JP2007169474A - Polymer light-emitting material, organic electroluminescent element and display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer light-emitting material which gives highly pure red light in high light-emitting efficiency, to provide an organic EL element whose production process is simplified and which realizes the increase of the area and has excellent durability, and to provide a display. <P>SOLUTION: This polymer light-emitting material is characterized by comprising a polymer containing structural units derived from an iridium complex represented by the general formula (1). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polymer light emitting material and an organic electroluminescence device. More specifically, the present invention relates to a high-purity red light emission, a polymer light-emitting material having a long driving life, a simplified manufacturing process, a large area, and an organic material with excellent durability. The present invention relates to an electroluminescence element.

  In recent years, development of materials used for organic electroluminescence (also referred to as “organic EL” in this specification) elements has been actively conducted. For example, in order to realize full-color display, materials that emit light of each of the three primary colors (RGB) (red, green, and blue) of light are required. There is a demand for a material having high purity light emission and a long driving life.

Recently, an orthometalated iridium complex containing a derivative having a phenanthridine structure as a ligand has been disclosed. (Patent Document 1)
In the present specification, “orthometalation” refers to a 5-membered or 6-membered aromatic ring or aromatic heterocyclic ring containing Z ¹ , C ¹ , C ² and Q ^{1 in} the general formula (1). A reaction in which a C—H bond in the ortho position with respect to the bonding position of a substituent having a positional atom generates a chelate ring containing a metal-carbon bond by an intramolecular reaction.

  According to Patent Document 1, it is described that an organic EL element capable of obtaining high-luminance red to orange light with high luminous efficiency can be obtained. However, there is a demand for further extending the life of the element.

In general, when a light emitting layer is formed, a vacuum vapor deposition method is used for a low molecular compound such as the above complex. However, the film thickness of the light emitting layer obtained by this method tends to be uneven.
In addition, the vacuum deposition method requires a large facility, and its conditions are strictly controlled, so it is sometimes not a simple manufacturing method for increasing the screen size.

On the other hand, when a light emitting layer is formed with a polymer composition in which the complex is dispersed in a polymer, that is, a doped light emitting material, a coating method may be used. However, doped light emitting materials have the disadvantage that they are poor in thermal stability and are liable to cause phase separation or segregation.
JP 2003-059667 A

  An object of the present invention is to provide a polymer light-emitting material from which high-purity red light can be obtained with high luminous efficiency. Another object of the present invention is to provide an organic EL element and a display device that have a simplified manufacturing process, can achieve a large area, and are excellent in durability.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polymer light-emitting material composed of a polymer containing a structural unit derived from a specific iridium complex has high-purity red light and has a driving life. We found a long time and came to complete the present invention.

That is, the present invention is summarized as follows.
[1]
A polymer light-emitting material comprising a polymer containing a structural unit derived from an iridium complex represented by the following general formula (1).

(In the general formula (1), R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OH, —SX ¹ , —OCOX ² , —COOX ³ , —SiX ⁴ X ^5. X ^6, -NH _2, -N
HX ⁷ , —NX ⁸ X ⁹ , an alkoxy group having 1 to 10 carbon atoms, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or a halogen in which some or all of the hydrogen atoms are substituted with halogen atoms A substituted alkyl group, an aryl group having 6 to 21 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, or a halogen in which part or all of the hydrogen atoms thereof are substituted with halogen atoms A substituted aryl group, a halogen-substituted heteroaryl group or a halogen-substituted aralkyl group is represented. (Here, X ^{1 to} X ⁹ are each independently a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 21 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or Represents an aralkyl group having 7 to 21 carbon atoms.)
Q ¹ represents a carbon atom, a nitrogen atom or a sulfur atom, and Z ¹ forms a 5-membered or 6-membered aromatic ring or aromatic heterocycle together with carbon atoms C ¹ and C ² and Q ¹ . Represents an atomic group, the ring may have a substituent, and may form a condensed ring with another ring.
L represents a monovalent anionic bidentate ligand having a polymerizable functional group. )

[2]
In the above general formula (1), a 5-membered or 6-membered aromatic ring or aromatic heterocyclic ring formed from C ¹ , C ² , Q ¹ and Z ^1, or the aromatic ring or aromatic heterocyclic ring and other ring From the group consisting of benzene, naphthalene, phenanthrene, anthracene, pyridine, quinoline, isoquinoline, benzoxazole, benzothiazole, benzimidazole, benzotriazole, imidazole, pyrazole, oxazole, thiazole, triazole, benzopyrazole and triazine The polymer luminescence according to [1], wherein the ring skeleton of one kind of selected compound is a skeleton and may have the same substituent as the group defined by R ^{1 to} R ⁸ material.

[3]
The polymer luminescent material according to [1], wherein the iridium complex is represented by any one of the following general formulas (2) to (8).

(In General Formula (2) to General Formula (8), R ^{1 to} R ³⁵ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OH, —SX ¹ , —OCOX ² , —COOX ^3. , —SiX ⁴ X ⁵ X ⁶ , —NH ₂ , —NHX ⁷ , —NX ⁸ X ⁹ , an alkoxy group having 1 to 10 carbon atoms, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or hydrogen thereof A halogen-substituted alkyl group in which some or all of the atoms are substituted with a halogen atom, an aryl group having 6 to 21 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, or hydrogen thereof some of the atoms or all represent a substituted halogen-substituted aryl group, halogen-substituted heteroaryl group or a halogen-substituted aralkyl group with a halogen atom. (the number of carbon atoms wherein, X ¹ to X ⁹ are each independently To 22 linear, cyclic or branched alkyl group, an aryl group of 6 to 21 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an aralkyl group having 7 to 21 carbon atoms.)
L represents a monovalent anionic bidentate ligand having a polymerizable functional group. )

[4]
The polymer light-emitting material according to any one of [1] to [3], wherein L is a bidentate ligand represented by the following general formula (9) or (10).

