JP2003171391A - Polymerizable compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polymerizable compound, and a polymeric light-emitting material obtained from the compound, capable of obtaining an organic light- emitting element therefrom that has a high luminous efficiency, can be formed into a large area and can be mass-produced. <P>SOLUTION: The polymerizable compound comprises a mononuclear iridium complex having two ligands derived from phenylpyridine and a bidentate ligand, wherein the phenylpyridine has a polymerizable functional group, such as a carbon-carbon double bond, and the bidentate ligand is derived from a monovalent anion. The polymeric light-emitting material is obtained from the compound. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flat display panel and an organic light emitting device (OL) for a backlight used in the flat display panel.
The present invention relates to a polymerizable compound that is a precursor of a polymeric light emitting material used for ED).

[0002]

2. Description of the Related Art Organic light emitting devices were manufactured by Kodak Corporation in C.I. W. Tang et al. Showed high-intensity luminescence (Appl. Phys. Lett., 51, 913.
(Page, 1987), the development of materials and the improvement of the device structure have progressed rapidly, and the practical application has recently started with displays for car audio systems and mobile phones. This organic EL
In order to further expand the applications of the above, development of materials for improving luminous efficiency and durability, development of full-color display, etc. are currently being actively conducted. Especially for medium and large size panels,
Alternatively, when considering expansion to lighting applications, it is necessary to establish higher mass production methods suitable for larger areas and higher brightness by improving luminous efficiency.

First, regarding the luminous efficiency, it is the light emission from the excited singlet state, that is, the fluorescence that is used in the present light emitting materials. Monthly display, 1998, 10
According to the monthly issue “Organic EL Display”, page 58,
Since the generation ratio of excitons in the excited singlet state and the excited triplet state in electric excitation is 1: 3, the upper limit of the internal quantum efficiency of light emission in organic EL is 25%.

On the other hand, M. A. Baldo et al. Obtained an external quantum efficiency of 7.5% by using an iridium complex that emits phosphorescence from an excited triplet state, which corresponds to an internal quantum efficiency of 37.5% assuming an external extraction efficiency of 20%. 25%, which is the upper limit when dyes are used
It is possible to exceed the value of (App
l. Phys. Lett. , 75, p. 4, 1999
Year, WO00 / 70655).

Next, as a mass production method of panels, a vacuum vapor deposition method has been conventionally used. However, this method has problems such as the need for vacuum equipment and the difficulty of forming an organic thin film with a uniform thickness as the area increases. Is not a suitable method for.

On the other hand, as a method for easily increasing the area, a manufacturing method using a polymer light emitting material, that is, an ink jet method or a printing method has been developed. In particular, the printing method is capable of continuously forming a long film and is excellent in large area and mass productivity.

As described above, in order to obtain an organic light emitting device having a high luminous efficiency and a large area, a phosphorescent polymer material is required. As such a phosphorescent polymer material, there is one in which a ruthenium complex is incorporated into the main chain or side chain of the polymer (Ng, PK et al., Polymer Prepr).
ints., 40 (2), 1212 (1999)). However, since these are ionic compounds, electrochemiluminescence due to the redox reaction at the electrodes occurs when a voltage is applied. This has a very slow response speed on the order of minutes and cannot be used as a normal display panel.

Although not a polymer material in a strict sense, there is a material obtained by mixing poly (N-vinylcarbazole) with an iridium complex which is a low molecular weight compound having phosphorescence (PJ Djurovich et al., Polymer Preprints,
41 (1), 770 (2000)). However, this is inferior in thermal stability to a homogeneous polymer material and may cause phase separation or segregation.

A compound (pendant type polymer complex) in which a phosphorescent metal complex is incorporated into the side chain of a polymer is also conceivable. Even in this case, the phosphorescent complex in the polymer matrix when formed into a film. Since the degree of freedom of
It may be disadvantageous in terms of thermal stability, life, brightness, luminous efficiency, etc. of the light emitting element.

[0010]

As described above, a practical polymer-based phosphorescent material that is required for mass-producing organic light-emitting devices having excellent stability, high luminous efficiency, and large area. Does not exist yet. Therefore, the present invention solves the problems of the prior art as described above, and provides a polymer light-emitting material for obtaining an organic light-emitting device capable of increasing the area with high luminous efficiency and being mass producible. Is an issue.

[0011]

As a result of various studies to solve the above problems, the present inventors succeeded in obtaining a crosslinkable polymerizable compound having an iridium complex portion, and completed the present invention. It was

That is, the present invention provides the following [1] to [3]
[0], a cross-linking polymerizable compound which is a novel compound, an intermediate which is a novel compound necessary for the synthesis of these cross-linking polymerizable compounds, and a method for producing these cross-linking polymerizable compounds are provided.

[1] A polymerizable compound represented by the formula (1).

[Chemical 14] [In the formula, L is a monovalent anionic bidentate ligand, X is a substituent having a polymerizable functional group, and R _{1 to} R ₇ are each independently a hydrogen atom, a halogen atom, a nitro group, an amino group, or a sulfone. It represents an acid group, a sulfonate group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]

[2] A polymerizable compound represented by the formula (2).

[Chemical 15] [In the formula, A _{1 to} A ₃ are each independently a hydrogen atom, a halogen atom or an organic group having 1 to 20 carbon atoms which may have a hetero atom, X is a substituent having a polymerizable functional group, R ₁ to R _7's each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. [3] The polymerizable compound according to [1] or [2], wherein the polymerizable functional group of X in the formula (1) or (2) is a group having a carbon-carbon double bond. . [4] The X in the above formula (1) or (2) is any of a methacryloyloxy group, a methacryloyloxyethylcarbamoyloxy group, and a vinylbenzyloxy group, [1] or [2] Polymerizable compound.

[5] A polymerizable compound represented by the formula (3).

[Chemical 16]

[6] A polymerizable compound represented by the formula (4).

[Chemical 17]

[7] A polymerizable compound represented by the formula (5).

[Chemical 18]

[8] After reacting the iridium binuclear complex represented by the formula (6) with the monovalent anionic bidentate ligand L, the reaction product, a polymerizable functional group and the formula (6) 1. A method for producing a polymerizable compound containing a mononuclear iridium complex moiety, which comprises reacting the substituent Y having a reactive functional group of 1) with a compound having a functional group capable of being bonded together.

[Chemical 19] [In the formula, Y represents a substituent having a reactive functional group, and R ₁
To R ₇ each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]

[9] The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to [8], wherein Y in the formula (6) is a group having active hydrogen. [10] The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to [8], wherein Y in the formula (6) is a hydroxyl group. [11] An acid chloride or a polymerizable functional compound in which a compound having a functional group capable of reacting and binding with a substituent Y having a polymerizable functional group and a reactive functional group derived from the formula (6) has a polymerizable functional group. The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to [10], which is an alkyl halide compound having a group. [12] The compound having a polymerizable functional group is an isocyanate compound having a polymerizable functional group [9] or [1
[0]] A method for producing a polymerizable compound containing a mononuclear iridium complex moiety.

[13] A method for producing a polymerizable compound containing a mononuclear iridium complex, which comprises reacting the iridium binuclear complex represented by the formula (7) with a monovalent anionic bidentate ligand L. .

