JP5043330B2 - Polymer light-emitting material, organic electroluminescence element, and display device - Google Patents

Description

  The present invention relates to a polymer light emitting material and an organic electroluminescence device. More specifically, the present invention has a high-purity green light emission, a polymer light-emitting material with 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, materials for use in organic electroluminescent elements (also referred to as “organic EL elements” in this specification) have been actively developed. 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 pyrazine ring as a ligand has been disclosed (see Patent Document 1).
In the present specification, “orthometalation” refers to the general formula (2) (see Patent Document 1) in which the aryl group represented by Ar is ortho to the bonding position of the substituent having a coordination atom. This is a reaction in which the C—H bond at the position generates a chelate ring containing a metal-carbon bond by an intramolecular reaction.

  According to Patent Document 1, an orthometalated iridium complex containing a derivative having a pyrazine ring as a ligand is described as being a compound that easily undergoes intersystem crossing to an excited triplet state and emits phosphorescence. Yes. However, although there is a description of the emission wavelength in this patent, there is not sufficient disclosure in terms of the lifetime of the element.

In general, when a light emitting layer is formed, a vacuum 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.
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 2005-314414 A

  An object of the present invention is to provide a polymer light emitting material from which high purity green 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 green 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 Formula (1), R < ¹ > -R < ⁴ > is respectively independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a C1-C10 alkoxy group, a C1-C22 linear, cyclic or A branched alkyl group or a halogen-substituted alkyl group in which a part or all of hydrogen atoms thereof are substituted with a halogen atom, an aryl group having 6 to 21 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or 7 to 21 carbon atoms Or a halogen-substituted aryl group, a halogen-substituted heteroaryl group or a halogen-substituted aralkyl group in which some or all of the hydrogen atoms are substituted with a halogen atom, Z ¹ is a 5-membered or 6-membered carbocyclic ring Or represents a group of atoms for completing a heterocyclic ring, and L represents a bidentate ligand of a monovalent anion having a polymerizable functional group.

[2] The polymer luminescent material as described in [1] above, wherein the iridium complex is represented by the following general formula (2) or (3).

(In formulas (2) and (3), R ^{1 to} R ¹¹ are each independently a hydrogen atom, a halogen atom,
A cyano group, a nitro group, 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-substituted alkyl in which some or all of hydrogen atoms thereof are substituted with halogen atoms Group, aryl group having 6 to 21 carbon atoms, heteroaryl group having 2 to 20 carbon atoms, or aralkyl group having 7 to 21 carbon atoms, or halogen-substituted aryl in which part or all of the hydrogen atoms thereof are substituted with halogen atoms A group, a halogen-substituted heteroaryl group or a halogen-substituted aralkyl group; L represents a monovalent anionic bidentate ligand having a polymerizable functional group. )

[3] At least one of R ^{1 to} R ⁷ in the above formula (2) and at least one of R ^{1 to} R ⁴ and R ^{7 to} R ^{11 in} the above formula (3) are each independently a fluorine atom or trifluoromethyl. The polymer light-emitting material according to [2] above, which is a group.

[4] The polymer light-emitting material according to [1], wherein the iridium complex is represented by the following general formula (4) or (5).

(In Formula (4) and (5), R < ¹ >, R < ² >, R < ⁴ > -R < ²³ > is respectively independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a C1-C10 alkoxy group, carbon number. 1 to 22 linear, cyclic or branched alkyl groups, or a halogen-substituted alkyl group in which part or all of the hydrogen atoms are substituted with a halogen atom, an aryl group having 6 to 21 carbon atoms, or 2 to 20 carbon atoms Or an arylalkyl group having 7 to 21 carbon atoms or a halogen-substituted aryl group, a halogen-substituted heteroaryl group or a halogen-substituted aralkyl group in which part or all of the hydrogen atoms are substituted with a halogen atom. Represents a monovalent anionic bidentate ligand having a polymerizable functional group.)

[5] R ¹ in at least one and the formula (5) ^{R 1, R 2, R 4} ~R 7, R 12 ~R 16 in the formula ^{(4), R 2, R} 4, R 7 ~R ^11. The polymer light-emitting material as described in [4] above, wherein at least one of R ^{17 to} R ²³ is independently a fluorine atom or a trifluoromethyl group.

[6] The polymer luminescence according to any one of [1] to [5], wherein L is a bidentate ligand represented by the following general formula (6) or (7): material.

(In the formula, X ¹ has the same meaning as R ¹ in the above formula (1), and Y ¹ and Y ² each independently represent a substituent having a polymerizable functional group.)

[7] The polymer further includes a structural unit derived from at least one polymerizable compound selected from the group consisting of a hole-transporting polymerizable compound and an electron-transporting polymerizable compound. The polymer light-emitting material according to any one of [1] to [6] above.