(Wherein X ¹⁰ has the same meaning as R ¹ in the above formula (1), Y ¹ and Y ² are each independently
A substituent having a polymerizable functional group is represented. )

[5]
The polymer further includes a structural unit derived from at least one polymerizable compound selected from the group consisting of a hole transport polymerizable compound and an electron transport polymerizable compound [1]. The polymer light-emitting material according to any one of to [4].

[6]
In the organic electroluminescence device including one or more organic polymer layers sandwiched between an anode and a cathode, at least one of the organic polymer layers is any one of [1] to [5] An organic electroluminescence device comprising a polymer light-emitting material.

[7]
The image display apparatus using the organic electroluminescent element as described in [6].

[8]
A surface-emitting light source using the organic electroluminescence element according to [6].

  According to the present invention, a polymer light emitting material having high purity red light and a long driving life can be provided. Especially, it is effective for extending the life of the element. In addition, according to the present invention, it is possible to provide an organic EL element and a display device that are simplified in manufacturing process, can be increased in area, and are excellent in durability.

  In organic EL devices, the lifetime of the excited triplet state is generally longer than the lifetime of the excited singlet, and the molecule stays in a high energy state, so that it reacts with surrounding substances, changes in the structure of the molecule itself, and reactions between excitons. Therefore, it is considered that the driving life of the phosphorescent light emitting device is short with the conventional metal coordination compounds.

  Accordingly, the present inventors have conducted various studies and found that a polymer light-emitting material characterized by comprising a polymer containing a structural unit derived from a specific iridium complex is effective. The cause is currently under investigation, but it seems that one factor is that the π-conjugated electron system is longer than the conventional ligand.

Hereinafter, the present invention will be specifically described.
1. Polymer Light-Emitting Material The polymer light-emitting material according to the present invention comprises a polymer containing a structural unit derived from a specific iridium complex. With such a material, light emission from the triplet excited state of the iridium complex can be obtained. The polymer light emitting material further comprises a polymer including a structural unit derived from at least one polymerizable compound selected from the group consisting of a hole transport polymerizable compound and an electron transport polymerizable compound. Is preferred.
<Polymer containing structural unit derived from iridium complex>
The polymer used in the present invention is obtained by polymerizing a monomer containing an iridium complex represented by the above formula (1). In the said polymer, you may use the monomer of the said iridium complex individually by 1 type or in combination of 2 or more types. In the present specification, the polymer includes a homopolymer of the complex and a copolymer of two or more of the complexes.

  The iridium complex represented by the above formula (1) contains a derivative having a phenanthridine structure as a ligand. A polymer light emitting material using the complex emits red light. Moreover, according to this polymer light emitting material, an organic EL device having excellent durability can be produced.

The symbols (R ^{1 to} R ³⁵ , C ¹ , C ² , Q ¹ , X ¹⁰ , Z ¹ , L, Y ¹ , Y ² ) described in the above general formula (1) to general formula (10) are more specifically described below. I will explain it.
In general formula (1) to general formula (10), R ^{1 to} R ³⁵ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OH, —SX ¹ , —OCOX ² , —COOX ³ , ^{-SiX 4 X 5 X 6, -NH} 2, -NHX 7, -NX 8 X 9, an alkoxy group having 1 to 10 carbon atoms, straight-chain, cyclic or branched alkyl group or their hydrogen atoms of 1 to 22 carbon atoms A halogen-substituted alkyl group, a C6-C21 aryl group, a C2-C20 heteroaryl group, a C7-C21 aralkyl group or a hydrogen atom thereof, part or all of which is substituted with a halogen atom It represents a halogen-substituted aryl group, a halogen-substituted heteroaryl group or a halogen-substituted aralkyl group, part or all of which are substituted with a halogen atom. (Here, X ^{1 to} X ⁹ are each independently a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 21 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or Represents an aralkyl group having 7 to 21 carbon atoms.)
Here, X ^{1 to} X ⁹ may have a substituent, and examples of the substituent include a halogen atom, a cyano group, an aldehyde group, an amino group, an alkyl group, an alkoxy group, an alkylthio group, a carboxyl group, a sulfone group. An acid group, a nitro group, etc. can be mentioned. These substituents may be further substituted with a halogen atom, a methyl group or the like.

  Examples of linear, cyclic or branched alkyl groups include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, tert-butyl, cyclobutyl, pentyl, isopentyl, A neopentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a heptyl group, a cycloheptyl group, an octyl group, a nonyl group, and a decyl group can be exemplified.

Examples of aryl or heteroaryl groups include phenyl, tolyl, xylyl, mesityl, cumenyl, benzyl, phenethyl, methylbenzyl, diphenylmethyl, styryl, cinnamyl, biphenyl residues, Terphenyl residue, naphthyl group, anthryl group, fluorenyl group, furan residue, thiophene residue, pyrrole residue, oxazole residue, thiazole residue, imidazole residue, pyridine residue, pyrimidine residue, pyrazine residue, A triazine residue, a quinoline residue, and a quinoxaline residue can be mentioned.

  Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, tert-butoxy, octyloxy, tert-octyloxy, phenoxy, 4-tert-butylphenoxy, 1-naphthyloxy , 2-naphthyloxy group, and 9-anthryloxy group.

Examples of —SX ¹ include a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group, an octylthio group, a phenylthio group, a 2-methylphenylthio group, and a 4-tert-butylphenylthio group.

Examples of —OCOX ² include an acetoxy group and a benzoyloxy group.
Examples of —COOX ³ include methoxycarbonyl group, ethoxycarbonyl group, tert
-A butoxycarbonyl group, a phenoxycarbonyl group, a naphthyloxycarbonyl group, etc. can be mentioned.

Examples of —SiX ⁴ X ⁵ X ⁶ include a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, and the like.
Examples of —NHX ⁷ include N-methylamino group, N-ethylamino group, N-benzylamino group, N-phenylamino group and the like.

Examples of —NX ⁸ X ⁹ include N, N-dimethylamino group, N, N-diethylamino group, N, N-diisopropylamino group, N, N-dibutylamino group, N, N-dibenzylamino group, N, N-diphenylamino group and the like can be mentioned.

The 5-membered or 6-membered ring formed by C ¹ , C ² , Q ¹ and Z ¹ is an aromatic ring or an aromatic heterocycle. Specifically, for example, from benzene, naphthalene, phenanthrene, anthracene, pyridine, quinoline, isoquinoline, furan, thiophene, benzoxazole, benzothiazole, benzimidazole, benzotriazole, imidazole, pyrazole, oxazole, thiazole, triazole, benzopyrazole and triazine An aromatic ring or an aromatic heterocyclic ring having a ring skeleton of one kind of compound selected from the group as a skeleton can be exemplified.

Of these, benzene, naphthalene, thiophene, pyridine, quinoline and isoquinoline are preferred.
As the derivative of the iridium complex represented by the general formula (1), the iridium complex represented by the following general formula (2) or (8) is more preferable in terms of the ease of synthesis, the lifetime of the prepared device, and the color purity. preferable.

In General Formula (1) to General Formula (8), L represents a monovalent anion bidentate ligand having a polymerizable functional group.
As a bidentate ligand of a monovalent anion, for example, from a compound having a structure in which one hydrogen ion is eliminated and a conjugated structure containing two coordination sites can be monovalent anionic as a whole, a hydrogen ion 1 is a monovalent anion; or a nonionic coordination site such as a pyridine ring, a carbonyl group or an imine group and one hydrogen ion such as a hydroxyl group or a carboxyl group in the molecule. Examples thereof include a compound having a site that can be eliminated to form a monovalent anionic coordination site.

  Preferably, it is a bidentate ligand represented by the general formula (9) or (10).

(Wherein X ¹⁰ has the same meaning as R ¹ in the above formula (1), Y ¹ and Y ² are each independently
A substituent having a polymerizable functional group is represented. )
The bidentate ligand represented by the general formula (9) or the general formula (10) has a polymerizable functional group represented by Y ¹ or Y ² . The functional group may be any of radical polymerizable, cationic polymerizable, anionic polymerizable, addition polymerizable, and condensation polymerizable functional groups. Of these, the radical polymerizable functional group is preferable because the production of the polymer is easy.

  Examples of the polymerizable functional group include urethane (meth) acrylate groups such as allyl group, alkenyl group, acrylate group, methacrylate group, methacryloyloxyethyl carbamate group, vinylamide group, and derivatives thereof. Of these, alkenyl groups are preferred.

  More specifically, L preferably has the functional group as a substituent represented by the following general formulas (A1) to (A12). Among these, the substituents represented by the following formulas (A1), (A5), (A8), and (A12) are more preferable because functional groups can be easily introduced into the iridium complex.

  From these ligands, the following iridium complexes (C1) to (C12) are preferable as the iridium complex represented by any one of the general formulas (1) to (8).

  The iridium complex represented by any one of the above general formulas (1) to (8) is produced, for example, as follows. First, using a 6-bromophenanthridine derivative as a starting material, a derivative having a desired phenanthridine ring is obtained by reaction with arylboric acid or the like.

Next, an iridium compound such as iridium chloride and a derivative having a phenanthridine ring (0.5 equivalent to iridium) are reacted in a solvent such as 2-ethoxyethanol. Next, the obtained iridium dinuclear complex and a bidentate derivative of a monovalent anion having a polymerizable functional group are heated together with sodium carbonate in a solvent such as 2-ethoxyethanol, and then purified. Thus, an iridium complex represented by the formula can be obtained.

Examples of the synthesis method of the iridium dinuclear complex include the method described in Inorganic Chemistry, 2001, 40, 1704.
The typical examples (D1) to (D12) of iridium dinuclear complexes used as raw materials for synthesizing the iridium complex used in the present invention are shown below.

  The weight average molecular weight of the polymer containing the structural unit derived from the iridium complex represented by any one of the general formulas (1) to (8) is preferably 1,000 to 2,000,000, More preferably, it is 5,000 to 1,000,000. The molecular weight in this specification means the polystyrene conversion molecular weight measured using GPC (gel permeation chromatography) method. It is preferable for the molecular weight to be in this range since the polymer is soluble in an organic solvent and a uniform thin film can be obtained.

