JP2011001553A - Phosphorescent compound, phosphorescent composition, organic light-emitting element and display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic polymeric phosphorescent compound able to be formed into films from the solution of an organic solvent, water or the like in a wet process and bring the films to have large surface areas at low cost, stable and having long life and able to emit very high efficient phosphorescence in the material of an organic phosphorescent element, and also provide an organic phosphorescent element using the phosphorescent compound.SOLUTION: The phosphorescent compound is soluble in an organic solvent or water and includes a phosphorescent unit which is a repeat unit for emitting phosphorescence, and a carrier transporting unit which is a repeat unit for transporting a carrier, in the main chain or side chains of the polymeric compound.

Description

  The present invention relates to an organic polymer phosphorescent compound, a phosphorescent composition, an organic light emitting element, and a display device used as a material for an organic light emitting element.

  2. Description of the Related Art Organic light-emitting elements that emit light from a thin film made of an organic compound are attracting attention as elements that can emit light with high brightness at a low voltage as display devices such as flat panel displays and backlights.

  Research and development for increasing the area using a light-emitting organic polymer soluble in an organic solvent or water as a thin film material in an organic light-emitting element has been actively conducted with a styrene-based or fluorene-based organic polymer. As a method for forming such an organic polymer, wet methods such as a spin coating method, a printing method, and an inkjet method are used. In particular, the inkjet method is expected as a realistic pixel forming method for a display screen of a full color display, and a small full color prototype panel has already been disclosed.

  On the other hand, in the low-molecular compound system formed by vacuum evaporation, research on ultra-high efficiency of light emission has been actively conducted, and platinum and other materials that utilize phosphorescence, which is light emission from triplet excited states of organic compounds, are being studied. An organometallic complex of iridium has been reported. The external light emission quantum efficiency of organic light-emitting devices using this phosphorescent compound exceeds the 5% of conventional devices using fluorescent light emission, and is as high as 8%. Most recently, the device structure has been devised. As a result, an ultra-high efficiency of 15% has been achieved (Appl. Phys. Lett., 77, 904 (2000)).

  There is also a research report of a doped organic polymer light emitting device in which this low molecular phosphorescent compound is dispersed in an organic polymer. In the device doped with iridium complex in poly (N-vinylcarbazole) (PVK), the external light emission quantum efficiency is 4 % Is obtained, and a significant improvement is recognized (Jpn. J. Appl. Phys, 39, L828 (2000)). In addition, an organic polymer containing a ruthenium complex has been reported to emit electrochemical light (J. Mater. Chem., 9, 2103 (1999)).

  However, conventional organic polymer light-emitting devices intended to realize a large area at a low cost are still not sufficient in terms of light emission efficiency. The reason for this is that there is a wall with an upper limit of 5% as the theoretical external light emission efficiency because fluorescence that is light emission from a singlet excited state of a conventional organic polymer is used. An organic polymer light-emitting element has a great feature that an organic polymer layer can be formed from a solution of an organic solvent or water by a wet method. However, further improvement in luminous efficiency is an issue for practical use in the future.

  In addition, ultra-high efficiency of light emission has been attempted by dispersing low-molecular phosphorescent compounds in organic polymer light-emitting elements, but small molecules dispersed in the host polymer are not stable. Therefore, a long-life display device that can withstand long-term reliability cannot be realized.

  Therefore, in consideration of the future practical application of organic light-emitting elements, it is possible to form a film from a solution of an organic solvent or water by a wet method, whereby a large area can be realized at low cost, and stable, that is, a long life, Development of a new organic polymer light-emitting material capable of realizing ultra-high efficiency light emission is desired.

Appl. Phys. Lett. , 77, 904 (2000) Jpn. J. et al. Appl. Phys, 39, L828 (2000) J. et al. Mater. Chem. , 9, 2103 (1999)

  The present invention has been made in view of the above problems, and provides a phosphorescent compound and a phosphorescent composition of an organic polymer that is used as a material for an organic light-emitting device and emits stable and ultrahigh-efficiency phosphorescence. The purpose is to do.

  Another object of the present invention is to provide an organic light-emitting device using the organic polymer phosphorescent compound and the phosphorescent composition, and a display device using the organic light-emitting device.

  The invention described in (1) is a phosphorescent compound of a neutral organic polymer that emits phosphorescence for use in an organic light-emitting device, a phosphorescent unit that is a repeating unit that emits phosphorescence, and a carrier And a carrier transporting unit, which is a repeating unit for transporting.