[8] In an 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 includes the above [1] to

[7] An organic electroluminescence device comprising the polymer light-emitting material according to any one of [7].

[9] An image display device using the organic electroluminescence element according to [8].

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

  According to the present invention, it is possible to provide a polymer light emitting material having high purity green light and having a long driving life. 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.
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) includes a derivative having a pyrazine ring as a ligand. A polymer light emitting material using the complex emits green 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 ²³ , Z ¹ , L ¹ , X ¹ , Y ¹ , Y ² ) described in the above formulas (1) to (7) will be specifically described below.
In the formula, R ^{1 to} R ^{23 in the} derivative having a pyrazine ring are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 10 carbon atoms, a linear chain having 1 to 22 carbon atoms, A cyclic or branched alkyl group, or a halogen-substituted alkyl group in which part or all of hydrogen atoms thereof are substituted with a halogen atom, an aryl group having 6 to 21 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or 7 carbon atoms Represents a halogen-substituted aryl group, a halogen-substituted heteroaryl group or a halogen-substituted aralkyl group in which -21 aralkyl groups or a part or all of hydrogen atoms thereof are substituted with halogen atoms.

Shows an example of the substituents represented by R ¹ to R ²³ in the following, the invention is not limited to the following.
Examples of R ^{1 to} R ²³ include a halogen atom such as a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a cyano group, a nitro group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. , Isobutoxy group, t-butoxy group, hexyloxy group, 2-ethylhexyloxy group, decyloxy group, methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, tert-butyl group, cyclobutyl Group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, cycloheptyl group, octyl group, nonyl group, decyl group, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group , Benzyl group, phenethyl group, methylbenzyl group, dipheny Methyl group, styryl group, cinnamyl group, biphenyl residue, 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, triazine residue, quinoline residue, quinoxaline residue, or halogen-substituted products in which these are substituted with fluorine atom, chlorine atom, bromine atom, iodine atom, etc. it can.

In each of the complexes represented by the above formulas (1) to (5), at least one of R ^{1 to} R ²³
From the viewpoint of being effective for shortening the emission wavelength, a halogen atom or a halogen-substituted alkyl group is preferable. Among these, a fluorine atom, a chlorine atom or a trifluoromethyl group is more preferable, a fluorine atom or a trifluoromethyl group is more preferable, and a fluorine atom is most preferable.

The complexes represented by the above (2) to (5) are more preferable, and in the above formula (2), it is preferable that at least one of R ^{1 to} R ⁷ is independently a fluorine atom or a trifluoromethyl group, In the above formula (3), it is preferable that at least one of R ^{1 to} R ⁴ and R ^{7 to} R ¹¹ is independently a fluorine atom or a trifluoromethyl group.

In the above formula (4), at least one of R ¹ , R ² , R ^{4 to} R ⁷ and R ^{12 to} R ¹⁶ is preferably independently a fluorine atom or a trifluoromethyl group, and the above formula (5) In the above, it is preferable that at least one of R ¹ , R ² , R ⁴ , R ^{7 to} R ¹¹ , and R ^{17 to} R ²³ is independently a fluorine atom or a trifluoromethyl group.

In each of the complexes represented by the above formulas (1) to (5), at least one of R ^{1 to} R ²³
When one has any of the above substituents, the other R ^{1 to} R ²³ are often hydrogen atoms, but may be other substituents.

As the 5-membered ring and 6-membered ring formed by Z ¹ , an aromatic or heteroaromatic ring is preferable. For example, an imidazole ring, a thiazole ring, an oxazole ring, a pyrrole ring, an oxadiazole ring, a thiadiazole ring, a pyrazole ring, Examples include 1,2,3-triazole ring, 1,2,4-triazole ring, selenazole ring, furan ring, thiophene ring, benzene ring, naphthyl ring, pyridine ring, pyrimidine ring, pyrazine ring and pyridazine ring. Of these, thiazole ring, pyrrole ring, benzene ring, naphthyl ring, and pyridine ring are preferable.

  The iridium complex represented by the following general formula (8) or (9) is more preferable from the viewpoint of the ease of synthesis, the lifetime of the produced device, and the color purity.

(In the formula, at least one of Z ^{2 to} Z ⁵ independently represents —F, —CF ₃ , —OCF _3, or —CN. Z ⁶ represents —H or

The expressed, wherein, Z ⁷ to Z ¹⁰ are, -H independently, -F, -CF _3, represents a -OCF ₃ or -CN. )

(In the formula, at least one of Z ¹¹ and Z ¹² independently represents —F, —CF ₃ or —OCF _3. Z ¹³ represents —H or

Wherein Z ¹⁴ and Z ¹⁵ are each independently —H, —F, —CF ₃ or —OC
F ₃ is represented. )
In the above formulas (1) to (9), 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 above formula (6) or (7).
In the formula, X ¹ has the same meaning as R ¹ in the above formula (1), and Y ¹ and Y ² each independently represent a substituent having a polymerizable functional group.

