JP2007099776A - Intermediate for polymerizable compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymeric light-emitting material for affording a mass-producible organic light-emitting element capable of providing a larger area with high luminescent efficiency. <P>SOLUTION: A precursor of a polymerizable compound having a bis(2-(2-pyridyl)benzothienyl)iridium complex moiety and a polymerizable functional group (e.g. a vinyl group) is provided. The polymerizable compound and a polymer thereof are provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to an intermediate of a polymerizable compound that is a precursor of a polymer light emitting material used in a flat display panel and an organic light emitting device (OLED) for a backlight used therein.

The organic light-emitting device was manufactured by Kodak C.I. W. Since Tang et al. Showed high-luminance light emission (Appl. Phys. Lett., 51, 913, 1987), material development and device structure improvements have progressed rapidly. Practical use began with telephone displays. In order to further expand the applications of this organic EL, development of materials for improving luminous efficiency and durability, development of full-color display, and the like are being actively carried out. In particular, when considering expansion to medium-sized panels, large-sized panels, or lighting applications, it is necessary to establish a mass production method suitable for further increase in luminance and increase in area by improving luminous efficiency.

First, regarding luminous efficiency, what is used in the current luminescent materials is light emission from an excited singlet state, that is, fluorescence. According to Monthly Display, October 1998, separate volume “Organic EL Display”, page 58. For example, since the generation ratio of excitons in the excited singlet state and excited triplet state in electrical excitation is 1: 3, the maximum internal quantum efficiency of light emission in organic EL (electroluminescence) is 25%. is there.

In contrast, M.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%. It was shown that it was possible to exceed the upper limit of 25% when using a dye (Appl. Phys. Lett., 75, 4, pp. 1999, WO 00/70655).

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

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

As described above, in order to obtain an organic light-emitting device with high luminous efficiency and a large area, a phosphorescent polymer material is required. Such phosphorescent polymer materials include those in which a ruthenium complex is incorporated in the main chain or side chain of a polymer (Ng, PK et al., Polymer Preprints., 40 (2), 1212 (1999 )). However, since these are ionic compounds, electrochemiluminescence due to an oxidation-reduction reaction at the electrode occurs when a voltage is applied. This is a very slow response speed on the order of minutes and cannot be used as a normal display panel.

Although it cannot be said to be a polymer material in a strict sense, there is a mixture of poly (N-vinylcarbazole) and an iridium complex that is a phosphorescent low-molecular compound (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.

As described above, there is no practical high-molecular phosphorescent material required for mass-producing organic light-emitting devices having high luminous efficiency and a large area. Accordingly, the present invention provides a polymer light-emitting material for solving the problems of the prior art as described above, and for obtaining an organic light-emitting device capable of large area production with high luminous efficiency and mass production. Is an issue.

As a result of various studies to solve the above problems, the present inventors have succeeded in obtaining a polymerizable compound having an iridium complex portion useful as a light emitting material of an organic light emitting device and an intermediate thereof, and completed the present invention. It came to do.

That is, the present invention relates to a polymerizable compound which is a novel compound represented by the following [1] to [42], an intermediate which is a novel compound necessary for the synthesis of these polymerizable compounds, and a method for producing these polymerizable compounds. .

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

Wherein, X _1, Y _1, at least one of Z ₁ represents a substituent having a polymerizable functional group, X _1, Y _1, each remaining independently a hydrogen atom of Z _1, halogen atom or The C1-C20 organic group which may have a hetero atom is represented. R _{1 to} R ₁₆ each independently represents 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. ]
[2] The polymerizable compound according to [1], wherein either X ₁ or Z ₁ in the formula (1) is a substituent having a polymerizable functional group.

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

[Wherein, X ₁ represents a substituent having a polymerizable functional group, and Q ₁ and Q ₂ each independently represents a C 1-20 organic group which may have a hydrogen atom, a halogen atom or a hetero atom. To express. ]
[4] The polymerizable compound according to any one of [1] to [3], wherein the polymerizable functional group is a carbon-carbon double bond.

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

[In formula, n represents the integer of 0-20. ]
[6] The polymerizable compound according to any one of [1] to [3], wherein the polymerizable functional group is a styryl group.

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

[In formula, n represents the integer of 0-20. ]

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

[9] The polymerizable compound according to any one of [1] to [3], wherein the polymerizable functional group is an alkenoyloxy group.

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

[In formula, n represents the integer of 0-20, A represents the C3-C20 organic group which has an acryloyl group or a methacryloyl group, or an acryloyloxy group or a methacryloyloxy group. ]

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

[Wherein, R represents a hydrogen atom or a methyl group. ]

[12] A polymerizable compound represented by the formula (8).

[Wherein, R represents a hydrogen atom or a methyl group. ]

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

[In formula, n represents the integer of 0-20, A represents the C3-C20 organic group which has an acryloyl group or a methacryloyl group, or an acryloyloxy group or a methacryloyloxy group. ]

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

[Wherein, R represents a hydrogen atom or a methyl group. ]

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

[Wherein, R represents a hydrogen atom or a methyl group. ]
[16] The polymerizable compound according to [1], wherein Y ₁ in the formula (1) is a substituent having a polymerizable functional group.

[17] A polymerizable compound represented by the formula (12).

[Wherein Y ₁ represents a substituent having a polymerizable functional group, and Q ₂ and Q ₃ each independently represents a hydrogen atom, a halogen atom or an organic group having 1 to 20 carbon atoms which may have a hetero atom. To express. ]

[18] The polymerizable compound according to [16] or [17], wherein the polymerizable functional group is a carbon-carbon double bond.
[19] The polymerizable compound according to [16] or [17], wherein the polymerizable functional group is a styryl group.
[20] The polymerizable compound according to [16] or [17], wherein the polymerizable functional group is an alkenoyloxy group.

[21] A polymerizable compound represented by the formula (13).

[Wherein, R represents a hydrogen atom or a methyl group. ]

[22] A polymerizable compound represented by the formula (14).

[Wherein, R represents a hydrogen atom or a methyl group. ]

[23] A method for producing a polymerizable compound containing a mononuclear iridium complex part, comprising reacting an iridium binuclear complex represented by formula (15) with a compound having a polymerizable functional group represented by formula (16) .

[Wherein, R _{1 to} R ₁₆ are each independently 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, and an organic group having 1 to 20 carbon atoms. Represents. ]

Wherein, X _1, Y _1, at least one of Z ₁ represents a substituent having a polymerizable functional group, X _1, Y _1, each remaining independently a hydrogen atom of Z _1, halogen atom or The C1-C20 organic group which may have a hetero atom is represented. ]

[24] The method for producing a polymerizable compound containing a mononuclear iridium complex part according to [23], wherein X ₁ or Z ₁ in the formula (16) is a substituent having a polymerizable functional group.
[25] The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to [23], wherein Y ₁ in the formula (16) is a substituent having a polymerizable functional group.

