m ¹ is preferably a combination of numbers in which the metal complex represented by the general formula (4) becomes a neutral complex.

The general formula (12) will be described. R ²¹ , n ² , m ² and L ² have the same meanings as R ¹¹ , n ¹ , m ¹ and L ¹ , respectively. q ²¹ represents 0 to 8, and 0 is preferable. When q ²¹ is 2 or more, the plurality of R ²¹ may be the same or different from each other, and may be connected to form a condensed ring.

The general formula (13) will be described. R ³¹ , R ³² , q ³¹ , q ³² , n ³ , m ³ , and L ³ have the same meanings as R ¹ , R ² , q ¹ , q ² , n ¹ , m ¹ , and L ¹ , respectively.

The general formula (14) will be described. R ³⁰¹ and R ³⁰² represent a substituent, and the substituent has the same meaning as described for Z ¹¹ and Z ¹² . q ³⁰¹ and q ³⁰² represent integers of 0 to 4, and when q ³⁰¹ and q ³⁰² are 2 to 4, R ³⁰¹ and R ³⁰² may be the same or different. Preferred q ³⁰¹ and q ³⁰² are 0 or 1-2, and more preferably 0-1. m ¹⁰¹ , L ¹⁰¹ , and n ¹⁰¹ have the same meanings as m ¹ , L ¹ , and n ¹ , respectively.

The general formula (15) will be described. L ¹⁰² has the same meaning as the L ^1, n ¹⁰² represents an integer of 0 to 5, 1 to 5 is preferred. m ¹⁰² is an integer of 1 to 6, 1 and 2 are preferred. The number of combinations of n ¹⁰² and m ¹⁰² is a combination of several metal complex represented by the general formula (15) becomes neutral complexes are preferred.

The general formula (16) will be described. L ¹⁰³ , n ¹⁰³ , and m ¹⁰³ are synonymous with L ¹ , n ¹⁰² , and m ¹⁰² , respectively.

The general formula (17) will be described. R ³⁰³ represents a substituent, and the substituent has the same meaning as described for Z ²¹ . Z ²³ , q ³⁰³ , L ¹⁰⁴ , n ¹⁰⁴ , and m ¹⁰⁴ have the same meanings as Z ²² , q ³⁰¹ , L ¹ , n ¹⁰¹ , and m ¹⁰¹ , respectively.

The general formula (18) will be described. In general formula (18), the ring formed by X ²⁰¹ , X ²⁰² , X ²⁰³ and X ²⁰⁴ together with —C═N— is the same as that described in general formula (8), and the preferred range is also the same. . Z ²⁰¹ represents an atomic group forming an aryl ring or a heteroaryl ring, which is the same as that described in the general formula (8), and the preferred range is also the same. n ²⁰¹ , m ²⁰¹ , and L ²⁰¹ have the same meanings as n ¹ , m ¹ , and L ¹ , respectively.

In the general formula (19), Z ²⁰¹ and Z ³⁰¹ are the same as those described in the general formula (9), and the preferred ranges are also the same. n ²⁰² , m ²⁰² , and L ²⁰² have the same meanings as n ¹ , m ¹ , and L ¹ , respectively.

In the general formula (20), Z ²⁰¹ and Z ⁴⁰¹ are the same as those described in the general formula (10), and the preferred ranges are also the same. n ²⁰³ , m ²⁰³ , and L ²⁰³ have the same meanings as n ¹ , m ¹ , and L ¹ , respectively.

  The compound of the present invention may be a so-called low-molecular compound having one repeating unit such as general formula (1), or a so-called oligomeric compound or polymer compound having a plurality of repeating units such as general formula (1). (The weight average molecular weight (in terms of polystyrene) may preferably be 1,000 to 5,000,000, more preferably 2,000 to 1,000,000, and still more preferably 3,000 to 100,000). The compound of the present invention is preferably a low molecular compound.

  Next, although the compound example used for this invention is shown, this invention is not limited to this.