  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.

  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.

  As the iridium complex represented by any one of the above formulas (1) to (9), the following iridium complexes are most preferable.

  The iridium complex represented by any of the above formulas (1) to (9) is produced, for example, as follows. First, a derivative having a desired pyrazine ring is obtained by the method described in JP-A-2005-314414.

  Next, a derivative having a pyrazine ring is reacted with an iridium compound (0.5 equivalent) such as iridium chloride 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 any one of the above formulas (1) to (9) can be obtained.

  Examples of the synthesis method of the iridium dinuclear complex include the method described in Inorganic Chemistry, 2001, 40, 1704. Below, the typical example of the iridium binuclear complex used by this invention is shown.

  The weight average molecular weight of the polymer containing the structural unit derived from the iridium complex represented by any of the above formulas (1) to (9) is preferably 1,000 to 2,000,000, It is more preferable that it is 000-1,000,000. 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 in} formula (6), and the preferred range is also the same.
More specifically, the polymerizable compound more preferably has the functional group as a substituent represented by the formulas (A1) to (A12).

  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), compounds in which the substituents represented by the above formula (A1) are replaced with the substituents represented by the above formulas (A2) to (A12) are also preferably used. However, since a functional group can be easily introduced into the polymerizable compound, compounds having substituents represented by the above formulas (A1) and (A5) are 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 formula (C2), (C4), or (C7) 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, and 6) a single layer of the light emitting material. 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.

  Further, a hole block layer may be provided adjacent to the cathode side of the light emitting layer for the purpose of suppressing holes from passing through the light emitting layer and efficiently recombining 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)

  To a mixture of 2.0 g (6.5 mmol) of compound (a) and 1.1 g (3.1 mmol) of iridium (III) chloride trihydrate, 30 ml of 2-ethoxyethanol and 10 ml of water were added, and the mixture was heated to reflux for 12 hours. did. The produced precipitate was washed with cold methanol and dried under reduced pressure to obtain 2.2 g (1.3 mmol) of the binuclear complex (D2). To 1.0 g (0.60 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. Purification by silica gel column chromatography gave 0.58 g (0.57 mmol) of an iridium complex (C2).

Identification data of the compound (C2) are as follows.
Calcd _{(C 45 H 29 F 8 IrN} 4 O 2) C, 54.49; H, 2.88%; N
, 5.53. Measurement C, 54.10; H, 3.03%; N, 5.68.
Mass spectrometry (FAB +): 1014 (M ⁺ ).
[Synthesis Example 2] Synthesis of iridium complex (C4)

To a mixture of 2.0 g (4.0 mmol) of compound (c) and 0.7 g (2.0 mmol) of iridium (III) chloride trihydrate, 30 ml of 2-ethoxyethanol and 10 ml of water were added, and heated under reflux for 12 hours. did. The generated brown precipitate was washed with cold methanol and dried under reduced pressure to obtain 1.7 g (0.69 mmol) of the binuclear complex (D4). Next, 50 ml of tetrahydrofuran was added to 1.7 g (0.69 mmol) of the obtained complex (D4), and 0.50 g (2.2 mmol) of compound (d) (synthesized according to the method described in JP-A No. 2003-113246). Then, 0.30 g (2.2 mmol) of potassium carbonate was added, and the mixture was heated to reflux for 48 hours. The resulting reaction solution was concentrated, and 0.6 g (2.1 mmol) of tetra-n-butylammonium fluoride was added while cooling the reaction solution with ice, followed by stirring at room temperature for 3 hours. After the solvent was distilled off under reduced pressure, 0.90 g (0.69 mmol) of an iridium complex (e) was obtained by purification by silica gel column chromatography. The obtained iridium complex (e) was dissolved in 50 ml of dichloromethane, and 0.10 g (1.0 mmol) of triethylamine and 0.10 g (1.0 mmol) of methacryloyl chloride were sequentially added dropwise with ice cooling, and then at room temperature for 3 hours. Stir. The resulting precipitate was filtered off, the solvent was distilled off from the filtrate under reduced pressure, and the product was produced by silica gel column chromatography to obtain 0.90 g (0.65 mmol) of an iridium complex (C4).