[26] After reacting the iridium binuclear complex represented by formula (15) with the compound having the reactive substituent represented by formula (17), the reactive substituent of the obtained mononuclear iridium complex and polymerization And a reactive substituent (at least one of X ₂ , Y ₂ , and Z ₂ ) derived from the formula (17) and a compound having a functional group that can be bonded to each other. The manufacturing method of the polymeric compound containing a mononuclear iridium complex part.

[Wherein, R _{1 to} R ₁₆ are each independently 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, and an organic group having 1 to 20 carbon atoms. Represents. ]

[Wherein, at least one of X ₂ , Y ₂ and Z ₂ is a reactive substituent, and the remainder of X ₂ , Y ₂ and Z ₂ each independently has a hydrogen atom, a halogen atom or a hetero atom. Or an organic group having 1 to 20 carbon atoms. ]

[27] The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to [26], wherein X _2, Y ₂ or Z ₂ in formula (17) is a substituent having active hydrogen.
[28] The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to [26], wherein X ₂ or Z ₂ in formula (17) is a substituent having a hydroxyl group.
[29] The method for producing a polymerizable compound containing a mononuclear iridium complex moiety according to [26], wherein Y ₂ in formula (17) is a substituent having a hydroxyl group.

[30] A compound represented by formula (18).

Wherein at least one of X _2, Y _2, Z ₂ represents a substituent having a hydroxyl group, X _2, Y _2, each remaining independently a hydrogen atom of Z _2, a halogen atom or a hetero atom The C1-C20 organic group which may have is represented. R _{1 to} R ₁₆ each independently represents 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. ]
[31] The compound according to [30], wherein X ₂ or Z ₂ in formula (18) is a substituent having a hydroxyl group.

[32] The compound represented by formula (19).

[Wherein, n represents an integer of 0 to 20, and Q ₁ and Q ₂ each independently represent a C 1-20 organic group which may have a hydrogen atom, a halogen atom or a hetero atom. ]

[33] A compound represented by the formula (20).

[Wherein, n represents an integer of 0 to 20, and Q ₁ and Q ₂ each independently represent a C 1-20 organic group which may have a hydrogen atom, a halogen atom or a hetero atom. ]
[34] The compound according to [30], wherein Y ₂ in formula (18) is a substituent having a hydroxyl group.

[35] A compound represented by formula (21).

Wherein, n represents an integer of 0 to 20, representing each Q ₂ and Q ₃ independently represent a hydrogen atom, a halogen atom or an organic group having 1 to 20 carbon atoms that may have a hetero atom. ]

[36] A polymer of the polymerizable compound according to any one of [1] to [22].
[37] A polymer obtained by polymerizing a composition containing one or more polymerizable compounds according to any one of [1] to [22].
[38] A composition comprising one or more polymerizable compounds according to any one of [1] to [22].
[39] A light-emitting material comprising the polymerizable compound according to any one of [1] to [22].
[40] A light emitting material obtained by polymerizing the polymerizable compound according to any one of [1] to [22].
[41] A light-emitting material obtained by polymerizing a composition containing one or more polymerizable compounds according to any one of [1] to [22].
[42] An organic light emitting device using the light emitting material according to any one of [39] to [41].

The novel polymerizable compound of the present invention gives a novel polymer containing an iridium complex portion, and is used as a light emitting material for an organic light emitting device, so that it can emit light with high efficiency, and can be enlarged in area and suitable for mass production. An organic light emitting device can be provided.

Hereinafter, the present invention will be specifically described.
According to the invention, the formula (1)

Wherein, X _1, Y _1, at least one of Z ₁ represents a substituent having a polymerizable functional group, X _1, Y _1, each remaining independently a hydrogen atom of Z _1, halogen atom or The C1-C20 organic group which may have a hetero atom is represented. R _{1 to} R ₁₆ each independently represents 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 polymerizable compound represented by this is provided.
The polymerizable functional group in the substituent having a polymerizable functional group among X ₁ , Y ₁ and Z ₁ in the formula (1) is radical polymerizable, cationic polymerizable, anionic polymerizable, addition polymerizable, condensation polymerizable. However, a radical polymerizable functional group is preferable. This polymerizable functional group is preferably a group having a carbon-carbon double bond, such as vinyl group, allyl group, alkenyl group, acryloyloxy group and methacryloyloxy group, alkenoyloxy group, methacryloyloxyethyl carbamate group, etc. And a substituent having a urethane (meth) acryloyloxy group, a styryl group and a derivative thereof, a vinyl acid group and a derivative thereof, and the like. Among these polymerizable functional groups, an acryloyloxy group, a methacryloyloxy group, and a urethane (meth) acryloyloxy group are preferable from the viewpoint of polymerizability.

The “organic group having 1 to 20 carbon atoms which may have a hetero atom” in the present invention is not limited as long as it does not impair the gist of the present invention, and is a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom. You may have an atom. Preferred examples include an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkoxyalkyl group, an allyl group, an allyloxy group, an aralkyl group, an aralkyloxy group, or a halogen-substituted product thereof.

Substituents having no polymerizable functional group among X ₁ , Y ₁ and Z ₁ in each formula, Q _{1 to} Q ₃ are a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, Examples include alkyl groups such as amyl and hexyl, aralkyl groups, alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy, and tertiary butoxy, ester groups such as acetoxy and propoxycarbonyl groups, and organic groups such as aryl groups. . In these, a hydrogen atom, a halogen atom, and a C1-C20 alkyl group are preferable.

As R _{1 to} R ₁₆ in each formula, a hydrogen atom, a halogen atom, a nitro group, an amino group, a sulfonic acid group, a sulfonic acid ester group such as methyl sulfonate, methyl, Alkyl groups such as ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, amyl, hexyl, aralkyl groups, and alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy, tertiary butoxy, acetoxy groups, propoxycarbonyl groups, etc. Organic groups such as ester groups and aryl groups can be mentioned. Further, these organic groups may further have a substituent such as a halogen atom, a nitro group, or an amino group. In these, a hydrogen atom, a halogen atom, and a C1-C20 alkyl group are preferable.

A in Formula (6) and Formula (9) is a C3-C20 organic group having an acryloyl group, a methacryloyl group, an acryloyloxy group, or a methacryloyloxy group. The organic group may have a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom as long as the gist of the present invention is not impaired. The organic group here is preferably an alkyl group, an allyl group, or an aralkyl group. Furthermore, an isocyanate bond may be included.

Next, although the example of the synthesis | combining method of the polymeric compound by this invention is given below, this invention is not limited to these at all.