The polymer may be any of a random copolymer, a block copolymer, and an alternating copolymer.
The polymerization method of the polymer may be any of radical polymerization, cationic polymerization, anionic polymerization, and addition polymerization, but radical polymerization is preferred.
<Polymer having a structural unit derived from a carrier transportable polymerizable compound>
The polymer used in the present invention is at least one selected from the group consisting of a hole transporting polymerizable compound and an electron transporting polymerizable compound together with one or more monomers of the above iridium complex. It is preferable that it is a polymer obtained by copolymerizing the monomer containing this polymeric compound. In the present specification, the hole transport polymerizable compound and the electron transport polymerizable compound are also collectively referred to as a carrier transport polymerizable compound.

  That is, the polymer light emitting material includes a structural unit derived from one or more hole transportable polymerizable compounds together with a structural unit derived from one or more iridium complexes, or one or more It is preferably made of a polymer containing a structural unit derived from two or more kinds of electron-transporting polymerizable compounds. In such a polymer light-emitting material, holes and electrons are efficiently recombined on the structural unit derived from the iridium complex, so that high luminous efficiency can be obtained.

  In addition, the polymer light-emitting material includes a structural unit derived from one or more hole transportable polymerizable compounds together with a structural unit derived from one or more iridium complexes, and one or more structural units. More preferably, it comprises a polymer containing a structural unit derived from two or more kinds of electron-transporting polymerizable compounds. Such a polymer light-emitting material has all the functions of light-emitting property, hole-transporting property, and electron-transporting property, so that holes and electrons recombine more efficiently on the iridium complex, resulting in higher light emission. Efficiency is obtained.

The hole-transporting polymerizable compound and the electron-transporting polymerizable compound are not particularly limited in addition to having a polymerizable functional group, and known carrier-transporting compounds are used.
The polymerizable functional group may be any of radical polymerizable, cationic polymerizable, anionic polymerizable, addition polymerizable, and condensation polymerizable functional groups. Of these, the radical polymerizable functional group is preferable because the production of the polymer is easy.

The polymerizable functional group has the same meaning as Y ¹ or Y ² in formula (9) or formula (10).
Specifically, it is more preferable to have the functional group as a substituent represented by the general formulas (A1) to (A12). Of these, substituents represented by the following formulas (A1), (A5), (A8), and (A12) are more preferable because functional groups can be easily introduced.

  As the hole transport polymerizable compound, specifically, compounds represented by the following general formulas (E1) to (E6) are preferable, and since the carrier mobility in the copolymer is high, the following formula (E1) The compound represented by (E3) is more preferable.

  Specifically, as the electron transport polymerizable compound, compounds represented by the following general formulas (E7) to (E15) are preferable, and since the carrier mobility in the copolymer is high, the following formula (E7) The compounds represented by (E12) to (E14) are more preferred.

  In the above formulas (E1) to (E15), a compound in which the substituent represented by the above formula (A1) is replaced with the substituent represented by the above general formula (A2) to (A12) is also preferably used. However, since a functional group can be easily introduced into the polymerizable compound, a compound having a substituent represented by the above formula (A1) or (A5) is particularly preferable.

  Among these, as the hole transport polymerizable compound, the compound represented by any one of the above formulas (E1) to (E3), and as the electron transport polymerizable compound, the above formula (E7), More preferably, the compound represented by any one of (E12) to (E14) is copolymerized in combination with the iridium complex. Such a polymer light emitting material has high luminous efficiency, high maximum luminance, and excellent durability.

In this case, as the iridium complex, it is particularly preferable to use a complex represented by the above formulas (C2), (C3), (C5), and (C8) because the life can be further extended.
The polymerizable compound represented by the above formulas (E1) to (E15) can be produced by a known method.

  The polymer may further have a structural unit derived from another polymerizable compound. Examples of the other polymerizable compounds include compounds having no carrier transport properties such as (meth) acrylic acid alkyl esters such as methyl acrylate and methyl methacrylate, and styrene and derivatives thereof. It is not limited.

  The weight average molecular weight of the polymer is preferably 1,000 to 2,000,000, and more preferably 5,000 to 1,000,000. It is preferable for the molecular weight to be in this range since the polymer is soluble in an organic solvent and a uniform thin film can be obtained.

  If the ratio of the iridium complex and the carrier-transporting polymerizable compound (hole-transporting and / or electron-transporting polymerizable compound) is appropriately set, the desired polymer can be obtained. Any of a copolymer, a block copolymer, and an alternating copolymer may be sufficient.

  The number of structural units derived from the iridium complex in the polymer is m, and the number of structural units derived from a carrier transporting compound (a structure derived from a hole transporting polymerizable compound and / or an electron transporting polymerizable compound). When the total number of units is n (m, n represents an integer of 1 or more), the ratio of the number of structural units derived from the iridium complex to the total number of structural units, that is, the value of m / (m + n) is 0. It is preferably in the range of 0.001 to 0.5, and more preferably in the range of 0.001 to 0.2. When the value of m / (m + n) is in this range, an organic EL element having high luminous efficiency with high carrier mobility and low influence of concentration quenching can be obtained.

  In addition, when the polymer includes a structural unit derived from a hole transporting compound and a structural unit derived from an electron transporting compound, the number of structural units derived from the hole transporting compound is derived from x and the electron transporting compound. Assuming that the number of structural units is y (x and y are integers of 1 or more), a relationship of n = x + y is established between n and the above. Optimum values of the ratio x / n of the number of structural units derived from the hole transporting compound and the ratio y / n of the number of structural units derived from the electron transporting compound to the number of structural units derived from the carrier transporting compound are as follows. It depends on the charge transport ability of the structural unit, the charge transportability of the structural unit derived from the iridium complex, the concentration, and the like. When this polymer is used as the only compound for forming the light emitting layer of the organic EL device, the values of x / n and y / n are preferably in the range of 0.05 to 0.95, and 0.20 More preferably in the range of ~ 0.80. Here, x / n + y / n = 1 holds.