  The compound of the present invention is obtained from Inorg. Chem. 1991, 30, page 1685, 1988, 27, page 3464, 1994, 33, page 545, Inorg. Chem. Acta 1991, 181. 245, J. Organomet. Chem. 1987, 335, 293, J. Am. Chem. Soc. 1985, 107, 1431, etc. it can.

  Some synthetic examples of the compounds of the present invention are shown below. As shown below, it is also possible to synthesize iridium hexahalide (III) compound and iridium hexahalide (IV) compound as starting materials.

(Synthesis Example 1)
Synthesis of Exemplified Compound (1-25) In a three-necked flask, 5.22 g of K ₃ IrCl ₆ , 16.9 g of 2-benzylpyridine, and 50 ml of glycerol were added, and the internal temperature was heated to 200 ° C. under an argon atmosphere. The mixture was stirred for 1 hour. Thereafter, the internal temperature was cooled to 40 ° C., and 150 ml of methanol was added. After stirring as it was for 1 hour, the crystals obtained by suction filtration were purified by silica gel column chromatography to obtain 4.34 g of the target exemplified compound (1-25) (yield 77%).

(Synthesis Example 2)
・ Synthesis of Exemplified Compound (1-24) 5.64 g of Exemplified Compound (1-25), 560 ml of chloroform, and 10.0 g of acetylacetone were placed in a three-necked flask, and sodium methylate was stirred here at room temperature. 20.1 ml of 28% methanol solution was added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours, and extracted with 40 ml of saturated saline and 400 ml of water. The obtained chloroform layer was washed four times with a mixed solution of 300 ml of saturated saline and 30 ml of water, dried over anhydrous sodium sulfate, and concentrated by a rotary evaporator. The residue thus obtained was purified by silica gel column chromatography to obtain 5.59 g of the desired exemplified compound (1-24) (yield 89%).

(Synthesis Example 3)
Synthesis of Exemplified Compound (1-26) In a three-necked flask, 6.28 g of Exemplified Compound (1-24), 15.5 g of 2-phenylpyridine, and 63 ml of glycerol were placed, and the internal temperature was 170 under an argon atmosphere. The mixture was stirred for 15 minutes while being heated to ° C. Thereafter, the mixture was cooled to 40 ° C., and extracted by adding 500 ml of chloroform, 40 ml of saturated saline, and 400 ml of water. The resulting chloroform layer was washed four times with a mixed solution of 40 ml of saturated saline and 400 ml of water, and dried over anhydrous sodium sulfate. The residue obtained by concentrating this with a rotary evaporator was purified by silica gel column chromatography to obtain 5.60 g of the target exemplified compound (1-26) (yield 82%).

(Synthesis Example 4)
-Synthesis | combination of exemplary compound (1-29) 5.64 g of exemplary compound (1-25) and 560 ml of chloroform were put into the 3 necked flask, and carbon monoxide was blown here for 10 minutes, stirring in a water bath. Thereafter, stirring was continued for 1 hour, and then 40 ml of saturated brine and 400 ml of water were added for extraction. The obtained chloroform layer was washed four times with a mixed solution of 300 ml of saturated saline and 30 ml of water, dried over anhydrous sodium sulfate, and concentrated by a rotary evaporator. The residue thus obtained was purified by silica gel column chromatography to obtain 4.38 g of the target exemplified compound (1-29) (yield 74%).

(Synthesis Example 5)
Synthesis of Exemplary Compounds (1-65) and (1-66)

To a solution of 1.35 g of K ₃ IrCl ₆ in 25 ml of water, 1.01 g of 3-chloro-6-phenylpyridazine and 100 ml of glycerin were added, and the mixture was heated and stirred at 180 ° C. for 4 hours. After completion of the reaction, the mixture was allowed to cool, water was added, and the dark brown solid precipitated was collected by filtration and dried. Next, 2.5 g of acetylacetone and 4.8 g of 28% sodium methoxide methanol solution were added to a solution obtained by dissolving the obtained solid in 1 L of chloroform, and reacted for 2 hours while heating under reflux. After completion of the reaction, the mixture was poured into 500 ml of water and extracted with chloroform. The extract was dried over anhydrous magnesium sulfate and concentrated, and the resulting solid was developed by silica gel column chromatography. The orange fraction eluted first was concentrated, recrystallized with chloroform-ethanol and dried to obtain 66 mg of the target exemplified compound 1-65. When a solution fluorescence spectrum of this compound was determined to be fluorescence λmax = 578nm (CHCl _3). Further, the red-orange fraction eluted next was concentrated, recrystallized with chloroform-ethanol and dried to obtain 294 mg of the target exemplified compound 1-66. When a solution fluorescence spectrum of this compound was determined to be fluorescence λmax = 625nm (CHCl _3).