The first synthesis method is a polymerizable compound containing a mononuclear iridium complex portion by reacting a binuclear complex of iridium represented by formula (15) with a compound having a polymerizable substituent represented by formula (16). Is the way to get.

[Wherein, R _{1 to} R ₁₆ are each independently 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, and an organic group having 1 to 20 carbon atoms. Represents. ]

Wherein, X _1, Y _1, at least one of Z ₁ represents a substituent having a polymerizable functional group, X _1, Y _1, each remaining independently a hydrogen atom of Z _1, halogen atom or The C1-C20 organic group which may have a hetero atom is represented. ]

The binuclear complex of iridium of the formula (15) can be synthesized by a known method (S. Lamansky et al., Inorganic Chemistry, 40, 1704 (2001)). R _{1 to} R _{16 in the} formula (15) are hydrogen atom, halogen atom, nitro group, amino group, sulfonic acid group, sulfonic acid ester group such as methyl sulfonate, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Alkyl groups such as tertiary butyl, amyl and hexyl; aralkyl groups such as benzyl groups; alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy and tertiary butoxy; and ester groups such as acetoxy and propoxycarbonyl groups. Mention may be made of organic groups. Further, these organic groups may further have a substituent such as a halogen atom, a nitro group, or an amino group. In these, a hydrogen atom, a halogen atom, and a C1-C20 alkyl group are preferable.

At least one of the substituents X ₁ , Y ₁ , and Z ₁ of the compound represented by the formula (16) is a substituent having a polymerizable functional group, and means the same as the description of the formula (1). Moreover, the substituent which does not have a polymerizable functional group among the substituents X ₁ , Y ₁ and Z ₁ of the compound represented by the formula (16) is the same as in the case of the formula (1).

The second synthesis method of the polymerizable compound according to the present invention comprises reacting a dinuclear complex of iridium represented by the formula (15) with a compound having a reactive substituent represented by the formula (17). In this method, a mononuclear iridium complex having a mononuclear iridium complex is obtained by reacting a reactive substituent of this intermediate with a compound having a polymerizable substituent.

[Wherein, R _{1 to} R ₁₆ are each independently 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, and a C 1-20 organic group. Represents. ]

[Wherein, at least one of X ₂ , Y ₂ and Z ₂ is a reactive substituent, and the remainder of X ₂ , Y ₂ and Z ₂ each independently has a hydrogen atom, a halogen atom or a hetero atom. Or an organic group having 1 to 20 carbon atoms. ]

At least one of X ₂ , Y ₂ and Z _{2 in} the formula (17) is a reactive substituent and has a functional group such as a hydroxyl group. Examples of the functional group include a functional group having an active hydrogen such as a hydroxyl group, a mercapto group, and an amino group, and a carboxyl group, but the functional group is not limited thereto. Examples of the reactive substituent having these functional groups include a hydroxyl group, a hydroxyalkyl group, a hydroxyphenyl group, a mercapto group, and an amino group.

Moreover, this reactive substituent may be protected with a protecting group. In this case, the mononuclear iridium complex having a reactive substituent is obtained as an intermediate by deprotection after carrying out the reaction while being protected by the protective group to obtain a mononuclear iridium complex. Then, the polymeric compound containing a mononuclear iridium complex part is obtained by making it react with the compound which has the reactive substituent of this intermediate body, and a polymeric functional group. In addition, the above-mentioned polymerizable functional group is excluded as a functional group of these reactive substituents.

Of the substituents X ₂ , Y ₂ , and Z ₂ of the compound represented by the formula (19), examples of the substituent that is not a reactive substituent include a hydrogen atom, a halogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tarsia. Examples include alkyl groups such as butyl, amyl, and hexyl; alkoxy groups such as methoxy, ethoxy, propoxy, isobutoxy, and tertiary butoxy; ester groups such as acetoxy and propoxycarbonyl groups; and organic groups such as aryl groups. . Further, these organic groups may further have a substituent such as a halogen atom.

A compound having a polymerizable functional group to be reacted with a mononuclear iridium complex having a reactive substituent obtained by reacting an iridium dinuclear complex with a compound represented by the formula (17) having a reactive substituent is a polymerizable group. In addition, it is necessary to have a group that reacts with the reactive substituents X ₂ , Y ₂ , and Z ₂ of formula (17). As such a functional group, when the reactive substituents X ₂ , Y ₂ , and Z ₂ contain a hydroxyl group such as a hydroxymethyl group and a hydroxyl group, an isocyanate group and a carboxyl group are used, and X ₂ , Y ₂ , and Z ₂ are a mercapto group. When an amino group is included, an isocyanato group or an acid chloride (R-COCl) group can be used, and when X ₂ , Y ₂ , or Z ₂ is a carboxyl group, a hydroxyl group can be used.

In the case of the second synthesis method of the polymerizable compound according to the present invention, R _{1 to} R _{16 in the} formula (15) are selected from groups that do not react with the compound having a polymerizable functional group to be reacted with the mononuclear iridium complex. It is necessary to keep.

Examples of the compound having a polymerizable functional group to be reacted with the mononuclear iridium complex include polymerizable acid chlorides and polymerizable isocyanates, 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 is preferably a radical polymerizable functional group. This polymerizable functional group is preferably a group having a carbon-carbon double bond, and urethane such as vinyl, allyl, alkenyl, acryloyloxy and methacryloyloxy groups and other alkenoyloxy groups, and methacryloyloxyethylcarbamate groups. Examples thereof include (meth) acryloyloxy group, styryl group and derivatives thereof, vinyl acid group and derivatives thereof. Among these polymerizable functional groups, an acryloyloxy group, a methacryloyloxy group, and a urethane (meth) acryloyloxy group are preferable from the viewpoint of polymerizability. Specifically, examples of the polymerizable acid chloride include acrylic acid chloride and methacrylic acid chloride, and examples of the polymerizable isocyanate include methacryloyl isocyanate and methacryloyloxyethyl isocyanate. In addition, although chemical formulas, such as Formula (1) which show the compound of this invention, represent a metal complex structure and O-C-C-C-O represents a resonance structure, it cannot be overemphasized that the structure accept | permitted chemically is included. Yes.

The polymerizable compound according to the present invention is easily polymerized by using a thermal polymerization initiator such as 2,2′-azobis (isobutyronitrile) (AIBN) or benzoyl peroxide or an ultraviolet polymerization initiator such as benzophenone. And a polymer containing an iridium complex moiety can be provided. The polymer is a homopolymer according to one of the polymerizable compounds according to the present invention, a copolymer according to two or more of the polymerizable compounds according to the present invention, and one of the polymerizable compounds according to the present invention. The copolymer may be any of the above and one or more kinds of polymerizable compounds other than the polymerizable compound of the present invention. Here, as a polymerizable compound other than the polymerizable compound of the present invention, a hole transporting compound such as vinyl carbazole, an electron transporting compound such as an oxadiazole derivative or a triazole derivative having a polymerizable functional group, methyl acrylate, Compounds having no carrier transport properties such as (meth) acrylic acid alkyl esters such as methyl methacrylate, styrene and derivatives thereof can be exemplified, but the present invention is not limited thereto.