  The polymerization method of the polymer may be any of radical polymerization, cationic polymerization, anionic polymerization, and addition polymerization, but radical polymerization is preferred.

2. Organic electroluminescent element The polymer light-emitting material according to the present invention is suitably used as a material for an organic EL element. The organic EL element includes one or more organic polymer layers sandwiched between an anode and a cathode, and at least one of the organic polymer layers includes the polymer light emitting material. With the polymer light emitting material according to the present invention, a light emitting layer can be formed by a simple coating method, and the area of the device can be increased.

An example of the configuration of the organic EL element according to the present invention is shown in FIG. 1, but the configuration of the organic EL element according to the present invention is not limited thereto. In FIG. 1, a hole transport layer (3), a light emitting layer (4) and an electron transport layer (5) are arranged in this order between an anode (2) and a cathode (6) provided on a transparent substrate (1). Provided. In the organic EL device, for example, either 1) a hole transport layer / light emitting layer or 2) a light emitting layer / electron transport layer may be provided between the anode (2) and the cathode (6). In addition, 3) a layer containing a hole transport material, a light emitting material, an electron transport material, 4) a layer containing a hole transport material, a light emitting material, 5) a layer containing a light emitting material, an electron transport material, 6) Any one of the layers may be provided. Further, two or more light emitting layers may be stacked.

  In the element as described above, the polymer light-emitting material according to the present invention is derived from a structural unit derived from the iridium complex, a structural unit derived from a hole-transporting polymerizable compound, and an electron-transporting polymerizable compound. In the case of a polymer containing a structural unit to be released, the organic polymer layer containing the material can be used as a light emitting layer having both hole transport properties and electron transport properties. For this reason, even if it is a case where the layer of another organic material is not provided, the organic EL element which has high luminous efficiency and durability can be produced. In addition, the manufacturing process can be further simplified.

  Each of the above layers may be formed by mixing a polymer material or the like as a binder. Examples of the polymer material include polymethyl methacrylate, polycarbonate, polyester, polysulfone, and polyphenylene oxide.

  In addition, the light emitting material, the hole transport material, and the electron transport material used for each of the above layers may be formed independently, or may be formed by mixing materials having different functions. In the light emitting layer in the organic EL device according to the present invention, in addition to the polymer light emitting material according to the present invention, other hole transport materials and / or electron transport materials are further included for the purpose of supplementing the carrier transport property. Also good. Such a transport material may be a low molecular compound or a high molecular compound.

  Examples of the hole transport material forming the hole transport layer or the hole transport material mixed with the light emitting layer include TPD (N, N′-dimethyl-N, N ′-(3-methylphenyl) -1,1 ′. -Biphenyl-4,4'diamine); α-NPD (4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl); m-MTDATA (4,4 ', 4' '- Low molecular weight triphenylamine derivatives such as tris (3-methylphenylphenylamino) triphenylamine); polyvinylcarbazole; a polymer compound obtained by polymerizing a triphenylamine derivative by introducing a polymerizable functional group; polyparaphenylene vinylene; Examples thereof include fluorescent light-emitting polymer compounds such as polydialkylfluorene. Examples of the polymer compound include a polymer compound having a triphenylamine skeleton disclosed in JP-A-8-157575. The hole transport materials may be used singly or in combination of two or more, or different hole transport materials may be laminated and used. The thickness of the hole transport layer depends on the conductivity of the hole transport layer, but is usually preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and particularly preferably 10 nm to 500 nm.

  Examples of the electron transport material forming the electron transport layer or the electron transport material mixed with the light emitting layer include quinolinol derivative metal complexes such as Alq3 (aluminum trisquinolinolate), oxadiazole derivatives, triazole derivatives, and imidazole derivatives. And low molecular compounds such as triazine derivatives and triarylborane derivatives; and polymer compounds obtained by introducing a polymerizable substituent into the above low molecular compounds. Examples of the polymer compound include poly PBD disclosed in JP-A-10-1665. The electron transport materials may be used singly or in combination of two or more, or different electron transport materials may be laminated and used. Although the thickness of the electron transport layer depends on the conductivity of the electron transport layer, etc., it is usually preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and particularly preferably 10 nm to 500 nm.

  In addition, a hole block layer may be provided adjacent to the cathode side of the light emitting layer in order to prevent holes from passing through the light emitting layer and efficiently recombine holes and electrons in the light emitting layer. Good. For the formation of the hole block layer, a known material such as a triazole derivative, an oxadiazole derivative, or a phenanthroline derivative is used.

  A buffer layer may be provided between the anode and the hole transport layer or between the anode and the organic layer stacked adjacent to the anode in order to relax the injection barrier in hole injection. In order to form the buffer layer, a known material such as copper phthalocyanine, a mixture of polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS) is used.

  An insulating layer having a thickness of 0.1 to 10 nm is provided between the cathode and the electron transport layer or between the cathode and the organic layer laminated adjacent to the cathode in order to improve the electron injection efficiency. May be. In order to form the insulating layer, known materials such as lithium fluoride, magnesium fluoride, magnesium oxide, and alumina are used.

  As the anode material used for the organic EL device according to the present invention, for example, a known transparent conductive material such as ITO (indium tin oxide), tin oxide, zinc oxide, polythiophene, polypyrrole, polyaniline or other conductive polymer is preferably used. Used. The surface resistance of the electrode formed of the transparent conductive material is preferably 1 to 50Ω / □ (ohm / square). The thickness of the anode is preferably 50 to 300 nm.