  Next, a light emitting device containing the compound of the present invention will be described. The light-emitting device of the present invention is not particularly limited as long as it is a device that uses the compound of the present invention, and the system, driving method, usage form, etc. are not particularly limited. The thing utilized as is preferable. An organic EL (electroluminescence) element can be mentioned as a typical light emitting element.

  The method for forming the organic layer of the light-emitting device containing the compound of the present invention is not particularly limited, but methods such as resistance heating vapor deposition, electron beam, sputtering, molecular lamination method, coating method, inkjet method, printing method, etc. Is used, and resistance heating vapor deposition and coating methods are preferable in terms of characteristics and production, and a coating method is more preferable from the viewpoint of avoiding thermal decomposition during vapor deposition.

  The light emitting device of the present invention is a device in which a plurality of organic compound thin films including a light emitting layer or a light emitting layer are formed between a pair of anode and cathode electrodes. In addition to the light emitting layer, a hole injection layer, a hole transport layer, and an electron injection It may have a layer, an electron transport layer, a protective layer, etc., and each of these layers may have other functions. Various materials can be used for forming each layer.

  The anode supplies holes to a hole injection layer, a hole transport layer, a light emitting layer, and the like, and a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Is a material having a work function of 4 eV or more. Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO), or metals such as gold, silver, chromium, and nickel, and these metals and conductive metal oxides. Inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO, preferably conductive metals It is an oxide, and ITO is particularly preferable from the viewpoint of productivity, high conductivity, transparency, and the like. Although the film thickness of the anode can be appropriately selected depending on the material, it is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, still more preferably 100 nm to 500 nm.

  As the anode, a layer formed on a soda-lime glass, non-alkali glass, a transparent resin substrate or the like is usually used. When glass is used, it is preferable to use non-alkali glass as the material in order to reduce ions eluted from the glass. Moreover, when using soda-lime glass, it is preferable to use what gave barrier coatings, such as a silica. The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength, but when glass is used, a thickness of 0.2 mm or more, preferably 0.7 mm or more is usually used. Various methods are used for producing the anode depending on the material. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method, etc.), a coating of a dispersion of indium tin oxide, etc. A film is formed by this method. The anode can be subjected to cleaning or other treatments to lower the drive voltage of the element or increase the light emission efficiency. For example, in the case of ITO, UV-ozone treatment, plasma treatment, etc. are effective.

  The cathode supplies electrons to the electron injection layer, the electron transport layer, the light emitting layer, etc., and the adhesion, ionization potential, stability, etc., between the negative electrode and the adjacent layer such as the electron injection layer, electron transport layer, light emitting layer, etc. Selected in consideration of As a material for the cathode, a metal, an alloy, a metal halide, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Specific examples include an alkali metal (for example, Li, Na, K, etc.) and its fluoride. , Alkaline earth metals (eg, Mg, Ca, etc.) and fluorides thereof, gold, silver, lead, aluminum, sodium-potassium alloys or mixed metals thereof, lithium-aluminum alloys or mixed metals thereof, magnesium-silver alloys Or a mixed metal thereof, a rare earth metal such as indium or ytterbium, and the like, preferably a material having a work function of 4 eV or less, more preferably aluminum, a lithium-aluminum alloy or a mixed metal thereof, a magnesium-silver alloy or These mixed metals. The cathode can take not only a single layer structure of the compound and the mixture but also a laminated structure including the compound and the mixture. The film thickness of the cathode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, still more preferably 100 nm to 1 μm. For production of the cathode, methods such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, and a coating method are used, and a metal can be vapor-deposited alone or two or more components can be vapor-deposited simultaneously. Furthermore, a plurality of metals can be vapor-deposited simultaneously to form an alloy electrode, or a pre-adjusted alloy may be vapor-deposited. The sheet resistance of the anode and the cathode is preferably low, and is preferably several hundred Ω / □ or less.