FIG. 1 is a cross-sectional view showing an example of the structure 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. In addition, the organic light emitting device configuration of the present invention is not limited to the example of FIG. 3) hole transport material, light emitting material, layer containing electron transport material, 4) hole transport material, layer containing light emitting material, 5) layer containing light emitting material, electron transport material, 6) Any one of the single layers of the light emitting material may be provided. Moreover, although the light emitting layer shown in FIG. 1 is one layer, two or more layers may be laminated | stacked.

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 applied to the lower layer and then polymerized, and a polymerized in advance may be applied (coated). Also good. In the case of application | coating, what melt | dissolved in the appropriate solvent can be apply | coated, and a solvent can also be dried after that.

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 a polymer thereof as a light emitting material, and contains other light emitting materials, hole transport materials, electron transport materials and the like. Also good.

In the organic light-emitting device according to the present invention, the luminous efficiency and / or durability can be further improved by forming the hole transport layer and the electron transport layer on both sides or one side of the light-emitting layer.

As a hole transport material for forming the hole transport layer, 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 ″ -tris (3-methylphenylphenylamino) triphenylamine), etc. Known hole transport materials such as triphenylamine derivatives, polyvinylcarbazole, and poly (3,4-ethylenedioxythiophene) can be used, but are not particularly limited thereto. These hole transport materials may be used alone, but may be mixed or laminated with different hole transport materials. The thickness of the hole transport layer depends on the conductivity of the hole transport layer and cannot be generally limited, but is preferably 10 nm to 10 μm, and more preferably 10 nm to 1 μm.

As the electron transport material for forming the electron transport layer, known electron transport materials such as quinolinol derivative metal complexes such as Alq3 (tris aluminum quinolinol), oxadiazole derivatives, and triazole derivatives can be used. There is nothing. These electron transport materials are used alone, but may be mixed or laminated with different electron transport materials. Although the thickness of the electron transport layer depends on the conductivity of the electron transport layer and cannot be generally limited, it is preferably 10 nm to 10 μm, and more preferably 10 nm to 1 μm.

In addition to the light emitting material, the hole transport material, and the electron transport material used for each of the above layers, each layer can be formed independently, and each layer can be formed using a polymer material as a binder. Examples of the polymer material used for this include, but are not limited to, polymethyl methacrylate, polycarbonate, polyester, polysulfone, polyphenylene oxide, and the like.

The light emitting material, hole transport material, and electron transport material used for each layer can be formed by resistance heating vapor deposition, electron beam vapor deposition, sputtering, coating, solution coating, and the like. In the case of a low molecular compound, resistance heating vapor deposition and electron beam vapor deposition are mainly used, and in the case of a polymer material, a coating method is mainly used in many cases.

As an anode material of the organic light emitting device according to the present invention, known transparent conductive materials such as conductive polymers such as ITO (indium tin oxide), tin oxide, zinc oxide, polythiophene, polypyrrole, polyaniline can be used. It is not limited to these. The surface resistance of the electrode made of this transparent conductive material is preferably 1 to 50Ω / □ (ohm / square). As a method for forming 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 there is no particular limitation thereto. The thickness of the anode is preferably 50 to 300 nm.

Further, 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 the injection barrier against hole injection. For this, a known material such as copper phthalocyanine is used, but it is not particularly limited thereto.

As the cathode material of the organic light emitting device according to the present invention, known cathode materials such as Al, MgAg alloys, alkali metals such as Ca, and alloys of Al and alkali metals such as AlCa can be used, but are particularly limited thereto. There is nothing. As a film forming method for these cathode materials, a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, an ion plating method, or the like can be used, but is not particularly limited thereto. The thickness of the cathode is preferably 10 nm to 1 μm, more preferably 50 to 500 nm.

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

Further, a hole block layer may be provided adjacent to the cathode side of the light emitting layer in order to prevent holes from passing through the light emitting layer and to efficiently recombine with electrons in the light emitting layer. For this, a known material such as a triazole derivative or an oxadiazole derivative is used, but it is not particularly limited thereto.

As the substrate of the organic light emitting device according to the present invention, an insulating substrate transparent to the emission wavelength of the light emitting material can be used. Although materials can be used, it is not limited to these.

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

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

<Measurement apparatus, etc.> 1) ¹ H-NMR JNM EXNM270270MHz Solvent: heavy chloroform 2) Element analyzer RECO CHNS-932 type 3) GPC measurement (molecular weight measurement)
Column: Shodex KF-G + KF804L + KF802 + KF801 Eluent: Tetrahydrofuran (THF)
Temperature: 40 ° C. Detector: RI (Shodex RI-71) 4) ICP elemental analysis ICPS manufactured by Shimadzu Corporation
8000

<Reagents> Unless otherwise specified, commercially available products (special grades) were used without purification.

(Example 1) Polymerizable compound: [6- (4-vinylphenyl) -2,4-hexanedionate] bis [2- (2-pyridyl) benzothienyl] iridium (III) {hereinafter Ir (btp) ₂ As shown in the synthesis scheme (1A) of [1- (StMe) -acac]}, acetylacetone and 4-vinylbenzyl chloride are reacted to give 6- (4-vinylphenyl) -2,4-hexanedione. Synthesized. That is, 1.23 g of sodium hydride (60%
in oil) (31 mmol) was weighed under a nitrogen atmosphere, 60 ml of dry tetrahydrofuran (hereinafter abbreviated as THF) was added thereto, and the mixture was cooled to 0 ° C. in an ice bath. When a mixed solution of 2.5 g (24 mmol) of acetylacetone and 1 ml of hexamethylphosphoric triamide (hereinafter abbreviated as HMPA) was added dropwise to this suspension, a colorless precipitate was formed. After stirring at 0 ° C. for 10 minutes, 17.5 ml (28 mol) of a n-butyllithium hexane solution (1.6 M) was added dropwise to dissolve the precipitate, and the mixture was further stirred at 0 ° C. for 20 minutes. To the obtained pale yellow solution, 4.0 g (26 mmol) of 4-vinylbenzyl chloride was added dropwise, the reaction solution was returned to room temperature and stirred for 20 minutes, and diluted hydrochloric acid was added to acidify the aqueous layer. The organic layer was washed with a saturated aqueous sodium chloride solution and dried over magnesium sulfate, and then the solvent was distilled off with a rotary evaporator. The obtained reaction mixture was added to a silica gel column and developed with a 1: 1 (volume ratio) mixed solvent of hexane / dichloromethane to fractionate the main product. The solvent was distilled off from the resulting solution under reduced pressure to obtain 3.0 g (14 mmol) of the intended 6- (4-vinylphenyl) -2,4-hexanedione as a brown liquid. Yield 56%. Identification was performed by CHN elemental analysis and ¹ H-NMR.