The identification data of the compound (C4) are as follows.
Calcd _{(C 49 H 25 F 24 IrN} 4 O 4) C, 42.59; H, 1.82%; N, 4.05. Measurement C, 42.88; H, 1.96%; N, 3.74.
Mass spectrometry (FAB +): 1382 (M ⁺ ).
[Synthesis Example 3] Synthesis of iridium complex (C7)

  30 ml of 2-ethoxyethanol and 10 ml of water were added to a mixture of 2.0 g (5.6 mmol) of compound (f) and 1.0 g (2.8 mmol) of iridium (III) chloride trihydrate, and the mixture was heated under reflux for 12 hours. did. The produced brown precipitate was washed with cold methanol and dried under reduced pressure to obtain 2.1 g (1.1 mmol) of the binuclear complex (D7). To 1.0 g (0.53 mmol) of the obtained complex (D7), 20 ml of N, N-dimethylformamide was added, and compound (g) (synthesized according to the method described in JP-A-2003-206320) 0.30 g (2 0.0 mmol) and 0.30 g (2.2 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, 0.80 g (0.76 mmol) of an iridium complex (C7) was obtained.

The identification data of the compound (C7) are as follows.
Calcd _{(C 44 H 16 F 8 IrN} 9 O 2) C, 50.48; H, 1.54%; N
, 12.04. Measurement C, 50.19; H, 1.67%; N, 11.83.
Mass spectrometry (FAB +): 1047 (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 56500, and the molecular weight distribution index (Mw / Mn) was 2.05. The m / (m + n) value of the copolymer estimated from the results of ICP elemental analysis and ¹³ C-NMR measurement was 0.029. In copolymer (I), the value of x / n was 0.41, and the value of y / n was 0.59.

[Example 2] Synthesis of copolymer (II) An iridium complex (C4) instead of a mixture of iridium complex (C2) is represented by the above formula (E2) instead of 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). It was. The copolymer (II) had a weight average molecular weight (Mw) of 58700 and a molecular weight distribution index (Mw / Mn) of 1.99. The m / (m + n) value of the copolymer estimated from the results of ICP elemental analysis and ¹³ C-NMR measurement was 0.030. In copolymer (II), the value of x / n was 0.49, and the value of y / n was 0.51.

[Example 3] Synthesis of copolymer (III) A copolymer (III) was obtained in the same manner as in Example 1 except that the iridium complex (C7) was used instead of the mixture of the iridium complex (C2). It was. The copolymer (III) had a weight average molecular weight (Mw) of 50200 and a molecular weight distribution index (Mw / Mn) of 2.01. The m / (m + n) value of the copolymer estimated from the results of ICP elemental analysis and ¹³ C-NMR measurement was 0.029. 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. Next, calcium and aluminum were co-evaporated at a weight ratio of 1:10, and the width was 3 m so as to be orthogonal to the extending direction of the anode.
Two cathodes of m were formed in stripes. 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 green light emission.
The resulting green light was x = 0.31 and y = 0.64 in CIE chromaticity coordinates. The maximum light emitting external quantum efficiency was 6.5%, and the maximum luminance was 23000 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.
It was 35000 hours until the brightness was halved.

[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 green light emission.
The resulting yellow light was x = 0.27 and y = 0.63 in CIE chromaticity coordinates. The maximum light emission external quantum efficiency was 5.9%, and the maximum luminance was 27000 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.
It was 2900 hours until the brightness was halved.

[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 green light emission.
The resulting red light was x = 0.26 and y = 0.62 in CIE chromaticity coordinates. The maximum light emitting external quantum efficiency was 6.0%, and the maximum luminance was 21000 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.
It was 3000 hours until the luminance was halved.

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 (4) .

(In Formula (4), R ¹ and R ² represent a hydrogen atom, R ^{4 to} R ⁷ and R ^{12 to} R ¹⁶ each independently represent a hydrogen atom, a fluorine atom, a cyano group, or a trifluoromethyl group, At least one of R ^{4 to} R ⁷ and R ^{12 to} R ¹⁶ represents a fluorine atom or a trifluoromethyl group, L is a bidentate of a monovalent anion represented by the following general formula (6) or (7) Represents a quantifier.)

(In the formula, X ¹ represents a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, and Y ¹ and Y ² are each independently a substituent represented by the following formula (A1) to (A12). Represents any of the groups.)

The polymer luminescent material according to claim 1, wherein the iridium complex is one or more selected from the group consisting of iridium complexes represented by the following formulas (C1) to (C3) and (C7). .

The polymer luminescent material according to claim 2, wherein the iridium complex is at least one selected from the group consisting of iridium complexes represented by formulas (C2) and (C7). A polymer light-emitting material comprising a polymer containing a structural unit derived from an iridium complex represented by the following formula (C4).

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 to 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 one layer of the organic polymer layer is a high layer according to any one of claims 1 to 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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