  According to the invention described in (1), a phosphorescent compound of a neutral organic polymer that emits phosphorescence used for an organic light-emitting device, and a phosphorescent unit that is a repeating unit that emits phosphorescence; And a carrier transporting unit, which is a repeating unit for transporting carriers, and is used as a material for an organic light emitting device, and provides a stable and ultrahigh efficiency phosphorescent compound of an organic polymer that emits phosphorescence. be able to.

  In the invention described in (2), in the phosphorescent compound described in (1), the number m of the phosphorescent units and the number n of the carrier transporting units satisfy the relationship m <n. It is characterized by that.

  According to the invention described in (2), since the repeating number m of the phosphorescent unit and the repeating number n of the carrier transporting unit satisfy the relationship m <n, the phosphorescence efficiency is further improved. be able to.

  The invention described in (3) is the phosphorescent compound described in (2), wherein the number of repetitions m of the phosphorescent unit and the number of repetitions n of the carrier transporting unit are 0.0001 ≦ m / ( m + n) ≦ 0.2 is satisfied.

  According to the invention described in (3), the repeating number m of the phosphorescent unit and the repeating number n of the carrier transporting unit satisfy a relationship of 0.0001 ≦ m / (m + n) ≦ 0.2. Therefore, phosphorescence can be generated more efficiently.

  The invention described in (4) is characterized in that, in the phosphorescent compound according to any one of (1) to (3), the phosphorescent compound is soluble in an organic solvent or water. .

  According to the invention described in (4), since the phosphorescent compound is soluble in an organic solvent or water, film formation by a wet method from a solution is possible.

  The invention described in (5) is characterized in that, in the phosphorescent compound according to any one of (1) to (4), the degree of polymerization of the phosphorescent compound is 5 to 5000.

  According to the invention described in (5), since the degree of polymerization of the phosphorescent compound is 5 to 5000, it is possible to form a uniform and stable film that is soluble in an organic solvent.

  The invention described in (6) is the phosphorescent compound according to any one of (1) to (5), wherein the phosphorescent site of the phosphorescent unit and / or the carrier transporting unit A carrier transporting site constitutes a side chain of the phosphorescent compound.

  According to the invention described in (6), the phosphorescent site of the phosphorescent unit and / or the carrier transporting site of the carrier transport unit constitutes a side chain of the phosphorescent compound. The phosphorescent compound can be easily synthesized and easily dissolved in an organic solvent.

  The invention described in (7) is the phosphorescent compound according to any one of (1) to (5), wherein the phosphorescent site of the phosphorescent unit and / or the carrier transporting unit A carrier transporting site constitutes a main chain of the phosphorescent compound.

  According to the invention described in (7), the phosphorescent site of the phosphorescent unit and / or the carrier transporting site of the carrier transport unit constitutes the main chain of the phosphorescent compound. The movement of the complex portion is suppressed, and a stable phosphorescent compound can be obtained even at a high temperature.

  The invention described in (8) is characterized in that in the phosphorescent compound according to any one of (1) to (7), the carrier transporting portion of the carrier transporting unit is a hole transporting portion. And

  According to the invention described in (8), since the carrier transporting part of the carrier transporting unit is a hole transporting part, the carrier balance is good by changing the ratio of the phosphorescent light emitting part and the hole transporting part. Thus, a phosphorescent compound having high luminous efficiency can be obtained.

  The invention described in (9) is characterized in that, in the phosphorescent compound according to any one of (1) to (7), the carrier transporting portion of the carrier transporting unit is an electron transporting portion. And

  According to the invention described in (9), since the carrier transporting part of the carrier transporting unit is an electron transporting part, the carrier balance is good by changing the ratio of the phosphorescent light emitting part and the electron transporting part. Thus, a phosphorescent compound having high luminous efficiency can be obtained.

  The invention described in (10) is the phosphorescent compound according to any one of (1) to (7), wherein the carrier transporting portion of the carrier transporting unit is a hole transporting portion and an electron transporting portion. It is characterized by comprising.

  According to the invention described in (10), in the phosphorescent compound according to any one of (1) to (7), the carrier transporting part of the carrier transporting unit is a hole transporting part and an electron transporting part. Since it is composed of an active site, it has all the functions of light emitting property, hole transporting property and electron transporting property, and is thermally stable and has a long life without blending other organic materials.

  The invention according to (11) is the phosphorescent compound according to any one of (1) to (10), wherein the phosphorescent unit is a complex of a transition metal or a rare earth metal in the phosphorescent part. It is a monovalent group or a divalent group.