  The material of the light emitting layer is a function capable of injecting holes from the anode or hole injection layer, hole transport layer and cathode or electron injection layer, electron transport layer when an electric field is applied, Any singlet exciton or triplet exciton can be used as long as it can form a layer having a function of transferring injected charges and a function of emitting light by providing a recombination field of holes and electrons. Any of these may emit light. For example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, perinone derivatives, oxadiazole derivatives, aldazine derivatives , Pyraziridine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidin compounds, 8-quinolinol derivatives, metal complexes and rare earth complexes Polymer compounds such as polythiophene, polyphenylene, polyphenylene vinylene, etc. represented by various metal complexes, Machine silane derivatives, the compounds of the present invention, and the like. Although the film thickness of a light emitting layer is not specifically limited, Usually, the thing of the range of 1 nm-5 micrometers is preferable, More preferably, it is 5 nm-1 micrometer, More preferably, it is 10 nm-500 nm. The formation method of the light emitting layer is not particularly limited, but resistance heating vapor deposition, electron beam, sputtering, molecular lamination method, coating method (spin coating method, casting method, dip coating method, etc.), inkjet method, LB method The printing method and the like are used, and the resistance heating vapor deposition and the coating method are preferable.

  The material of the hole injection layer and the hole transport layer may be any one having a function of injecting holes from the anode, a function of transporting holes, or a function of blocking electrons injected from the cathode. Good. Specific examples include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives. , Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline compounds Examples include copolymers, thiophene oligomers, conductive polymer oligomers such as polythiophene, organic silane derivatives, carbon films, and the compounds of the present invention. The film thicknesses of the hole injection layer and the hole transport layer are not particularly limited, but are usually preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 500 nm. . The hole injection layer and the hole transport layer may have a single layer structure composed of one or more of the materials described above, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. As a method for forming the hole injection layer and the hole transport layer, a vacuum deposition method, an LB method, a method in which the hole injection / transport agent is dissolved or dispersed in a solvent (a spin coating method, a casting method, a dip coating method). Etc.), an inkjet method, and a printing method are used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. Examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, and poly (N -Vinyl carbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, and the like.

  The material for the electron injection layer and the electron transport layer may be any material having any one of a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode. Specific examples include triazole derivatives, oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyryl. Various metal complexes typified by pyrazine derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, metal complexes having benzoxazole or benzothiazole as a ligand, And organic silane derivatives. Although the film thickness of an electron injection layer and an electron carrying layer is not specifically limited, The thing of the range of 1 nm-5 micrometers is preferable normally, More preferably, it is 5 nm-1 micrometer, More preferably, it is 10 nm-500 nm. The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. As a method for forming the electron injection layer and the electron transport layer, a vacuum deposition method, an LB method, a method in which the electron injection transport agent is dissolved or dispersed in a solvent (a spin coating method, a casting method, a dip coating method, etc.), An ink jet method, a printing method, or the like is used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. As the resin component, for example, those exemplified in the case of the hole injection transport layer can be applied.

As a material for the protective layer, any material may be used as long as it has a function of preventing substances that promote device deterioration such as moisture and oxygen from entering the device. Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, and Fe ₂ O. ₃ , metal oxides such as Y ₂ O ₃ and TiO ₂ , metal fluorides such as MgF ₂ , LiF, AlF ₃ and CaF ₂ , polyethylene, polypropylene, polymethyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychloro Trifluoroethylene, polydichlorodifluoroethylene, a copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, a copolymer obtained by copolymerizing a monomer mixture containing tetrafluoroethylene and at least one comonomer, copolymerization Fluorine-containing copolymer having a cyclic structure in the main chain, water-absorbing substance with water absorption of 1% or more And moisture-proof substances having a water absorption rate of 0.1% or less. There is no particular limitation on the method for forming the protective layer. For example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency excitation ions) Plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, and printing method can be applied.

  Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Comparative Example 1
Poly (N-vinylcarbazole) 40 mg, PBD (2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole) 12 mg, Compound A 1 mg was added to dichloroethane 2.5 ml. And spin-coated on the cleaned substrate (1500 rpm, 20 sec). The film thickness of the organic layer was 98 nm. A patterned mask (a mask having a light emission area of 4 mm × 5 mm) was placed on the organic thin film, and magnesium: silver = 10: 1 was co-evaporated to 50 nm in a deposition apparatus, and then 50 nm of silver was deposited. Using a source measure unit model 2400 made by Toyo Technica, applying a DC constant voltage to the EL element to emit light, using a luminance meter BM-8 from Topcon and a spectrum analyzer PMA-11 from Hamamatsu Photonics. Measured. As a result, green light emission of λmax = 500 nm was obtained. When the external quantum yield in the vicinity of 100 cd / m ² was calculated, it was 0.1%. When left standing under nitrogen for 1 hour, many dark spots were visually observed on the light emitting surface.

Example 1
A device was prepared in the same manner as in Comparative Example 1 using (1-1) instead of Compound A in Comparative Example 1. A green light emission of λmax = 510 nm was obtained, and the external quantum yield in the vicinity of 100 cd / m ² was 2.9%. When left for 1 hour under nitrogen, a small amount of dark spots were visually observed on the light emitting surface.
Example 2
A device was fabricated in the same manner as in Comparative Example 1 using (1-2) instead of Compound A in Comparative Example 1. Green light emission of λmax = 510 nm was obtained. Although it was allowed to stand under nitrogen for 1 hour, dark spots were not visible.

Example 3
A device was fabricated in the same manner as in Comparative Example 1 using (1-3) instead of Compound A in Comparative Example 1. An orange light emission of λmax = 590 nm was obtained. Although it was allowed to stand under nitrogen for 1 hour, dark spots were not visible.
Example 4
A device was fabricated in the same manner as in Comparative Example 1 using (1-4) instead of Compound A in Comparative Example 1. Green light emission of λmax = 510 nm was obtained. Although it was allowed to stand under nitrogen for 1 hour, dark spots were not visible.

Example 5
A device was prepared in the same manner as in Comparative Example 1 using (1-20) instead of Compound A in Comparative Example 1. Green light emission of λmax = 547 nm was obtained. Although it was allowed to stand under nitrogen for 1 hour, dark spots were not visible.
Example 6
A device was prepared in the same manner as in Comparative Example 1 using (1-24) instead of Compound A in Comparative Example 1. Green light emission of λmax = 530 nm was obtained. Although it was allowed to stand under nitrogen for 1 hour, dark spots were not visible.

Example 7
A device was prepared in the same manner as in Comparative Example 1 using (1-25) instead of Compound A in Comparative Example 1. Light emission of λmax = 564 nm was obtained. Although it was allowed to stand under nitrogen for 1 hour, dark spots were not visible.
Example 8
A device was prepared in the same manner as in Comparative Example 1 using (1-36) instead of Compound A in Comparative Example 1. A green light emission of λmax = 520 nm was obtained. Although it was allowed to stand under nitrogen for 1 hour, dark spots were not visible.

Example 9
A device was prepared in the same manner as in Comparative Example 1 using (1-41) instead of Compound A in Comparative Example 1. A green light emission of λmax = 513 nm was obtained, and the external quantum efficiency in the vicinity of 100 cd / m ² was 5.1%. Although it was allowed to stand under nitrogen for 1 hour, dark spots were not visible.
Example 10
A device was fabricated in the same manner as in Comparative Example 1 using (1-42) instead of Compound A in Comparative Example 1. Green light emission of λmax = 535 nm was obtained. Although it was allowed to stand under nitrogen for 1 hour, dark spots were not visible.