[Chemical 20] [In the formula, X is a substituent having a polymerizable functional group, R _{1 to} R ₇ each independently have a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a hetero atom. Optionally represents an organic group having 1 to 20 carbon atoms. ]

[14] Polymerization containing a mononuclear iridium complex moiety according to [13], wherein X in the formula (7) is one of a methacryloyloxy group, a methacryloyloxyethylcarbamoyloxy group and a vinylbenzyloxy group. Of producing a volatile compound.

[15] An iridium binuclear complex represented by the formula (6).

[Chemical 21] [In the formula, Y represents a substituent having a reactive functional group, and R ₁
To R ₇ each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. [16] Y in the formula (6) is a hydroxyl group [1
[5] The iridium binuclear complex according to [5].

[17] An iridium binuclear complex represented by the formula (8).

[Chemical formula 22]

[18] A compound represented by the formula (9).

[Chemical formula 23] [In the formula, L is a monovalent anionic bidentate ligand, Y is a substituent having a reactive functional group, R _{1 to} R ₇ are each independently a hydrogen atom, a halogen atom, a nitro group, an amino group, or a sulfone. It represents an acid group, a sulfonate group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]

[19] A compound represented by the formula (10).

[Chemical formula 24] [In the formula, A _{1 to} A ₃ are each independently an organic group having 1 to 20 carbon atoms which may have a hydrogen atom, a halogen atom or a hetero atom, Y is a substituent having a reactive functional group, R ₁ to R _7's each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. [20] The compound according to [18] or [19], wherein Y in the formula (9) or (10) is a hydroxyl group.

[21] A compound represented by the formula (11).

[Chemical 25]

[22] An iridium binuclear complex represented by the formula (7).

[Chemical formula 26] [In the formula, X is a substituent having a polymerizable functional group, R _{1 to} R ₇ each independently have a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a hetero atom. Optionally represents an organic group having 1 to 20 carbon atoms. [23] The iridium binuclear complex according to [22], wherein X in the formula (7) is any one of a methacryloyloxy group, a methacryloyloxyethylcarbamoyloxy group, and a vinylbenzyloxy group.

[24] A composition containing the polymerizable compound according to any one of [1] to [7]. [25] A polymer of the polymerizable compound according to any one of [1] to [7]. [26] A polymer obtained by polymerizing a composition containing at least one polymerizable compound according to any one of [1] to [7].

[27] A luminescent material containing the polymerizable compound according to any one of [1] to [7]. [28] A luminescent material obtained by polymerizing the polymerizable compound according to any one of [1] to [7]. [29] A luminescent material obtained by polymerizing a composition containing at least one polymerizable compound according to any one of [1] to [7]. [30] An organic light emitting device using the light emitting material according to any one of [27] to [29].

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below.

The present invention provides a polymerizable compound represented by the formula (1).

[Chemical 27] [In the formula, L is a monovalent anionic bidentate ligand, X is a substituent having a polymerizable functional group, and R _{1 to} R ₇ are each independently a hydrogen atom, a halogen atom, a nitro group, an amino group, or a sulfone. It represents an acid group, a sulfonate group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]

The monovalent anionic bidentate ligand represented by L in the formula (1) is a nonionic coordination site such as a pyridine ring, a carbonyl group or an imine group in the molecule, a phenyl group, A compound having a site capable of desorbing one hydrogen ion such as a hydroxyl group or a carboxyl group to form a monovalent anionic coordination site, or one hydrogen ion such as β-diketone.
It is a compound in which one hydrogen ion is eliminated from a compound having a structure in which a conjugated structure containing two coordination sites can be monovalent anionic as a whole by elimination. Especially, in these compounds, two coordination sites have 1
A compound capable of forming a 5-membered ring or 6-membered ring structure including an iridium atom when coordinated to two iridium atoms is preferable. Examples thereof include 2-phenylpyridine,
A compound in which one hydrogen ion is eliminated from β-diketone, picolinic acid, N-alkylsalicylimine, 8-hydroxyquinoline and their derivatives to become a monovalent anion can be mentioned. Among these bidentate ligands, a compound in which one hydrogen ion is desorbed from β-diketone, picolinic acid or N-alkylsalicylimine to form a monovalent anion is preferable from the viewpoint of light emitting properties.

The polymerizable functional group in the substituent having a polymerizable functional group represented by X in the formula (1) is radical polymerizable, cationic polymerizable, anionic polymerizable, addition polymerizable,
It may be either condensation-polymerizable, but a radical-polymerizable functional group is preferred. The polymerizable functional group is carbon-
A group having a carbon double bond is preferable, and an alkenoyloxy group such as a vinyl group, an allyl group, an alkenyl group, an acryloyloxy group and a methacryloyloxy group, and a urethane (meth) such as a methacryloyloxyethyl carbamate group.
Examples thereof include a substituent having an acryloyloxy group, a styryl group and its derivative, a vinyl acid group and its derivative, and the like. Among these polymerizable functional groups, an acryloyloxy group, a methacryloyloxy group, a urethane (meth) acryloyloxy group, and a styryl group are preferable from the viewpoint of the polymerizability. Examples of the substituent having a polymerizable functional group include a methacryloyloxy group, a methacryloyloxyethylcarbamoyloxy group, and a vinylbenzyloxy group, but the substituent is not limited thereto. The position at which these substituents are bonded may be any of the 3-position, 4-position, 5-position and 6-position of the phenyl group of the phenylpyridine ligand.

The "organic group having 1 to 20 carbon atoms which may have a hetero atom" in each formula of the present invention is not limited as long as the gist of the present invention is not impaired, but preferably 1 to 10 carbon atoms.
20 alkyl groups, alkoxy groups, alkoxyalkyl groups, allyl groups, allyloxy groups, aralkyl groups or aralkyloxy groups, or halogen-substituted products thereof.

R _{1 to} R ₇ in the formula (1) are hydrogen atom, halogen atom, nitro group, amino group, sulfonic acid group, sulfonic acid ester group such as methyl sulfonate, methyl, ethyl, propyl, isopropyl and butyl. , Alkyl groups such as isobutyl, tert-butyl, amyl and hexyl, and alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy and tert-butoxy, aralkyl groups, and organic groups such as acetoxy group and propoxycarbonyl group. A group can be mentioned.
Further, these organic groups may further have a substituent such as a halogen atom, a nitro group or an amino group. Among these, a hydrogen atom, a halogen atom and an alkyl group having 1 to 20 carbon atoms are preferable. In the formula (1), R _{1 to} R ₇ bonded to the two phenylpyridine skeletons are the same, but the two phenylpyridine skeletons may be different.

Among the compounds represented by the formula (1), a compound in which the monovalent anionic bidentate ligand represented by L is a compound in which one hydrogen ion is eliminated from β-diketone is represented by the formula ( 2).

[Chemical 28] [In the formula, A _{1 to} A ₃ are each independently a hydrogen atom, a halogen atom or an organic group having 1 to 20 carbon atoms which may have a hetero atom, X is a substituent having a polymerizable functional group, R ₁ to R _7's each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]

As A _{1 to} A ₃ in the formula (2), a hydrogen atom, a halogen atom, an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl and hexyl, methoxy, ethoxy, Examples thereof include alkoxy groups such as propoxy, isobutoxy and tert-butoxy, aralkyl groups, and organic groups such as acetoxy groups and ester groups such as propoxycarbonyl groups. Moreover, these organic groups may further have a substituent such as a halogen atom.