¹ H NMR: enol; d 7.33 (d, J = 8.1 Hz, 2 H, aromatic), 7.14 (d, J = 8.4
Hz, 2 H, aromatic), 6.68 (dd, J = 8.1 Hz, 1 H, vinylic), 5.70 (d, J = 17.0 Hz, 1
H, vinylic), 5.46 (s, 1 H, enol-methine), 5.20 (d, J = 11.1 Hz, 1H, vinylic),
2.91 (t, J = 5.7 Hz, 2 H, methylene), 2.58 (t, J = 7.3 Hz, 2 H, methylene), 2.03
(s, 3 H, methyl) .keto; d 7.33 (d, J = 8.1 Hz, 2H, aromatic), 7.14 (d, J = 8.4
Hz, 2 H, aromatic), 6.68 (dd, J = 8.1 Hz, 1 H, vinylic), 5.70 (d, J = 17.0 Hz,
1 H, vinylic), 5.20 (d, J = 11.1Hz, 1 H, vinylic), 3.53 (s, 2 H, C (= O) CH ₂ C (= O)),
2.89 (m, 4 H, ethylene), 2.19 (s, 3 H, methyl) .enol: keto = 6: 1. EA:
Calcd for C ₁₄ H ₉ O ₂ : C, 77.75; H, 7.46. Found: C,
77.49; H, 7.52.

Then, as shown in Scheme (1B), this 6- (4-vinylphenyl) -2,4-hexanedione and conventional methods (for example, S. Lamansky, et al., Inorganic Chemistry, 40, 1704 (2001)) Di (μ-chloro) tetrakis (2- (2-pyridyl) benzothienyl) diiridium (hereinafter abbreviated as [Ir (btp) ₂ Cl] ₂ ) synthesized in accordance with the description, and Ir (btp) ₂ [1- (StMe) -acac] was synthesized. That is, [Ir (btp) ₂ Cl] ₂
253 mg (0.20 mmol) was suspended in 10 ml of N, N-dimethylformamide (hereinafter abbreviated as DMF), and 161 mg of 6- (4-vinylphenyl) -2,4-hexanedione (0.74 mmol) and 64 mg were suspended. Of sodium carbonate and 1.9 mg of 2,6-di-tert-butyl-4- and methylphenol (hereinafter abbreviated as BHT) (0.0086 mmol) were added and stirred with heating at 80 ° C. for 1 hour. 100 ml of water and 50 ml of chloroform were added to the resulting reaction mixture and shaken well. The organic layer was dried over magnesium sulfate and then dried under reduced pressure on a rotary evaporator. Next, the crude product was purified with a silica gel column using dichloromethane as an eluent to obtain a reddish brown solution. The solution was concentrated under reduced pressure, hexane was added and recrystallized at −20 ° C. to obtain 153 mg (0.18 mmol) of the target Ir (btp) ₂ [1- (StMe) -acac] as a reddish brown solid. Obtained (yield 47%). Identification was performed by CHN elemental analysis and ¹ H-NMR.

¹ H NMR: d 8.40 (d, J = 5.4 Hz, 1 H, btp), 7.97 (d, J = 5.4 Hz, 1 H,
btp), 7.65 (m, 6 H, btp), 7.1 6.7 (m, 10 H, aromatic), 6.63 (dd, J = 17.8, 11.1
Hz, 1 H, vinylic), 6.24 (d, J = 8.1 Hz, 1 H, btp), 6.16 (d, J = 7.8 Hz, 1 H,
btp), 5.65 (d, J = 17.8 Hz, 1 H, vinylic), 5.22 (s, 1 H, diketonate-methine),
5.18 (d, J = 11.1 Hz, 1 H, vinylic), 2.56 (m, 2 H, ethylene), 2.37 (m, 2 H,
ethylene), 1.75 (s, 3 H, methyl) .EA: Calcd for C ₄₀ H ₃₁ IrN ₂ O ₂ S ₂ :
C, 58.02; H, 3.77; N, 3.38.Found: C, 57.79; H, 3.81; N, 3.55.

Example 2 Polymerizable Compound: [6- (4-Methacryloyloxyphenyl) -2,4-hexanedionate] bis [2- (2-pyridyl) benzothienyl] iridium (III) {hereinafter Ir (btp) ₂ Synthesis of [1- (MA-Ph-Me) -acac]} As shown in Scheme 2A, acetylacetone and a known method (C. Cativiela, et al., J. Org. Chem., 60, 3074 (1995)) was reacted with (4-benzyloxy) benzyl iodide to synthesize 6- (4-benzyloxyphenyl) -2,4-hexanedione. That is, sodium hydride (60%
in oil) 0.30 g (7.5 mmol) was weighed under a nitrogen atmosphere, 20 ml of THF was added thereto, and the mixture was cooled to 0 ° C. in an ice bath. When a mixed solution of 0.75 g (7.5 mmol) of acetylacetone and 0.5 ml of HMPA was added dropwise to this suspension, a colorless precipitate was formed. After stirring at 0 ° C. for 10 minutes, 4.6 ml (7.5 mmol) of a hexane solution (1.6 M) of n-butyllithium was added dropwise, and the mixture was further stirred at 0 ° C. for 20 minutes. A solution prepared by dissolving 2.28 g (7.0 mmol) of (4-benzyloxy) benzyl iodide in 10 ml of THF was added dropwise to the obtained pale yellow transparent solution. The reaction solution was stirred at room temperature for 1 hour, cooled again to 0 ° C., and neutralized with dilute hydrochloric acid. The organic layer was washed with a saturated aqueous sodium chloride solution, and then the solvent was distilled off with a rotary evaporator. The residue is passed through a silica gel column (developing solution: dichloromethane / hexane 1: 1 (volume ratio) mixed solvent), the main product is separated and dried under reduced pressure to give the desired 6- (4-benzyloxy Phenyl) -2,4-hexanedione 1.31 g (4.4 mmol) was obtained as a pale yellow solid (yield 63%). Identification was performed by CHN elemental analysis and ¹ H-NMR.