  Examples of the cathode material used in the organic EL device according to the present invention include alkali metals such as Li, Na, K, and Cs; alkaline earth metals such as Mg, Ca, and Ba; Al; MgAg alloys; AlLi, AlCa, and the like. A known cathode material such as an alloy of Al and an alkali metal is preferably used. The thickness of the cathode is preferably 10 nm to 1 μm, more preferably 50 to 500 nm. When a highly active metal such as an alkali metal or alkaline earth metal is used, the thickness of the cathode is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm. In this case, a metal layer that is stable to the atmosphere is laminated on the cathode for the purpose of protecting the cathode metal. Examples of the metal forming the metal layer include Al, Ag, Au, Pt, Cu, Ni, and Cr. The thickness of the metal layer is preferably 10 nm to 1 μm, more preferably 50 to 500 nm.

  As the substrate of the organic EL device according to the present invention, an insulating substrate that is transparent with respect to the emission wavelength of the light emitting material is preferably used. Specifically, in addition to glass, PET (polyethylene terephthalate), polycarbonate, etc. Transparent plastics are used.

  Examples of the film formation method of the hole transport layer, the light emitting layer, and the electron transport layer include a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, an ink jet method, a spin coating method, a printing method, a spray method, and a dispenser method. Can be used. In the case of a low molecular compound, resistance heating vapor deposition or electron beam vapor deposition is preferably used, and in the case of a polymer material, an ink jet method, a spin coating method, or a printing method is suitably used.

  In the case of forming a light emitting layer using the polymer light emitting material according to the present invention, an inkjet method, a spin coating method, a dip coating method or a printing method is preferably used, so that the manufacturing process is simplified, and the large area of the device Can also be achieved.

In addition, as a method for forming the anode material, for example, an electron beam evaporation method, a sputtering method, a chemical reaction method, a coating method, or the like is used. As a method for forming the cathode material, for example, a resistance heating evaporation method, An electron beam evaporation method, a sputtering method, an ion plating method, or the like is used.

3. Use The organic EL device according to the present invention is suitably used in an image display device as a pixel by a matrix method or a segment method by a known method. The organic EL element is also suitably used as a surface light source without forming pixels.

  Specifically, the organic EL device according to the present invention is suitably used for displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
[Example]
Synthesis Example 1 Synthesis of Iridium Complex (C2) (1-1) Synthesis of Compound (a)

This will be described with reference to the above scheme.
2.0 g (7.7 mmol) of 6-bromophenanthridine (synthesized according to the method described in Journal of the Chemical Society, Chemical Communications, 1995, page 2295), 1.4 g of 4-t-butylphenylboronic acid ( 7.7 mmol) and 0.23 g (0.20 mmol) of tetrakis (triphenylphosphine) palladium were added with 50 ml of an aqueous solution of 50 ml of 1,2-dimethoxyethane and 3.0 g (22 mol) of potassium carbonate and heated for 5 hours. Refluxed. After cooling the reaction solution to room temperature, the organic layer was extracted, and the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography gave 2.5 g of compound (a).
(1-2) Synthesis of iridium complex (C2)

This will be described with reference to the above scheme.
To a mixture of 2.5 g (8.0 mmol) of compound (a) and 1.4 g (4.0 mmol) of iridium (III) chloride trihydrate, 90 ml of 2-ethoxyethanol and 30 ml of water were added, and heated under reflux for 12 hours. did. The resulting brown precipitate was washed with cold methanol and dried under reduced pressure to obtain a binuclear complex (D2). To 1.0 g (0.59 mmol) of the obtained complex (D2), 20 ml of N, N-dimethylformamide was added, and compound (b) (synthesized according to the method described in JP-A No. 2003-113246) 0.50 g (2 0.3 mmol) and 0.32 g (2.3 mmol) of potassium carbonate were added, and the mixture was heated and stirred at 90 ° C. for 4 hours. The obtained reaction solution was poured into water, and the resulting precipitate was washed with water and dried under reduced pressure. By purification by silica gel column chromatography, 0.85 g (0.83 mmol) of an iridium complex (C2) was obtained.

Identification data of the compound (C2) are as follows.
Calcd _{(C 60 H 55 IrN 2 O} 2) C, 70.08; H, 5.39; N, 2.72. Measurement C, 69.88; H, 5.61; N, 2.90.
Mass spectrometry (FAB +): 1028 (M ⁺ ).
[Synthesis Example 2] Synthesis of iridium complex (C5)

This will be described with reference to the above scheme.
Compound (c) was synthesized by the same method as the synthesis of compound (a) except that 2-naphthaleneboronic acid was used instead of 4-t-butylphenylboronic acid. Next, the iridium complex (C2) was used except that the compound (c) was used instead of the compound (a), and the compound (d) (synthesized according to the method described in JP-A-2003-206320) was used instead of the compound (b). The iridium complex (C5) was obtained by a method similar to the synthesis of

The identification data of the compound (C5) are as follows.
Calcd _{(C 54 H 34 IrN 3 O} 2) C, 68.34; H, 3.61; N, 4.43. Measurement C, 68.56; H, 3.47; N, 4.22.
Mass spectrometry (FAB +): 949 (M ⁺ ).
[Synthesis Example 3] Synthesis of iridium complex (C8)

This will be described with reference to the above scheme.
Compound (e) was synthesized by the same method as the synthesis of compound (a) except that 2-thiopheneboronic acid was used instead of 4-t-butylphenylboronic acid. Next, the iridium complex (C2) was used except that the compound (e) was used instead of the compound (a), and the compound (f) (synthesized according to the method described in JP-A-2003-206320) was used instead of the compound (b). The iridium complex (C8) was obtained by the same method as in the synthesis of.