In the formula (2), the substituent having a polymerizable functional group represented by X and R _{1 to} R ₇ have the same meanings as in the case of the formula (1).

Next, examples of the method for synthesizing the polymerizable compound according to the present invention will be given below, but the present invention is not limited thereto.

The first synthetic method is to prepare a dinuclear complex of iridium having a reactive substituent represented by the formula (6) and a compound capable of desorbing one hydrogen ion to form a monovalent anionic bidentate ligand. By reacting, a mononuclear iridium complex having a reactive substituent is obtained as an intermediate, and by reacting the reactive substituent of this intermediate with a compound having a polymerizable substituent, polymerization containing a mononuclear iridium complex portion. Is a method of obtaining a volatile compound.

[Chemical 29] [In the formula, Y represents a substituent having a reactive functional group, and R ₁
To R ₇ each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ]

The iridium binuclear complex of the formula (6) can be prepared by a known method (S. Lamansky et al., Inorganic Chemistry, 40,
1704 (2001)).

Y in the formula (6) is a substituent having a reactive functional group, and as the functional group, a hydroxyl group, a mercapto group,
Examples thereof include an amino group and a carboxyl group, but the present invention is not limited thereto. The substituent Y having a reactive functional group may be the above-mentioned functional group itself or a substituent containing a functional group such as a hydroxymethyl group. Moreover, the reactive functional group of Y may be protected by a protecting group. In this case, the reaction is carried out while being protected by a protecting group to obtain an iridium mononuclear complex having a monovalent anionic bidentate ligand L, and then deprotection is carried to provide a substituent Y having a reactive functional group. The iridium complex is obtained as an intermediate. Then, by reacting with a compound having a reactive functional group of this intermediate and a polymerizable functional group, a polymerizable compound containing a mononuclear iridium complex portion is obtained. still,
As the functional groups of these reactive substituents, the above-mentioned polymerizable substituents are excluded.

R _{1 to} R _{7 in the} formula (6) mean the same as in the case of the formula (1). Further, as in the case of formula (1), R bonded to the four phenylpyridine skeletons of formula (6)
_{1 to} R ₇ may be different in each phenylpyridine skeleton.

As compounds capable of eliminating one hydrogen ion to form a monovalent anionic bidentate ligand, 2-phenylpyridine, β-diketone, picolinic acid, N-alkylsalicylimine, 8-hydroxyquinoline and those Examples thereof include, but are not limited to.

Substituent Y having a reactive functional group of formula (6)
Iridium binuclear complex having a hydrogen atom and one hydrogen ion
And a compound that can become a monovalent anionic bidentate ligand
And a substituent Y having a reactive functional group.
Compounds with polymerizable functional groups that react with nuclear iridium complexes
The compound has a reactive functional group of the formula (6) in addition to the polymerizable group.
Must have a functional group that reacts with the substituent Y
It Also, R in the formula (6) ₁~ R₇Is the mononuclear iridium
Reacts with a compound having a polymerizable functional group that reacts with the complex
It is necessary to select a group that does not exist.

Examples of the compound having a polymerizable functional group which reacts with the above intermediate include a polymerizable acid chloride, a polymerizable alkyl halide and a polymerizable isocyanate, but are not limited thereto. . The polymerizable functional group in these compounds may be any of radical polymerizable, cationic polymerizable, anionic polymerizable, addition polymerizable, and condensation polymerizable, but a radical polymerizable functional group is preferable. As the polymerizable functional group, a group having a carbon-carbon double bond is preferable, and urethane such as vinyl group, allyl group, alkenyl group, acryloyloxy group and methacryloyloxy group, and alkenoyloxy group and methacryloyloxyethyl carbamate group are used. Examples thereof include those having a (meth) acryloyloxy group, a styryl group and its derivative, a vinyl acid group and its derivative. Among these polymerizable functional groups, an acryloyloxy group, a methacryloyloxy group, a urethane (meth) acryloyloxy group, and a styryl group are preferable from the viewpoint of the polymerizability. Specifically, examples of the polymerizable acid chloride include acrylic acid chloride and methacrylic acid chloride, examples of the polymerizable alkyl halide include vinylbenzyl chloride, and examples of the polymerizable isocyanate include methacryloyl isocyanate and methacryloyloxyethyl isocyanate. Etc.

The second method for synthesizing a polymerizable compound according to the present invention is a monovalent anionic bidentate in which one hydrogen ion is desorbed from an iridium binuclear complex having a polymerizable functional group represented by the above formula (7). It is a method of directly obtaining a polymerizable compound containing a mononuclear iridium complex portion by reacting a compound capable of forming a ligand.

[0048]

[Chemical 30] [In the formula, X is a substituent having a polymerizable functional group, R _{1 to} R ₇ each independently have a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a hetero atom. Optionally represents an organic group having 1 to 20 carbon atoms. ]

The substituent having a polymerizable functional group represented by X in formula (7) means the same as in formula (1). In addition, R _{1 to} R ₇ are the same as in formula (6).

As compounds capable of eliminating one hydrogen ion to form a monovalent anionic bidentate ligand, 2-phenylpyridine, β-diketone, picolinic acid, N-alkylsalicylimine, 8-hydroxyquinoline and those Examples thereof include, but are not limited to.

The crosslinkable polymerizable compound according to the present invention is 2,2 '.
-By using a thermal polymerization initiator such as azobis (isobutyronitrile) (AIBN) or benzoyl peroxide, or an ultraviolet polymerization initiator such as benzophenone, polymerization can be easily carried out, and a polymer containing an iridium complex portion can be obtained. Can be provided. The polymer is a homopolymer of one kind of the polymerizable compound of the present invention, a copolymer of two or more kinds of the polymerizable compound of the present invention, and one kind of the polymerizable compound of the present invention. It may be a copolymer of the above and one or more kinds of polymerizable compounds other than the polymerizable compound of the present invention. Here, as the polymerizable compound other than the polymerizable compound of the present invention, a hole-transporting compound such as vinylcarbazole, an electron-transporting compound such as an oxadiazole derivative or a triazole derivative having a polymerizable functional group, methyl acrylate, Examples thereof include (meth) acrylic acid alkyl esters such as methyl methacrylate, and compounds having no carrier transporting property such as styrene and derivatives thereof, but the compounds are not limited thereto.

Since the homopolymer of the crosslinkable polymerizable compound according to the present invention has a crosslinked structure, it is generally difficult to form the crosslinked polymer itself into a film.
When the cross-linking polymerizable compound of the present invention is homopolymerized by the solution polymerization method, the cross-linked polymer is precipitated as an insoluble matter. Therefore,
In general, it is dissolved in a solvent or other liquid monomer, and a film is formed by various printing methods such as a spin coating method, a dip coating method, an inkjet printing method, a screen printing method and a microgravure method, and then polymerized by the above method. Then, a film-like crosslinked polymer can be obtained. However, the cross-linking polymerizable compound according to the present invention can be obtained as a solvent-soluble polymer by copolymerizing with a large amount of other monofunctional monomer, and can be applied in a solution state onto an organic light-emitting device substrate or the like. You can However, in this case, it is necessary to use the ratio of the monofunctional monomer in a large excess relative to the crosslinking polymerizable compound according to the present invention.