¹ H NMR: enol; d 7.5 6.8 (m, 9 H, aromatic), 5.46 (s, 1 H,
enol-methine), 5.04 (s, 2 H, -O-CH _2- ), 2.88 (t, J = 7.6 Hz, 2 H,
ethylene), 2.55 (t, J = 8.4 Hz, 2 H, ethylene), 2.04 (s, 3 H, methyl) .keto; d
7.5 6.8 (m, 9 H, aromatic), 5.04 (s, 2 H, -O-CH _2- ), 3.53 (s, 2 H,
C (= O) CH ₂ C (= O)), 2.84 (m, 4 H, ethylene), 2.19 (s, 3 H, methyl) .enol
: keto = 5: 1.EA: Calcd for C ₁₉ H ₂₀ O ₃ : C,
77.00; H, 6.86. Found: C, 77.46; H, 6.77.

Then, as shown in Scheme (2B), 6- (4-hydroxyphenyl) -2,4-hexanedione is obtained by hydrogenating the 6- (4-benzyloxyphenyl) -2,4-hexanedione. Synthesized. That is, 1.5 g of Pd-activated carbon (10%) was weighed under a nitrogen atmosphere, and 20 ml of dichloromethane and 1.31 g (4.4 mmol) of 6- (4-benzyloxyphenyl) -2,4-hexanedione were added. . The reaction system was replaced with 1 atm of hydrogen and stirred at room temperature for 11 hours. The obtained reaction solution was filtered to remove insoluble matters, and the solvent was distilled off under reduced pressure. The residue was added to a silica gel column and first developed with dichloromethane to remove by-products. Subsequently, the solution containing the compound eluted with a 1: 1 (volume ratio) mixed solvent of acetone / hexane was dried under reduced pressure to obtain 0.70 g of the intended 6- (4-hydroxyphenyl) -2,4-hexanedione. (3.4 mmol) was obtained as a pale yellow liquid (yield 77%). Identification was performed by CHN elemental analysis and ¹ H-NMR.

¹ H NMR: enol; d 7.04 (d, J = 8.4 Hz, 2 H, aromatic), 6.65 (d, J = 8.4
Hz, 2 H, aromatic), 5.55 (br, 1 H, OH), 5.47 (s, 1 H, enol-methine), 2.86 (t, J
= 7.3 Hz, 2 H, ethylene), 2.55 (t, J = 7.3 Hz, 2 H, ethylene), 2.04 (s, 3 H,
methyl) .keto; d 7.04 (d, J = 8.4 Hz, 2 H, aromatic), 6.65 (d, J = 8.4 Hz, 2 H,
aromatic), 5.55 (br, 1 H, OH), 3.55 (s, 2 H, C (= O) CH ₂ C (= O)), 2.83
(m, 4 H, ethylene), 2.19 (s, 3 H, methyl) .enol: keto = 5: 1.EA: Calcd for
C ₁₂ H ₁₄ O ₃ : C, 69.88; H, 6.84. Found: C, 69.67;
H, 6.79.

Next, as shown in Scheme (2C), this 6- (4-hydroxyphenyl) -2,4-hexanedione was reacted with [Ir (btp) ₂ Cl] ₂ synthesized according to a conventional method to produce [6- ( 4-hydroxyphenyl) -2,4-hexanedionate] bis [2- (2-pyridyl) benzothienyl] iridium (III) {hereinafter Ir (btp) ₂ [1- (OH-Ph-Me) -acac] Was abbreviated}. That is, 245 mg (0.19 mmol) of [Ir (btp) ₂ Cl] ₂ and 111 mg of sodium carbonate (1.06 mmol) were converted into 141 mg of [6- (4-hydroxyphenyl) -2,4-hexanedione] (0. 68 mmol) in 10 ml DMF solution and heated and stirred at 80 ° C. for 1.5 hours. Next, chloroform and an aqueous solution of ammonium chloride were added to the reaction mixture cooled to room temperature, and the mixture was shaken well. The organic layer was dried over magnesium sulfate, and the solvent was distilled off with a rotary evaporator. The residue was passed through a silica gel column (eluent: hexane / dichloromethane / acetone = 5/10/1 (volume ratio)), and the separated band containing the main product of reddish brown was separated and dried under reduced pressure. Ir (btp) ₂ [1- (OH-Ph-Me) -acac] 215 mg (0.26 mmol) was obtained as a reddish brown solid (yield 70%). Identification was performed by CHN elemental analysis and ¹ H-NMR.

¹ H NMR: d 8.40 (d, J = 5.4 Hz, 1 H, btp), 8.06 (d, J = 5.4 Hz, 1 H,
btp), 7.63 (m, 6 H, btp), 7.04 (m, 3 H, btp), 6.81 (m, 3 H, btp), 6.66 (d, J =
8.4 Hz, 2 H, -C ₆ H ₄ -OH), 6.38 (d, J = 8.4 Hz, 2 H, -C ₆ H ₄ -OH),
5.22 (s, 1 H, diketonate-methine), 5.20 (br, 1 H, OH), 2.48 (m, 2 H,
methylene), 2.31 (m, 2 H, methylene), 1.75 (s, 3 H, methyl) .EA: Calcd for C ₃₈ H ₂₉ IrN ₂ O ₃ S ₂ :
C, 55.80; H, 3.57; N, 3.42. Found: C, 56.19; H, 3.57; N, 3.31.

Next, as shown in scheme (2D), Ir (btp) ₂ [1- (OH-Ph-Me) -acac] is reacted with methacrylic acid chloride to react with Ir (btp) ₂ [1- (MA- Ph-Me) -acac] was synthesized. Specifically, 248 mg (0.32 mmol) of Ir (btp) ₂ [1- (OH-Ph-Me) -acac] was dissolved in 20 ml of dry dichloromethane, and 0.25 ml (1.8 mmol) of triethylamine and 0.20 ml of methacrylic acid were dissolved. Chloride (2.0 mmol) was added and stirred at room temperature for 1 hour. Next, the reaction solution was washed with 20 ml of an aqueous sodium carbonate solution, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / dichloromethane / acetone 2: 4: 1 (volume ratio) mixed solvent), and the reddish brown solution eluted first was separated and dried under reduced pressure. The target Ir (btp) ₂ [1- (MA-Ph-Me) -acac] (180 mg, 0.20 mmol) was obtained as a reddish brown solid (yield 64%). Identification was performed by CHN elemental analysis and ¹ H-NMR.