Example 11
A device was fabricated in the same manner as in Comparative Example 1 using (1-44) instead of Compound A in Comparative Example 1. An orange light emission of λmax = 532 nm was obtained. Although it was allowed to stand under nitrogen for 1 hour, dark spots were not visible.
Example 12
A device was fabricated in the same manner as in Comparative Example 1 using (1-46) instead of Compound A in Comparative Example 1. A yellow light emission of λmax = 568 nm was obtained. Although it was allowed to stand under nitrogen for 1 hour, dark spots were not visible.

Example 13
A device was fabricated in the same manner as in Comparative Example 1 using (1-65) instead of Compound A in Comparative Example 1. Yellow-orange light emission with a light emission of λmax = 578 nm was obtained. Although it was allowed to stand under nitrogen for 1 hour, dark spots were not visible.
Example 14
A device was fabricated in the same manner as in Comparative Example 1 using (1-66) instead of Compound A in Comparative Example 1. A red-orange light emission of λmax = 625 nm was obtained. Although it was allowed to stand under nitrogen for 1 hour, dark spots were not visible.

Example 15
The cleaned ITO substrate was put into a vapor deposition apparatus, and α-NPD (N, N′-diphenyl-N, N′-di (α-naphthyl) -benzidine) was vapor-deposited to a thickness of 40 nm. 1-46) was co-evaporated at a ratio of (10: 1) to 24 nm, and Compound C was deposited thereon by 24 nm. A patterned mask (a mask with a light emitting area of 4 mm × 5 mm) was placed on the organic thin film, and magnesium: silver = 10: 1 was co-evaporated to 250 nm in an evaporation apparatus, and then 250 nm of silver was evaporated. As a result of emitting light by applying a DC constant voltage to the EL element, yellow light emission of λmax = 567 nm was obtained, and the external quantum efficiency was 13.6% (at 185 cd / m ² ).

Example 16
The cleaned ITO substrate was put into a vapor deposition apparatus, and α-NPD (N, N′-diphenyl-N, N′-di (α-naphthyl) -benzidine) was vapor-deposited to 40 nm, on which the compound of the present invention (1-42 ) Was co-evaporated to 20 nm, and Compound C was deposited thereon to 40 nm. A patterned mask (a mask with a light emitting area of 4 mm × 5 mm) was placed on the organic thin film, and magnesium: silver = 10: 1 was co-evaporated to 250 nm in an evaporation apparatus, and then 250 nm of silver was evaporated. As a result of applying a constant DC voltage to the EL element to emit light, yellow-green light emission of λmax = 535 nm was obtained, and the external quantum efficiency was 3.1% (at 120 cd / m ² ).

Example 17
Poly (N-vinylcarbazole) 40 mg, PBD (2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole) 12 mg, Compound of the present invention (1-49) 1 mg was dissolved in 2.5 ml of dichloroethane and spin-coated on the washed substrate (1500 rpm, 20 sec). The film thickness of the organic layer was 98 nm. It was put in a vapor deposition apparatus, and Compound C was vapor deposited to 40 nm on the organic film. A patterned mask (a mask having a light emission area of 4 mm × 5 mm) was placed on the organic thin film, and after 5 nm of lithium fluoride was deposited in the deposition apparatus, 500 nm of aluminum was deposited. As a result of applying a constant DC voltage to the EL element to emit light, an orange light emission of λmax = 580 nm was obtained, and the external quantum efficiency was 4.2% (at 1000 cd / m ² ).