FIG. 1 is a sectional view showing an example of the constitution of the organic light emitting device of the present invention, in which a hole transport layer, a light emitting layer and an electron transport layer are sequentially provided between an anode and a cathode provided on a transparent substrate. is there. Further, the structure of the organic light emitting device of the present invention is not limited to the example of FIG. 1, and any one of 1) hole transport layer / light emitting layer and 2) light emitting layer / electron transport layer may be sequentially provided between the anode and the cathode. It may be provided, and further, 3) a layer containing a hole transporting material, a light emitting material and an electron transporting material, 4) a layer containing a hole transporting material and a light emitting material, 5) a layer containing a light emitting material and an electron transporting material, 6). It is also possible to provide only one layer of the single layer of the light emitting material. Further, the light emitting layer shown in FIG. 1 is one layer, but two or more layers may be laminated.

When the polymerizable compound of the present invention is formed as a light emitting layer of an organic light emitting device, the polymerizable compound of the present invention may be coated on the lower layer and then polymerized, or a prepolymerized polymer is applied (coating). ) May be. For application,
It is also possible to apply the product dissolved in a suitable solvent and then dry the solvent.

The light emitting layer of the organic light emitting device of the present invention is a layer containing the polymerizable compound of the present invention and / or its polymer as a light emitting material, but other light emitting substances, hole transporting substances, electron transporting substances and the like are included. It may be.

In the organic light emitting device according to the present invention, the hole transport layer and the electron transport layer are formed on both sides or one side of the light emitting layer, whereby the emission efficiency and / or the durability can be further improved.

The hole transport material forming the hole transport layer is 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-M
Triphenylamine derivatives such as TDATA (4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine), known holes such as polyvinylcarbazole, poly (3,4-ethylenedioxythiophene) Transport materials can be used, but are not limited to these. These hole transporting materials may be used alone or may be mixed or laminated with different hole transporting materials. The thickness of the hole transport layer depends on the conductivity of the hole transport layer and cannot be unconditionally limited, but is 10n.
m to 10 μm is preferable, and 10 nm to 1 μm is more preferable.

As the electron transporting material for forming the electron transporting layer, known electron transporting materials such as quinolinol derivative metal complex such as Alq ₃ (tris aluminum quinolinol), oxadiazole derivative and triazole derivative can be used. It is not limited to. These electron transporting materials may be used alone, or may be mixed or laminated with different electron transporting materials. The thickness of the electron-transporting layer depends on the conductivity of the electron-transporting layer and cannot be unconditionally limited, but is preferably 10 nm to 10 μm.
nm to 1 μm is more preferable.

The light emitting material, the hole transporting material and the electron transporting material used in each of the above layers may be used alone to form each layer, or each layer may be formed using a polymer material as a binder. Examples of the polymer material used for this purpose include polymethylmethacrylate, polycarbonate, polyester, polysulfone, and polyphenylene oxide, but are not particularly limited thereto.

As a film forming method of the light emitting material, the hole transporting material and the electron transporting material used for each of the above layers, a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, a coating method, a printing method and the like can be used. Although not particularly limited thereto, resistance heating vapor deposition and electron beam vapor deposition are mainly used for low molecular weight compounds, and coating methods are mainly used for high molecular weight materials.

Known transparent conductive materials such as conductive polymers such as ITO (indium tin oxide), tin oxide, zinc oxide, polythiophene, polypyrrole and polyaniline can be used as the anode material of the organic light emitting device according to the present invention. However, it is not particularly limited to these. The surface resistance of the electrode made of this transparent conductive material is 1 to 50 Ω / □ (ohm /
It is preferably square). As a film forming method of these anode materials, an electron beam vapor deposition method, a sputtering method, a chemical reaction method, a coating method and the like can be used, but the method is not particularly limited thereto. The thickness of the anode is preferably 50 to 300 nm.

In addition, a buffer layer may be inserted between the anode and the hole transport layer or the organic layer laminated adjacent to the anode for the purpose of relaxing an injection barrier for hole injection. A known material such as copper phthalocyanine is used for this, but the material is not particularly limited thereto.

As the cathode material of the organic light emitting device according to the present invention, Al, MgAg alloy, alkali metal such as Ca,
Known cathode materials such as Al and alkali metal alloys such as AlCa can be used, but are not limited thereto. As a film forming method of these cathode materials, a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, an ion plating method and the like can be used, but the method is not particularly limited thereto. The thickness of the cathode is 10 nm
˜1 μm is preferable, and 50 to 500 nm is more preferable.

An insulating layer having a thickness of 0.1 to 10 nm is inserted between the cathode and the electron transport layer or the organic layer laminated adjacent to the cathode for the purpose of improving electron injection efficiency. May be. As the insulating layer, known cathode materials such as lithium fluoride, magnesium fluoride, magnesium oxide, and alumina can be used, but the insulating layer is not particularly limited thereto.

Further, adjacent to the cathode side of the light emitting layer, a hole blocking layer may be provided for the purpose of suppressing passage of holes through the light emitting layer and efficiently recombining with electrons in the light emitting layer. Good. Known materials such as a triazole derivative and an oxadiazole derivative are used for this, but the material is not particularly limited thereto.

As the substrate of the organic light emitting device according to the present invention, an insulating substrate which is transparent to the emission wavelength of the light emitting material can be used. In addition to glass, PET (polyethylene terephthalate), polycarbonate and other transparent plastics can be used. Known materials can be used, but are not particularly limited thereto.

The organic light emitting device of the present invention can form pixels by a matrix method or a segment method by a known method, and can also be used as a backlight without forming pixels.

[0068]

The present invention will be described in more detail below by showing typical examples. Note that these are merely examples for description, and the present invention is not limited to these.

<Measurement device, etc.> 1) ¹ H-NMR JNM EX270 270Mz made by JEOL (solvent: deuterated chloroform or deuterated dimethylsulfoxide 2) Elemental analysis device RENS CHNS-932 type 3) GPC measurement ( Molecular weight measurement) Column: Shodex KF-G + KF804L + KF
802 + KF801 Eluent: Tetrahydrofuran (THF) Temperature: 40 ° C. Detector: RI (Shodex RI-71) 4) ICP elemental analysis Shimadzu Corporation ICPS 8000