¹ H NMR: d 8.42 (d, J = 5.4 Hz, 1 H, btp), 8.10 (d, J = 5.4 Hz, 1 H,
btp), 7.65 (m, 6 H, btp), 7.1 6.7 (m, 10 H, aromatic), 6.40 (d, J = 8.1 Hz, 1 H,
btp), 6.27 (d, J = 8.1 Hz, 1 H, btp), 6.12 (s, 1 H, olefinic), 5.71 (s, 1 H,
olefinic), 5.19 (s, 1 H, diketonate-methine), 2.51 (m, 2 H, C ₂ H ₄ ),
2.39 (m, 2 H, C ₂ H ₄ ), 1.89 (s, 3 H, methacryl-methyl),
1.80 (s, 3 H, diketonate-methyl). EA: Calcd for C ₄₂ H ₃₃ IrN ₂ O ₄ S ₂ :
C, 56.93; H, 3.75; N, 3.16.Found: C, 57.09; H, 3.77; N, 4.18.

Example 3 Polymerizable compound: {6- [4- (2-methacryloyloxy) carbamoyloxyphenyl] -2,4-hexanedionate} bis [2- (2-pyridyl) benzothienyl] iridium (III) As shown in the synthesis scheme (3A) of {hereinafter referred to as Ir (btp) ₂ [1- (MOI-Ph-Me) -acac]}, Ir (btp) ₂ [1- (OH -(Ph-Me) -acac] and methacryloyloxyethyl isocyanate (trade name: MOI, Showa Denko) were reacted to synthesize Ir (btp) ₂ [1- (MOI-Ph-Me) -acac]. . That is, Ir (btp) ₂ [1- (OH-Ph-Me) -acac] 215 mg (0.26 mmol) was dissolved in 10 ml of THF, 4.0 mg of BHT (0.18 mmol) and 35 mg of dibutyltin (IV ) Dilaurate (hereinafter abbreviated as DBTL) and 401 mg of MOI (2.58 mmol) were added, and the mixture was heated to reflux for 3 hours on a hot water bath. Next, the reaction solution cooled to room temperature was dried under reduced pressure, and the residue was purified by a silica gel column (eluent: hexane / dichloromethane / acetone 5: 10: 1 (volume ratio) mixed solvent). The first reddish brown main product band eluted was collected and dried under reduced pressure to give 223 mg (0.23 mmol) of the desired Ir (btp) ₂ [1- (MOI-Ph-Me) -acac]. Was obtained as a reddish brown solid (yield 87%). Identification was performed by CHN elemental analysis and ¹ H-NMR.

¹ H NMR: d 8.40 (d, J = 5.7 Hz, 1 H, btp), 8.12 (d, J = 5.1 Hz, 1 H,
btp), 7.65 (m, 6 H, btp), 7.1 6.7 (m, 10 H, aromatic), 6.25 (d, J = 8.4 Hz, 1 H,
btp), 6.20 (d, J = 8.1 Hz, 1 H, btp), 6.16 (s, 1 H, olefinic), 5.63 (s, 1 H,
olefinic), 5.26 (br-s, 1 H, NH), 5.21 (s, 1 H, diketonate-methine), 4.31 (t, J
= 5.4 Hz, 2 H, NC ₂ H ₄ -O), 3.59 (t, J = 5.4 Hz, 2 H, NC ₂ H ₄ -O),
2.55 (m, 2 H, CC ₂ H ₄ -C), 2.34 (m, 2 H, CC ₂ H ₄ -C),
1.98 (s, 3 H, methacryl-methyl), 1.76 (s, 3 H, diketonate-methyl). EA: Calcd
for C ₄₅ H ₃₈ IrN ₃ O ₆ S ₂ : C,
55.54; H, 3.94; N, 4.32. Found: C, 55.13; H, 3.89; N, 4.58.

(Example 4) Polymerizable compound: [1- (2-methacryloyloxy) carbamoyloxy-2,4-pentanedionate] bis [2- (2-pyridyl) benzothienyl] iridium (III) {hereinafter Ir (btp ) ₂ (abbreviated as 1-MA-acac)} (4A), referring to [Ir (btp) ₂ Cl] ₂ synthesized according to a conventional method and a known method (European Patent EP0514217) Ir (btp) ₂ (1-OH-acac) was synthesized by reacting the synthesized 1- (tert-butyldimethylsilyloxy) -2,4-pentanedione (1-TBDMSO-2,4-pentanedione). . That is, 449 mg (0.35 mmol) of [Ir (btp) ₂ Cl] ₂ and 137 mg of sodium carbonate (1.29 mmol) were mixed with 310 mg of (1-TBDMSO-2,4-pentanedione) (1.35 mmol) in a 15 ml DMF solution. And stirred with heating at 80 ° C. for 1 hour. The resulting reaction solution was cooled to room temperature, and chloroform and dilute hydrochloric acid were added and shaken well. Subsequently, the organic layer was washed with water, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluent: dichloromethane), and the reddish brown compound eluted first was collected and dried under reduced pressure. The obtained solid was dissolved in 10 ml of dry THF, and 1.0 M of tetra-n-butylammonium fluoride (n-Bu ₄ NF) was dissolved.
0.60 ml (0.60 mmol) of THF solution was added dropwise with vigorous stirring. The solution was stirred at room temperature for 0.5 hour, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / dichloromethane / acetone 5: 10: 2 (volume ratio) mixed solvent), and the reddish brown main product was separated and dried under reduced pressure. Ir (btp) ₂ (1-OH-acac) 360 mg (0.49 mmol) was obtained as a reddish brown solid (yield 71%). Identification was performed by CHN elemental analysis and ¹ H-NMR.

¹ H NMR: d 8.40 (d, J = 5.4 Hz, 1 H, btp), 8.35 (d, J = 5.1 Hz, 1 H,
btp), 7.79 (m, 2 H, btp), 7.63 (m, 4 H, btp), 7.04 (m, 4 H, btp), 6.81 (t, J =
7.3 Hz, 2 H, btp), 6.20 (t, J = 6.8 Hz, 2 H, btp), 5.24 (s, 1 H,
diketonate-methine), 3.89 (dd, J = 8.1, 5.1 Hz, 1 H, -CHH-OH), 3.80 (dd, J
= 8.1, 5.1 Hz, 1 H, -CHH-OH), 2.92 (t, J = 5.1 Hz, 1 H, OH), 1.83 (s, 3 H,
diketonate-methyl). EA: Calcd for C ₃₁ H ₂₃ IrN ₂ O ₃ S ₃ :
C, 51.15; H, 3.18; N, 3.85. Found: C, 51.41; H, 3.36; N, 3.49.