Example 18
Baytron P (PEDOT-PSS solution (polyethylenedioxythiophene-polystyrenesulfonic acid dope) / manufactured by Bayer) was spin-coated on a cleaned substrate (1000 rpm, 30 sec) and vacuum dried at 150 ° C. for 1.5 hours. did. The film thickness of the organic layer was 70 nm. On top of this, 40 mg of poly (N-vinylcarbazole), 12 mg of PBD (2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole), the compound of the present invention (1 -42) 1 mg was dissolved in 2.5 ml of dichloroethane and spin-coated on the cleaned substrate (1500 rpm, 20 sec). The total organic layer thickness was 170 nm. A patterned mask (a mask with a light emitting area of 4 mm × 5 mm) was placed on the organic thin film, and magnesium: silver = 10: 1 was co-evaporated to 250 nm in an evaporation apparatus, and then 250 nm of silver was evaporated. As a result of applying a DC constant voltage to the EL element to emit light, yellow-green light emission of λmax = 540 nm was obtained, and the external quantum efficiency was 6.2% (2000 cd / m ² ). Similarly, when the compound-containing EL device of the present invention was produced and evaluated, it was confirmed that high-efficiency EL devices having various emission colors could be produced and the durability was excellent. Moreover, the vapor deposition type dope element using the compound of the present invention can emit light with high efficiency and can emit light with high efficiency even in an element using a light emitting material as a single layer film.

Claims (14)

A light emitting device material comprising a compound having a partial structure represented by the general formula (1) or a tautomer thereof.

A light emitting device material comprising a compound having a partial structure represented by the general formula (2) or a tautomer thereof.

A light emitting device material comprising a compound having a partial structure represented by the general formula (3) or a tautomer thereof.

In the formula, R ¹ and R ² each represent a substituent. q ¹ and q ² represent integers of 0 to 4, and q ¹ + q ² is 1 or more. A compound having a partial structure represented by the general formula (4) or a tautomer thereof.

In the formula, each of Z ¹¹ and Z ¹² represents a nonmetallic atomic group necessary for forming a 5-membered ring or a 6-membered ring with a carbon atom and / or a nitrogen atom, and this ring may have a substituent. Further, a condensed ring may be formed with another ring. Ln ¹ represents a divalent group. Y ¹ represents a nitrogen atom or a carbon atom, and b ¹ represents a single bond or a double bond.   A light emitting material comprising the compound according to claim 4. A light emitting material comprising a compound having a partial structure represented by the general formula (5).

A light emitting material comprising a compound having a partial structure represented by the general formula (6).

A light emitting material comprising a compound having a partial structure represented by the general formula (7) or a tautomer thereof.

In the formula, Z ²¹ and Z ²² each represent a nonmetallic atomic group necessary for forming a 5-membered ring or a 6-membered ring with a carbon atom and / or a nitrogen atom, and this ring may have a substituent. It may also form a condensed ring with another ring. Y ² represents a nitrogen atom or a carbon atom, and b ² represents a single bond or a double bond. A luminescent material comprising a compound having a partial structure represented by the general formula (8) or a tautomer thereof.

In the formula, X ²⁰¹ , X ²⁰² , X ²⁰³ and X ²⁰⁴ represent a nitrogen atom or C—R, and together with —C═N— form a nitrogen-containing heteroaryl 6-membered ring, and X ²⁰¹ , X ²⁰² , X ²⁰³ And at least one of X ²⁰⁴ represents a nitrogen atom. R represents a hydrogen atom or a substituent. Z ²⁰¹ represents an atomic group forming an aryl ring or a heteroaryl ring. A light emitting material comprising a compound having a partial structure represented by the general formula (9) or a tautomer thereof.

In the formula, Z ²⁰¹ and Z ³⁰¹ represent an atomic group forming an aryl ring or a heteroaryl ring. A light emitting material comprising a compound having a partial structure represented by the general formula (10) or a tautomer thereof.

In the formula, Z ²⁰¹ and Z ⁴⁰¹ each represents an atomic group forming an aryl ring or a heteroaryl ring.   12. A light emitting device in which a light emitting layer or a plurality of organic compound thin layers including a light emitting layer is formed between a pair of electrodes, and the organic light emitting device containing the light emitting material according to claim 1, 2, 3, 5 to 11 in at least one layer. .   A light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes, and has at least one layer made of a single light-emitting material according to claim 1, 2, 3, 5 to 11. An organic light emitting device characterized by the above.   In a light emitting device in which a light emitting layer or a plurality of organic compound thin layers including a light emitting layer is formed between a pair of electrodes, a coating process including a layer having an orthometalated iridium complex in at least one layer and containing an orthometalated iridium complex A light-emitting element formed by film formation.