(Example 1) Polymerizable compound: iridium
(III) Bis (2- (4-methacryloyloxyphene)
(Nil) pyridinate) (acetylacetonate) (hereinafter
Below, Ir (4-MA-ppy)₂Abbreviated as (acac)
You ) Synthesis As shown in scheme (1A), 2- (4-methoxyphenyl)
Phenyl) pyridine (hereinafter abbreviated as 4-MeO-Hppy)
Was synthesized. That is, under argon flow
Dehydrated from 22.4 g (120 mmol) of lomoanisol
Mug in tetrahydrofuran (hereinafter abbreviated as THF)
Using 3.4 g of nesium (Mg) (4-methoxyphen
Nil) magnesium bromide was synthesized and
Lomopyridine 15.8 g (100 mmol) and (1,2
-Bis (diphenylphosphino) ethane) dichloronitro
Kell (II) (Ni (dppe) Cl₂) 1.8 g
It was slowly added to the dehydrated THF solution and refluxed for 1 hour. reaction
After adding 250 ml of 5% hydrochloric acid aqueous solution to the solution, chloroform was added.
I washed it. The aqueous layer was neutralized with sodium hydrogen carbonate
After that, the target substance was extracted with chloroform, and the organic layer was decompressed.
Distilled. The distillate solidified immediately at room temperature to give a white solid.
Thus, 15.1 g of 4-MeO-Hppy was obtained. Yield 68
%. Identification¹H-NMR and CHN elemental analysis were performed.¹H
NMR (270MHz, CDCl ₃), ppm: 8.65 (d, 1H), 7.95 (d, 2H),
 7.71 (t, 1H), 7.66 (d, 1H), 7.16 (t, 1H), 7.00 (d, 2
H), 3.86 (s, 3H). Anal. Found: C 77.52, H 6.10, N
7.40.Calcd: C 77.81, H 5.99, N 7.56.

[0071]

[Chemical 31]

Then, as shown in Scheme (1B),
2- (4-hydroxyphenyl) pyridine (hereinafter 4-
Abbreviated as OH-Hppy. ) Was synthesized. That is, 4-Me
15.0 g (80.1 mmol) of O-Hppy was dissolved in concentrated hydrochloric acid and stirred in a closed container at 130 ° C. for 4 hours.
The reaction solution was neutralized with an aqueous sodium hydrogen carbonate solution, the target product was extracted with chloroform, and the extract was crystallized from a chloroform / hexane solution to give colorless crystals.
10.0 g of -OH-Hppy was obtained. Yield 73%. Identification was performed by ¹ H-NMR and CHN elemental analysis. ¹ H NMR (27
0MHz, CDCl ₃ ), ppm: 8.63 (d, 1H), 7.82 (d, 2H), 7.74
(t, 1H), 7.65 (d, 1H), 7.20 (t, 1H), 6.85 (d, 2H). An
al. Found: C 76.91, H 5.39, N 8.02. Calcd: C 77.1
7, H 5.30, N 8.18.

[0073]

[Chemical 32] Then, as shown in scheme (1C), bis (μ-chloro) tetrakis (2- (4-
Hydroxyphenyl) pyridine) diiridium (II
I) (hereinafter, abbreviated as [Ir (4-OH-ppy) ₂ Cl] ₂ ) was synthesized. That is, 4-OH-Hppy 0.8
6 g (5.0 mmol) and hexachloroiridium (I
II) 1.00 g of sodium acid hydrate was dissolved in 40 ml of a mixed solvent of 2-ethoxyethanol: water = 3: 1 (volume ratio), and argon gas was blown therein for 30 minutes, followed by stirring under reflux for 6 hours. The solvent was distilled off, the remaining solid was washed with distilled water and chloroform, and dried under vacuum for 5 hours to obtain [Ir (4-OH-ppy) ₂ as a yellow powder.
Cl] ₂ 0.63 g was obtained. Yield 74%. Identification is ¹ H-
It was performed by NMR and CHN elemental analysis. ¹ H NMR (270 MHz, DM
SO-d ₆ ), ppm: 9.66 (d, 2H, J = 5.9 Hz), 9.38 (d, 2H, J
= 5.7 Hz), 8.0-7.9 (m, 8H), 7.61 (d, 2H, J = 8.1 H
z), 7.54 (d, 2H, J = 8.4 Hz), 7.38 (dd, 2H, J = 6.2,
6.2 Hz), 7.26 (dd, 2H, J = 5.7, 5.7 Hz), 6.33 (dd,
2H, J = 8.6, 2.4 Hz), 6.28 (dd, 2H, J = 8.4, 2.4 H
z), 5.67 (d, 2H, J = 2.2 Hz), 5.12 (d, 2H, J = 2.4 H
z). Anal. Found: C 46.66, H 2.89, N 4.90. Calcd: C
46.52, H 2.84, N 4.93.

[0074]

[Chemical 33] Then, as shown in Scheme (1D), iridium (III) bis (2- (4-hydroxyphenyl) pyridinate) (acetylacetonate) (hereinafter Ir (4
Abbreviated as -OH-ppy) ₂ (acac). ) Was synthesized. That is, [Ir (4-OH-ppy) ₂ Cl] ₂ 22
7.2 mg (0.2 mmol), sodium carbonate 21
Dehydrated N, N-dimethylformamide (hereinafter abbreviated as DMF) 20 ml and 2.0-pentanedione 60.0 m in 2.0 mg (2.0 mmol) under an argon stream.
g (0.6 mmol) was added, and the mixture was stirred at 80 ° C. for 2 hours. After adding 100 ml of water to the reaction solution, it was extracted with chloroform and washed with saturated saline and distilled water. The organic layer was dried over magnesium sulfate, concentrated, and subjected to column chromatography (silica gel, methanol: chloroform = 5:
95, volume ratio). Further, it was recrystallized from hexane / acetone to obtain Ir as yellow crystals.
(4-OH-ppy) ₂ (acac) 152.0 mg
Got Yield 60%. Identification was carried out by ¹ H-NMR and CHN elemental analysis. ¹ H NMR (270 MHz, CDCl ₃ ), ppm: 8.35 (d,
2H, J = 5.7 Hz), 7.7-7.6 (m, 4H), 7.41 (d, 2H, J =
10.6 Hz), 7.04 (ddd, 2H, J = 5.8, 5.8, 2.4 Hz), 6.
33 (dd, 2H, J = 8.4, 2.4 Hz), 5.70 (d, 2H, J = 2.7 H
z), 5.24 (s, 1H), 1.78 (s, 6H). Anal. Found: C 51.3
1, H 3.76, N 4.40.Calcd: C 51.34, H 3.67, N 4.43.

[0075]

[Chemical 34]

Then, as shown in Scheme (1E),
Ir (4-MA-ppy) ₂ (acac) was synthesized.
That is, Ir (4-OH-ppy) ₂ (acac) 6
3.2 mg (0.1 mmol) and 2,6-di-tert
-Butyl-4-methylphenol (hereinafter abbreviated as BHT) 0.1 mg was dehydrated under an argon stream.
Dissolved in 10 ml, triethylamine 81.0 mg
(0.8 mmol) and methacrylic acid chloride 41.8
mg (0.4 mmol) was added, and the mixture was stirred at room temperature for 2 hours. 50 ml of water was added to the reaction solution, extracted with chloroform, and washed with saturated saline and distilled water. The organic layer was dried over magnesium sulfate, concentrated, and subjected to column chromatography (silica gel, methanol: chloroform = 2: 98,
(Volume ratio). Further, by recrystallizing it from hexane / chloroform, Ir was obtained as yellow crystals.
65.3 mg of (4-MA-ppy) ₂ (acac) was obtained. Yield 85%. Identification was carried out by ¹ H-NMR and CHN elemental analysis. ¹ H NMR (270 MHz, DMSO-d ₆ ), ppm: 8.38 (d,
2H, J = 5.7 Hz), 8.15 (d, 2H, J = 8.6 Hz), 7.95 (m,
2H), 7.78 (d, 2H, J = 8.9 Hz), 7.39 (m, 2H), 6.61 (d
d, 2H, J = 8.4, 2.4 Hz), 6.09 (s, 2H), 5.76 (s, 2H),
5.71 (d, 2H, J = 2.4 Hz), 5.27 (s, 1H), 1.86 (s, 3H),
1.73 (s, 3H). Anal. Found: C 54.68, H 4.13, N 3.6
1.Calcd: C 54.75, H 4.07, N 3.65.