Next, as shown in scheme (4B), Ir (btp) ₂ (1-MA-acac) was synthesized by addition reaction of this Ir (btp) ₂ (1-OH-acac) and MOI. That is, 177 mg of Ir (btp) ₂ (1-OH-acac), 3.0 mg of BHT (0.0086 mmol) and 20 mg of DBTL (0.032 mmol) were dissolved in 10 ml of THF, and 100 mg of MOI (0.64 mmol) was dissolved. ) And heated to reflux on an oil bath for 2 hours. Next, the reaction solution cooled to room temperature was dried under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: 10: 20: 3 (volume ratio) mixed solvent of hexane / dichloromethane / acetone). The red-brown main product eluted second was collected, dried under reduced pressure, dissolved in a dichloromethane / hexane mixed solvent, and recrystallized at −20 ° C. to obtain the target Ir (btp) ₂ (1- MA-acac) (173 mg, 0.20 mmol) was obtained as reddish brown needles (yield 81%). Identification was performed by CHN elemental analysis and ¹ H-NMR.

¹ H NMR: d 8.49 (d, J = 5.7 Hz, 1 H, btp), 8.40 (d, J = 5.4 Hz, 1 H,
btp), 7.74 (m, 2 H, btp), 7.61 (m, 4 H, btp), 7.03 (m, 4 H, btp), 6.80 (m, 2H,
btp), 6.21 (m, 2 H, btp), 6.06 (s, 1 H, olefinic), 5.55 (s, 1 H, olefinic),
5.31 (s, 1 H, diketonate-methine), 4.92 (br-s, 1 H, NH), 4.25 (s, 2 H,
NC (= O) -O-CH _2- ), 3.97 (m, 2 H, N-CH ₂ -CH ₂ -O),
3.16 (m, 2 H, N-CH ₂ -CH ₂ -O), 1.91 (s, 3 H, CH ₃ C (= CH ₂ )-),
1.81 (s, 3 H, diketonate-methyl). EA: Calcd for C ₃₈ H ₃₂ IrN ₃ O ₆ S ₂ :
C, 51.69; H, 3.65; N, 4.76.Found: C, 51.88; H, 3.65; N, 4.51.

(Example 5) N-vinylcarbazole-Ir (btp) ₂ [1- (StMe) -acac] copolymer (hereinafter abbreviated as VCz-co-Ir (btp) ₂ [1- (StMe) -acac] The above copolymer was synthesized as a light emitting material containing Ir (btp) ₂ [1- (StMe) -acac] as a unit having a synthetic light emitting function and N-vinylcarbazole as a unit having a hole transporting function. N-vinylcarbazole 1.55 g (8.0 mmol), Ir (btp) ₂ [1- (StMe) -acac] 33 mg (0.04 mmol), AIBN 13 mg (0.08 mmol) were dissolved in dehydrated toluene 40 ml, Argon was blown in for 1 hour. This solution was heated to 80 ° C. to initiate the polymerization reaction and stirred as it was for 8 hours. After cooling, the reaction solution was dropped into 250 ml of methanol to precipitate a polymer, and recovered by filtration. Further, the recovered polymer was dissolved in 25 ml of chloroform, and this solution was added dropwise to 250 ml of methanol and purified by reprecipitation, followed by vacuum drying at 60 ° C. for 12 hours to obtain the target product VCz-co-. 1.11 g of Ir (btp) ₂ [1- (StMe) -acac] was obtained. Table 1 shows the recovery rate, GPC measurement results, and Ir complex content by ICP elemental analysis.

(Examples 6 to 8) In the same manner as in Example 5 except that the polymerizable compound prepared in Examples 2 to 4 was used instead of Ir (btp) ₂ [1- (StMe) -acac], respectively. A polymer was synthesized. Table 1 shows the recovery rate, GPC measurement results, and Ir complex content by ICP elemental analysis.

(Examples 9 to 12) Production and evaluation of organic light-emitting elements On one side of a 25 mm square glass substrate, ITO (indium tin oxide) with two ITO electrodes with a width of 4 mm formed as an anode is provided in a stripe shape An organic light emitting device was fabricated using a substrate (Nippo Electric Co., LTD.). First, poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (trade name “Vitron P”, manufactured by Bayer Co., Ltd.) on the ITO (anode) of the substrate with ITO is rotated at 3500 rpm. After coating under the condition of a coating time of 40 seconds, drying was performed at 60 ° C. for 2 hours under reduced pressure in a vacuum dryer to form an anode buffer layer. The film thickness of the obtained anode buffer layer was about 50 nm. Next, a coating solution for forming a layer containing a light emitting material and an electron transport material was prepared. 21.0 mg of the light emitting material shown in Table 2, and 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (PBD) (Tokyo Chemical Industry) as an electron transport material 9.0 mg) was dissolved in 2970 mg chloroform (special grade, manufactured by Wako Pure Chemical Industries, Ltd.), and the resulting solution was filtered through a filter having a pore size of 0.2 μm to obtain a coating solution. Next, the prepared coating solution is applied onto the anode buffer layer by a spin coating method 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. A layer containing an electron transport material was formed. The thickness of the layer containing the obtained light emitting material and electron transporting material was about 100 nm. Next, a substrate on which a layer containing a light-emitting material and an electron transport material is formed is placed in a vapor deposition apparatus, and silver and magnesium are co-deposited at a weight ratio of 1:10. Two cathodes were 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, in an argon atmosphere, lead wires (wirings) were attached to the anode and the cathode to produce four organic light emitting elements having a length of 4 mm and a width of 3 mm. A voltage was applied to the organic EL element by using a programmable DC voltage / current source TR6143 manufactured by Advantest Co., Ltd. to emit light, and the luminance was measured using a luminance meter BM-8 manufactured by Topcon Corporation. As a result, the initial luminance at a light emission starting voltage of 20 V was as shown in Table 2 (average of four elements using each light emitting material).

It is an example of sectional drawing of the organic light emitting element of this invention.

Explanation of symbols

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

Claims (6)

A compound represented by formula (18):

Wherein at least one of X _2, Y _2, Z ₂ represents a substituent having a hydroxyl group, X _2, Y _2, each remaining independently a hydrogen atom of Z _2, a halogen atom or a hetero atom The C1-C20 organic group which may have is represented. R _{1 to} R ₁₆ each independently represents 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 compound according to claim 1, wherein X ₂ or Z ₂ in formula (18) is a substituent having a hydroxyl group. A compound represented by formula (19):

[Wherein, n represents an integer of 0 to 20, and Q ₁ and Q ₂ each independently represent a C 1-20 organic group which may have a hydrogen atom, a halogen atom or a hetero atom. ] The compound shown by Formula (20).

[Wherein, n represents an integer of 0 to 20, and Q ₁ and Q ₂ each independently represent a C 1-20 organic group which may have a hydrogen atom, a halogen atom or a hetero atom. ] The compound according to claim 1, wherein Y ₂ in formula (18) is a substituent having a hydroxyl group. A compound represented by formula (21):

Wherein, n represents an integer of 0 to 20, representing each Q ₂ and Q ₃ independently represent a hydrogen atom, a halogen atom or an organic group having 1 to 20 carbon atoms that may have a hetero atom. ]