The identification data of the compound (C8) are as follows.
Calcd _{(C 49 H 32 IrN 3 O} 3 S 2) C, 60.85; H, 3.33; N,
4.34. Measurement C, 60.51; H, 3.39; N, 4.70.
Mass spectrometry (FAB +): 967 (M ⁺ ).

[Example 1] Synthesis of copolymer (I) In a sealed container, 80 mg of an iridium complex (C2), 460 mg of a compound represented by the above formula (E1), and 460 mg of a compound represented by the above formula (E7) were placed. , Dehydrated toluene (9.9 mL) was added. Subsequently, a toluene solution (0.1 M, 198 μL) of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the freeze degassing operation was repeated 5 times. It sealed in vacuum and stirred at 60 ° C. for 60 hours. After the reaction, the reaction solution was dropped into 500 mL of acetone to obtain a precipitate. Further, reprecipitation purification with toluene-acetone was repeated twice, followed by vacuum drying at 50 ° C. overnight to obtain a copolymer (I). The weight average molecular weight (Mw) of the copolymer (I) was 35800, and the molecular weight distribution index (Mw / Mn) was 2.06. The m / (m + n) value of the copolymer estimated from the results of ICP elemental analysis and ¹³ C-NMR measurement was 0.035. In copolymer (I), the value of x / n was 0.42, and the value of y / n was 0.58.

[Example 2] Synthesis of copolymer (II) An iridium complex (C5) is substituted for the iridium complex (C2), and the compound represented by the above formula (E2) is substituted for the compound represented by the above formula (E1). A copolymer (II) was obtained in the same manner as in Example 1 except that the compound represented by the above formula (E14) was used instead of the compound represented by the above formula (E7). The copolymer (II) had a weight average molecular weight (Mw) of 32300 and a molecular weight distribution index (Mw / Mn) of 2.15. The m / (m + n) value of the copolymer estimated from the results of ICP elemental analysis and ¹³ C-NMR measurement was 0.050. In copolymer (II), the value of x / n was 0.50, and the value of y / n was 0.50.

[Example 3] Synthesis of copolymer (III) A copolymer (III) was obtained in the same manner as in Example 1 except that the iridium complex (C8) was used instead of the mixture of the iridium complex (C2). It was. The weight average molecular weight (Mw) of the copolymer (III) was 37100, and the molecular weight distribution index (Mw / Mn) was 2.31. The m / (m + n) value of the copolymer estimated from the results of ICP elemental analysis and ¹³ C-NMR measurement was 0.040. In copolymer (III), the value of x / n was 0.40, and the value of y / n was 0.60.

[Example 4] Preparation of organic EL element and evaluation of light emission characteristics A substrate with ITO (manufactured by Nippon Electric Co., Ltd.) was used. This was a substrate in which two ITO (indium tin oxide) electrodes (anodes) having a width of 4 mm were formed in one stripe on one surface of a 25 mm square glass substrate.

  First, poly (3,4-ethylenedioxythiophene) / polystyrenesulfonic acid (manufactured by Bayer Co., Ltd., trade name “BYTRON P”) on the above-mentioned ITO-attached substrate under conditions of a rotation speed of 3500 rpm and a coating time of 40 seconds. Then, it was applied by spin coating. Then, it dried for 2 hours at 60 degreeC under pressure reduction with the vacuum dryer, and formed the anode buffer layer. The film thickness of the obtained anode buffer layer was about 50 nm. Next, 90 mg of copolymer (I) was dissolved in 2910 mg of toluene (special grade, manufactured by Wako Pure Chemical Industries, Ltd.), and this solution was filtered with a filter having a pore size of 0.2 μm to prepare a coating solution. Next, the coating solution was coated on the anode buffer layer by spin coating under the conditions of a rotation speed of 3000 rpm and a coating time of 30 seconds. After the application, it was dried at room temperature (25 ° C.) for 30 minutes to form a light emitting layer. The film thickness of the obtained light emitting layer was about 100 nm.

  Next, the substrate on which the light emitting layer was formed was placed in a vapor deposition apparatus. Subsequently, calcium and aluminum were co-evaporated at a weight ratio of 1:10, and two cathodes having a width of 3 mm were formed in a stripe shape so as to be orthogonal to the extending direction of the anode. The film thickness of the obtained cathode was about 50 nm.

  Finally, lead wires (wirings) were attached to the anode and the cathode in an argon atmosphere, and four organic EL elements measuring 4 mm in length and 3 mm in width were produced. A voltage was applied to the organic EL element to emit light using a programmable DC voltage / current source (TR6143, manufactured by Advantest Corporation). The emission luminance was measured using a luminance meter (BM-8, manufactured by Topcon Corporation).

The produced organic EL element showed red light emission.
The obtained red light had x = 0.68 and y = 0.33 in CIE chromaticity coordinates. The maximum light-emitting external quantum efficiency was 6.3%, and the maximum luminance was 11400 cd / m ² . In addition, when the initial luminance is 100 cd / m ² and the current value is kept constant, the light is continuously emitted and is forcedly deteriorated.
The time until the luminance was halved was 2200 hours.
[Example 5] Production of organic EL device and evaluation of light emission characteristics An organic EL device was produced in the same manner as in Example 4 except that copolymer (II) was used instead of copolymer (I). Measurement of emission color and the like was performed.