[0077]

[Chemical 35]

Example 2 Polymerizable compound: Iridium (III) bis (2- (4- (2- (methacryloyloxy) ethylcarbamoyloxy) phenyl) pyridinate) (acetylacetonate) (hereinafter Ir (4- M
Abbreviated as OI-ppy) ₂ (acac). ), As shown in the synthetic scheme (2A) of Ir (4-MOI-p
py) ₂ (acac) was synthesized. That is, Ir (4-OH-ppy) ₂ (aca which is the intermediate in Example 1
c) 63.2 mg (0.1 mmol), BHT 0.
2 mg, dibutyltin (IV) dilaurate (hereinafter DBT
Abbreviated as L. ) 1.3 mg was dissolved in 10 ml of dehydrated THF under an argon stream, and 62.0 mg (0.4 mmol) of methacryloyloxyethyl isocyanate (manufactured by Showa Denko, trade name "Karenzu MOI") was added to obtain 5
The mixture was stirred at 0 ° C for 1 hour. 50 ml of water was added to the reaction solution, extracted with chloroform, and washed with saturated saline and distilled water.
The organic layer was dried over magnesium sulfate, concentrated, and purified by column chromatography (silica gel, methanol: chloroform = 5: 95, volume ratio). Further, it was recrystallized from hexane / chloroform to obtain Ir (4-MOI-ppy) ₂ (acac) as yellow crystals.
73.5 mg was obtained. Yield 78%. Identification is ¹ H-NM
R and CHN elemental analysis was performed. ¹ H NMR (270 MHz, DMSO-d
₆ ), ppm: 8.37 (d, 2H, J = 5.9 Hz), 8.1 (d, 2H, J = 7.
8 Hz), 7.93 (dd, 2H, J = 8.0, 8.0 Hz), 7.70 (d, 2H,
J = 8.6 Hz), 7.64 (t, 2H), 7.4 (dd, 2H, J = 6.3, 6.3
Hz), 6.56 (dd, 2H, J = 8.2,2.3 Hz), 6.02 (s, 2H),
5.7-5.6 (m, 4H), 5.26 (s, 1H), 4.06 (t, 4H, J = 5.
4), 3.3 (m, 4H, overwrapped with H ₂ O), 1.85 (s, 6H),
1.73 (s, 6H). Anal. Found: C 52.22, H 4.47, N 5.8
6. Calcd: C 52.28, H 4.39, N 5.95.

[0079]

[Chemical 36]

Example 3 Polymerizable compound: iridium (III) bis (2- (4- (4-vinylbenzyloxy) phenyl) pyridinate) (acetylacetonate) (hereinafter Ir (4-ST-ppy)) ₂ (acac)
Abbreviated. ), As shown in the synthetic scheme (3A) of Ir (4-ST-pp
y) ₂ (acac) was synthesized. That is, Ir (4-OH-ppy) ₂ (aca which is the intermediate in Example 1
c) 63.2 mg (0.1 mmol), BHT 0.
2 mg, potassium carbonate 138.2 mg (1.0 mmo
l) was dissolved in 10 ml of dehydrated DMF under an argon stream, and 4-vinylbenzyl chloride (61.0 m) was further added.
g (0.4 mmol) was added, and the mixture was stirred at 80 ° C. for 6 hours. 50 ml of water was added to the reaction solution, extracted with chloroform, and washed with saturated saline and distilled water. The organic layer was dried over magnesium sulfate, concentrated, and subjected to column chromatography (silica gel, methanol: chloroform = 5: 95,
(Volume ratio). By recrystallizing it from hexane / chloroform, Ir (4-S) was obtained as yellow crystals.
62.2 mg of T-ppy) ₂ (acac) was obtained. Yield 72%. Identification was carried out by ¹ H-NMR and CHN elemental analysis. ¹ H NMR (270 MHz, DMSO-d ₆ ), ppm: 8.37 (d, 2H, J =
5.9 Hz), 8.13 (d, 2H, J = 8.4 Hz), 8.0-7.9 (m, 2
H), 7.75 (d, 2H, J = 8.9 Hz), 7.5- 7.3 (m, 10H), 6.7
3 (m, 2H), 6.59 (dd, 2H, J = 8.2, 2.4 Hz), 5.88 (d, 2
H, J = 17.8 Hz), 5.73 (d, 2H, J = 2.4 Hz), 5.3-5.
2 (m, 7H), 1.78 (s, 3H). Anal. Found: C62.58, H 4.6
5, N 3.20.Calcd: C 62.55, H 4.55, N 3.24.

[0081]

[Chemical 37]

Example 4 Polymerizable compound: Ir (4-M
A-ppy)₂Second synthetic method of (acac) As shown in scheme (4A), 2- (4-methacryloyl
Iloxyphenyl) pyridine (hereinafter 4-MA-Hp
Abbreviated as py. ) Was synthesized. That is, in the first embodiment
3.42 g (20.0) of 4-OH-Hppy which is an intermediate
mmol) under an argon stream to dehydrate dichlorometa
Dissolved in 20 ml of triethylamine, 6.07 g (6
0.0 mmol), and methacrylic acid chloride 3.
After dropping 14 g (30.0 mmol) in 1 hour,
Stir at warm temperature for 2 hours. Add 100 ml of water to the reaction mixture and
It was extracted with loroform and washed with saturated saline and water. Organic
The layer was dried over magnesium sulfate, concentrated, and then subjected to column chromatography.
Purified by chromatography (silica gel, chloroform)
It was Then recrystallize it from hexane / chloroform.
To give 4-MA-Hppy as colorless crystals.
4.16 g was obtained. Yield 87%. Identification¹With H-NMR
CHN elemental analysis was performed.¹H NMR (270 MHz, CDCl ₃), p
pm: 8.63 (d, 1H, J = 4.9 Hz), 7.98 (d, 2H, J = 8.6 H
z), 7.5-7.6 (m, 2H), 7.2-7.1 (m, 3H), 6.01 (s, 1
H), 5.53 (s 1H), 1.83 (s, 3H). Anal. Found: C 75.26,
 H 5.53, N 5.79. Calcd: C 75.30, H 5.48, N 5.85.