The produced organic EL element showed red light emission.
The resulting red light was x = 0.68 and y = 0.32 in CIE chromaticity coordinates. The maximum light-emitting external quantum efficiency was 5.7%, and the maximum luminance was 8900 cd / m ² . In addition, when the initial luminance was 100 cd / m ² and the current value was kept constant, the current was continuously emitted and the light was forcibly deteriorated, and the time until the luminance was reduced to half was 2100 hours.
[Example 6] Production of organic EL device and evaluation of light emission characteristics An organic EL device was produced in the same manner as in Example 4 except that copolymer (III) was used instead of copolymer (I). Measurement of emission color and the like was performed.

The produced organic EL element showed red light emission.
The obtained red light had x = 0.66 and y = 0.33 in CIE chromaticity coordinates. The maximum light emitting external quantum efficiency was 5.8%, and the maximum luminance was 9200 cd / m ² . In addition, when the initial luminance was 100 cd / m ² and the current value was kept constant, the current was continuously emitted and the light was forcibly deteriorated, and the time until the luminance was reduced to half was 2200 hours.

FIG. 1 is a cross-sectional view of an example of an organic EL element according to the present invention.

Explanation of symbols

1: Glass substrate 2: Anode 3: Hole transport layer 4: Light emitting layer 5: Electron transport layer 6: Cathode

Claims (8)

A polymer light-emitting material comprising a polymer containing a structural unit derived from an iridium complex represented by the following general formula (1).

(In the general formula (1), R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OH, —SX ¹ , —OCOX ² , —COOX ³ , —SiX ⁴ X ^5. X ^6, -NH _2, -N
HX ⁷ , —NX ⁸ X ⁹ , an alkoxy group having 1 to 10 carbon atoms, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or a halogen in which some or all of the hydrogen atoms are substituted with halogen atoms A substituted alkyl group, an aryl group having 6 to 21 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, or a halogen in which part or all of the hydrogen atoms thereof are substituted with halogen atoms A substituted aryl group, a halogen-substituted heteroaryl group or a halogen-substituted aralkyl group is represented. (Here, X ^{1 to} X ⁹ are each independently a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 21 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or Represents an aralkyl group having 7 to 21 carbon atoms.)
Q ¹ represents a carbon atom, a nitrogen atom or a sulfur atom, and Z ¹ forms a 5-membered or 6-membered aromatic ring or aromatic heterocycle together with carbon atoms C ¹ and C ² and Q ¹ . Represents an atomic group, the ring may have a substituent, and may form a condensed ring with another ring.
L represents a monovalent anionic bidentate ligand having a polymerizable functional group. ) In the above general formula (1), a 5-membered or 6-membered aromatic ring or aromatic heterocyclic ring formed from C ¹ , C ² , Q ¹ and Z ^1, or the aromatic ring or aromatic heterocyclic ring and other ring From the group consisting of benzene, naphthalene, phenanthrene, anthracene, pyridine, quinoline, isoquinoline, benzoxazole, benzothiazole, benzimidazole, benzotriazole, imidazole, pyrazole, oxazole, thiazole, triazole, benzopyrazole and triazine 2. The polymer light-emitting device according to claim 1, wherein a ring skeleton of a selected compound is used as a skeleton and may have a substituent similar to the group defined by R ^{1 to} R ^8. material. The polymer luminescent material according to claim 1, wherein the iridium complex is represented by any one of the following general formulas (2) to (8).

(In General Formula (2) to General Formula (8), R ^{1 to} R ³⁵ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OH, —SX ¹ , —OCOX ² , —COOX ^3. , —SiX ⁴ X ⁵ X ⁶ , —NH ₂ , —NHX ⁷ , —NX ⁸ X ⁹ , an alkoxy group having 1 to 10 carbon atoms, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or hydrogen thereof A halogen-substituted alkyl group in which some or all of the atoms are substituted with a halogen atom, an aryl group having 6 to 21 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, or hydrogen thereof some of the atoms or all represent a substituted halogen-substituted aryl group, halogen-substituted heteroaryl group or a halogen-substituted aralkyl group with a halogen atom. (the number of carbon atoms wherein, X ¹ to X ⁹ are each independently To 22 linear, cyclic or branched alkyl group, an aryl group of 6 to 21 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an aralkyl group having 7 to 21 carbon atoms.)
L represents a monovalent anionic bidentate ligand having a polymerizable functional group. ) The polymer light-emitting material according to claim 1, wherein L is a bidentate ligand represented by the following general formula (9) or (10).

(Wherein X ¹⁰ has the same meaning as R ¹ in the above formula (1), Y ¹ and Y ² are each independently
A substituent having a polymerizable functional group is represented. ) 2. The polymer further comprises a structural unit derived from at least one polymerizable compound selected from the group consisting of a hole transport polymerizable compound and an electron transport polymerizable compound. The polymer light-emitting material according to any one of -4.   In the organic electroluminescent element containing the organic polymer layer of 1 layer or 2 layers or more sandwiched between the anode and the cathode, at least 1 layer of the said organic polymer layer is high in any one of Claims 1-5. An organic electroluminescence device comprising a molecular light emitting material.   The image display apparatus using the organic electroluminescent element of Claim 6.   A surface-emitting light source using the organic electroluminescence element according to claim 6.

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