[0083]

[Chemical 38] Then, as shown in scheme (4B), bis (μ-chloro) tetrakis (2- (4-
Methacryloyloxyphenyl) pyridine) diiridium (III) (hereinafter, [Ir (4-MA-ppy) ₂ C
l] ₂ is abbreviated. ) Was synthesized. That is, 4-MA-Hpp
y 1.20 g (5.0 mmol) and sodium hexachloroiridium (III) hydrate 1.00 g
Ethoxyethanol: water = 3: 1, volumetric mixed solvent 4
It was dissolved in 0 ml, and after blowing argon gas for 30 minutes, the mixture was stirred under reflux for 6 hours. The resulting precipitate was collected by filtration, washed with ethanol and a small amount of acetone, and dried under vacuum for 5 hours to obtain [Ir (4-MA-
0.87 g of ppy) ₂ Cl] ₂ was obtained. Yield 82%. Identification was carried out by ¹ H-NMR and CHN elemental analysis. ¹ H NMR (27
0 MHz, DMSO-d ₆ ), ppm: 9.64 (d, 2H, J = 5.7 Hz), 9.37
(d, 2H, J = 5.7 Hz), 8.2-8.1 (m, 4H), 7.75 (m, 4
H), 7.6-7.5 (m, 8H), 6.56 (m, 4H), 5.87 (d, 2H, J =
2.4 Hz), 5.38 (d, 2H, J = 2.4 Hz), 6.09 (s, 2H), 6.0
3 (s, 2H), 5.79 (s, 2H), 5.74 (s, 2H), 1.89 (s, 6H),
1.87 (s, 6H). Anal. Found: C 51.13, H 3.51, N 3.97.
Calcd: C 51.17, H 3.44, N 3.98.

[0084]

[Chemical Formula 39]

Then, as shown in Scheme (4C),
Ir (4-MA-ppy) ₂ (acac) was synthesized.
That is, [Ir (4-MA-ppy) ₂ Cl] ₂ 281.
7 mg (0.2 mmol), sodium carbonate 212.0
20 mg of dehydrated DMF and 60.0 mg of 2,4-pentanedione under a stream of argon.
(0.6 mmol) was added, and the mixture was stirred at 80 ° C. for 2 hours.
After adding 100 ml of water to the reaction solution, it was extracted with chloroform and washed with saturated saline and distilled water. The organic layer was dried over magnesium sulfate, concentrated, and subjected to column chromatography (silica gel, methanol: chloroform = 2: 9).
(8, volume ratio). Further, it was recrystallized from hexane / chloroform to give I as yellow crystals.
r (4-MA-ppy) ₂ (acac) 221.1m
g was obtained. Yield 72%. Identification was conducted by ¹ H-NMR and CHN elemental analysis, and it was confirmed that the compound was the same as the compound synthesized in Example 1.

[0086]

[Chemical 40]

Example 5 N-Vinylcarbazole-I
r (4-MA-ppy) ₂ (acac) copolymer (hereinafter, VCz-co-Ir (4-MA-ppy) ₂ (ac
Abbreviated as ac). ) As a unit having a synthetic light emitting function of Ir (4-MA-ppy)
₂ (acac), N as a unit having a hole transport function
The above copolymer was synthesized as a light emitting material containing vinylcarbazole. N-Vinylcarbazole 966m
g (5.0 mmol), Ir (4-MA-ppy)
₂ (acac) 38.4 mg (0.05 mmol),
AIBN (8.2 mg, 0.05 mmol) was dissolved in dehydrated toluene (25 ml), and argon was further bubbled in for 1 hour. The temperature of this solution was raised to 80 ° C., the polymerization reaction was started, and the mixture was stirred as it was for 8 hours. After cooling, the reaction solution was dropped into 250 ml of methanol to precipitate a polymer, and the polymer was collected by filtration. Furthermore, the recovered polymer was dissolved in 25 ml of chloroform, and this solution was added to methanol 25
After purification by dropping into 0 ml and reprecipitating, the product was vacuum-dried at 60 ° C. for 12 hours to obtain VCz-co-Ir (4-MA-ppy) ₂ (a) as a target product.
ac) 755 mg was obtained. Table 1 shows the recovery rate, GPC measurement result, and Ir complex content by ICP elemental analysis. Ir (4-MA-ppy) ₂ (acac) is a bifunctional monomer, but its amount is extremely smaller than that of N-vinylcarbazole, so that the degree of crosslinking is low and no insoluble matter is formed.

(Examples 6 to 7) Ir (4-MA-pp)
y) A copolymer was synthesized in the same manner as in Example 5 except that the polymerizable compounds prepared in Examples 2 to 3 were used in an equimolar number instead of ₂ (acac). Recovery rate, GPC
The measurement results and the Ir complex content by ICP elemental analysis are shown in Table 1.
Shown in.

[0089]

[Table 1]

(Examples 8 to 10) Preparation of organic light emitting device,
The width 4 serving as an anode is formed on one surface of a glass substrate having an evaluation of 25 mm square
2 mm of two ITO electrodes formed in stripes
Substrate with TO (Indium Tin Oxide) (Nippon Electric, Nipp
Organic Co., LTD.) was used to fabricate an organic light emitting device. First, poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (manufactured by Bayer Co., Ltd., trade name “Baytron P”) was spin-coated on the ITO (anode) of the above-mentioned substrate with ITO by a rotation speed of 3500 r.
After application under the conditions of pm and application time of 40 seconds, it was dried under reduced pressure in a vacuum dryer at 60 ° C. for 2 hours to form an anode buffer layer. The thickness of the obtained anode buffer layer is about 50 n.
It was m. Next, a coating solution for forming a layer containing a light emitting material and an electron transporting material was prepared. 21.0 mg of the light emitting material shown in Table 2 and 2- (4-biphenyl) -5- (4-tert-butylphenyl) -as an electron transport material
9.0 mg of 1,3,4-oxadiazole (PBD) (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 2970 mg of chloroform (manufactured by Wako Pure Chemical Industries, special grade), and the resulting solution had a pore size of 0.2.
A coating solution was obtained by filtering with a μm filter. Next, the prepared coating solution was applied onto the anode buffer layer by spin coating under the conditions of a rotation speed of 3000 rpm and a coating time of 30 seconds, and dried at room temperature (25 ° C.) for 30 minutes to obtain a light emitting material. A layer containing an electron transport material was formed. The thickness of the obtained layer containing the light emitting material and the electron transporting material is about 10
It was 0 nm. Next, the substrate on which a layer containing a light emitting material and an electron transporting material is formed is placed in a vapor deposition apparatus, and silver and magnesium are co-evaporated at a weight ratio of 1:10, and are arranged in stripes and have a width of 3 mm. The cathode of the book was formed 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 to fabricate four organic light emitting devices each having a length of 4 mm and a width of 3 mm.
ADVANTEST CORPORATION programmable DC voltage /
A voltage was applied to the organic EL device by using a current source TR6143 to cause the organic EL device to emit light, and the emission brightness was measured using a brightness meter BM-8 manufactured by Topcon Corporation. As a result, the light emission start voltage, the initial luminance at 15 V, and the luminance after 200 hours when fixed at 15 V and continuously emitting light were as shown in Table 2 (average of four elements using each light emitting material).

Comparative Example 1 Poly (N-vinylcarbazole) as a hole-transporting material (manufactured by Tokyo Kasei Kogyo) 19.
5 mg, a method known as a luminescent material (S. Lamansky et a
l., Inorganic Chemistry, 40, 1704 (2001)), the compound represented by the formula (12) 1.5 mg, and 2- (4-biphenyl) -5- (4-te as an electron transport material.
9.0 mg of rt-butylphenyl) -1,3,4-oxadiazole (PBD) (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 2970 mg of chloroform (manufactured by Wako Pure Chemical Industries, special grade),
An organic light emitting device was produced in the same manner as in Examples 8 to 10 except that the obtained solution was filtered through a filter having a pore size of 0.2 μm to obtain a coating solution, and the emission brightness was measured. As a result, the light emission start voltage, the initial luminance at 15 V, and the luminance after 200 hours when fixed at 15 V and continuously emitting light were as shown in Table 2 (average of four elements using each light emitting material).

[0092]

[Chemical 41]

[0093]

[Table 2]

[0094]

INDUSTRIAL APPLICABILITY The novel crosslinkable polymerizable compound of the present invention gives a novel polymer containing an iridium complex moiety, and by using this polymer as a light emitting material of an organic light emitting device, it emits light with high efficiency from an excited triplet state. Thus, it is possible to provide an organic light-emitting device that is excellent in stability, can have a large area, and is suitable for mass production.

[0095]

[Brief description of drawings]

FIG. 1 is an example of a cross-sectional view of an organic light emitting device of the present invention.

[0096]

[Explanation of symbols]

1 glass substrate 2 anode 3 hole transport layer 4 Light emitting layer 5 Electron transport layer 6 cathode

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Naoko Ito             1-1-1, Onodai, Midori-ku, Chiba City, Chiba Prefecture             Showa Denko Co., Ltd. (72) Inventor Hiroro Shirane             1-1-1, Onodai, Midori-ku, Chiba City, Chiba Prefecture             Showa Denko Co., Ltd. F-term (reference) 3K007 AB03 AB11 DB03                 4H050 AA01 AA02 AA03 AB46 AB84                       BD70 WB11 WB17 WB21 WB22                 4J100 AB15P AL66P BA02P BA34P                       BA93P BC43P BC65P CA01                       CA04 CA05 DA61 JA32

Claims (30)

[Claims] 1. A polymerizable compound represented by formula (1). [Chemical 1] [In the formula, L is a monovalent anionic bidentate ligand, X is a substituent having a polymerizable functional group, and R _{1 to} R ₇ are each independently a hydrogen atom, a halogen atom, a nitro group, an amino group, or a sulfone. It represents an acid group, a sulfonate group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ] 2. A polymerizable compound represented by formula (2). [Chemical 2] [In the formula, A _{1 to} A ₃ are each independently a hydrogen atom, a halogen atom or an organic group having 1 to 20 carbon atoms which may have a hetero atom, X is a substituent having a polymerizable functional group, R ₁ to R _7's each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ] 3. The polymerizable compound according to claim 1 or 2, wherein the polymerizable functional group of X in the formula (1) or (2) is a group having a carbon-carbon double bond. 4. The X according to the formula (1) or (2) is any of a methacryloyloxy group, a methacryloyloxyethylcarbamoyloxy group and a vinylbenzyloxy group. Polymerizable compound. 5. A polymerizable compound represented by formula (3). [Chemical 3] 6. A polymerizable compound represented by formula (4). [Chemical 4] 7. A polymerizable compound represented by formula (5). [Chemical 5] 8. A reaction product of the iridium binuclear complex represented by the formula (6) with the monovalent anionic bidentate ligand L, the polymerizable functional group and the compound represented by the formula (6). A method for producing a polymerizable compound containing a mononuclear iridium complex moiety, which comprises reacting a substituent Y having a reactive functional group with a compound having a functional group capable of binding to the substituent. [Chemical 6] [In the formula, Y represents a substituent having a reactive functional group, and R ₁
To R ₇ each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ] 9. The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to claim 8, wherein Y in the formula (6) is a group having active hydrogen. 10. The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to claim 8, wherein Y in the formula (6) is a hydroxyl group. 11. A compound having a functional group capable of reacting and binding with a substituent Y having a polymerizable functional group and a reactive functional group derived from the formula (6) has a polymerizable functional group or an acid chloride. The method for producing a polymerizable compound containing a mononuclear iridium complex portion according to claim 10, which is an alkyl halide compound having a functional group. 12. The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to claim 9, wherein the compound having a polymerizable functional group is an isocyanate compound having a polymerizable functional group. 13. A method for producing a polymerizable compound containing a mononuclear iridium complex moiety, which comprises reacting the iridium binuclear complex represented by the formula (7) with a monovalent anionic bidentate ligand L. [Chemical 7] [In the formula, X is a substituent having a polymerizable functional group, R _{1 to} R ₇ each independently have a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a hetero atom. Optionally represents an organic group having 1 to 20 carbon atoms. ] 14. The polymerizable compound containing a mononuclear iridium complex moiety according to claim 13, wherein X in the formula (7) is any one of a methacryloyloxy group, a methacryloyloxyethylcarbamoyloxy group and a vinylbenzyloxy group. Method for producing compound. 15. An iridium binuclear complex represented by the formula (6). [Chemical 8] [In the formula, Y represents a substituent having a reactive functional group, and R ₁
To R ₇ each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ] 16. The iridium binuclear complex according to claim 15, wherein Y in the formula (6) is a hydroxyl group. 17. An iridium binuclear complex represented by the formula (8). [Chemical 9] 18. A compound represented by the formula (9): [Chemical 10] [In the formula, L is a monovalent anionic bidentate ligand, Y is a substituent having a reactive functional group, R _{1 to} R ₇ are each independently a hydrogen atom, a halogen atom, a nitro group, an amino group, or a sulfone. It represents an acid group, a sulfonate group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ] 19. A compound represented by the formula (10): [Chemical 11] [In the formula, A _{1 to} A ₃ are each independently an organic group having 1 to 20 carbon atoms which may have a hydrogen atom, a halogen atom or a hetero atom, Y is a substituent having a reactive functional group, R ₁ to R _7's each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or an organic group having 1 to 20 carbon atoms which may have a hetero atom. ] 20. Y in the formula (9) or (10)
The compound according to claim 18 or 19, wherein is a hydroxyl group. 21. A compound represented by the formula (11): [Chemical 12] 22. An iridium binuclear complex represented by the formula (7). [Chemical 13] [In the formula, X is a substituent having a polymerizable functional group, R _{1 to} R ₇ each independently have a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group or a hetero atom. Optionally represents an organic group having 1 to 20 carbon atoms. ] 23. The iridium binuclear complex according to claim 22, wherein X in the formula (7) is any one of a methacryloyloxy group, a methacryloyloxyethylcarbamoyloxy group and a vinylbenzyloxy group. 24. A composition comprising the polymerizable compound according to any one of claims 1 to 7. 25. A polymer of the polymerizable compound according to claim 1. 26. A polymer obtained by polymerizing a composition containing at least one polymerizable compound according to any one of claims 1 to 7. 27. A light emitting material comprising the polymerizable compound according to any one of claims 1 to 7. 28. A luminescent material obtained by polymerizing the polymerizable compound according to any one of claims 1 to 7. 29. A luminescent material obtained by polymerizing a composition containing at least one polymerizable compound according to any one of claims 1 to 7. 30. An organic light emitting device using the light emitting material according to any one of claims 27 to 29.