  According to the invention described in (11), since the phosphorescent site of the phosphorescent unit is a monovalent or divalent group of a transition metal or rare earth metal complex, phosphorescence is high. It can be a site.

  The invention described in (12) is the phosphorescent compound described in (11), wherein the monovalent group of the transition metal or rare earth metal complex is bonded to the main chain as a side chain via a spacer moiety. The spacer portion includes an organic group having 1 to 30 carbon atoms which may have a hetero atom or an inorganic group having 1 to 10 hetero atoms which does not have a carbon atom.

  According to the invention described in (12), the monovalent group of the transition metal or rare earth metal complex is bonded to the main chain as a side chain via a spacer moiety, and the spacer moiety has a hetero atom. Since it may contain an organic group having 1 to 30 carbon atoms or an inorganic group having 1 to 10 hetero atoms that does not have carbon atoms, the degree of freedom of movement of the complex portion is increased and the solubility in organic solvents is increased. In addition, since a uniform thin film can be produced by a coating method, a stable and high luminous efficiency can be obtained.

  The invention described in (13) is the phosphorescent compound according to any one of (1) to (11), wherein the carrier transporting portion of the carrier transporting unit is a monovalent group of carbazole, a tertiary group A group of groups consisting of a monovalent group of an amine, a monovalent group of an imidazole derivative, a monovalent group of a triazole derivative, a monovalent group of an oxadiazole derivative, a divalent group of styrene, and a divalent group of fluorene, and the group It contains at least one group selected from the group of groups substituted with a substituent.

  According to the invention described in (13), in the carrier transporting unit, the carrier transporting site has a monovalent group of carbazole, a monovalent group of a tertiary amine, a monovalent group of an imidazole derivative, or a monovalent group of a triazole derivative. At least one selected from the group consisting of a group, a monovalent group of an oxadiazole derivative, a divalent group of styrene, and a divalent group of fluorene, and a group of groups in which the group is substituted with a substituent. Since it contains a group, it can be a carrier transporting site having high performance for transporting carriers.

  The invention described in (14) is the phosphorescent compound according to any one of (1) to (13), wherein one kind of light emitting one predetermined color or two or more different colors are emitted. And having two or more types of phosphorescent units.

  According to the invention described in (14), since it has one kind of light emitting in one predetermined color or two or more kinds of phosphorescent light emitting units emitting in two or more different colors, a single color selected arbitrarily or Light can be suitably emitted for a plurality of colors.

  The invention described in (15) is the phosphorescent compound described in (14), wherein the phosphorescent unit is composed of two types emitting blue, green and yellow or red, and emits white as a whole. It is characterized by.

  According to the invention described in (15), the phosphorescent unit is composed of two types that emit blue, green, and yellow or red, and emits white as a whole. Therefore, the phosphorescent unit preferably emits light in a white color. Can do.

  The invention described in (16) is the phosphorescent compound described in (14), wherein the phosphorescent unit is composed of three types that emit blue, green and red, and emits white as a whole. Features.

  According to the invention described in (16), the phosphorescent unit is composed of three types that emit blue, green, and red, and emits white as a whole. Therefore, the phosphorescent unit can suitably emit light in white color. .

  The invention described in (17) is a phosphorescent composition comprising the phosphorescent compound described in any one of (1) to (16).

  According to the invention described in (17), since the phosphorescent compound described in any one of (1) to (16) is included, a suitable phosphorescent composition can be provided.

  The invention described in (18) is characterized in that the phosphorescent compound described in (14) is blended with a plurality of phosphorescent units having one or more types of phosphorescent units that emit light of mutually different colors. And a phosphorescent composition.

  According to the invention described in (18), since the phosphorescent compound described in (14) is blended with a plurality of phosphorescent units having one or more types of phosphorescent units that emit light of mutually different colors. A suitable phosphorescent composition can be provided.

  The invention described in (19) is characterized in that the phosphorescent composition according to (18) emits white light as a whole.

  According to the invention described in (19), since it emits white light as a whole, a suitable phosphorescent composition can be provided.

  The invention described in (20) includes a phosphorescent compound having a phosphorescent unit emitting blue or green and a phosphorescent unit emitting yellow or red in the phosphorescent composition described in (18). It is characterized by comprising a phosphorescent compound having a light-emitting property as a whole and emitting white light.

  According to the invention described in (20), a phosphorescent compound having a phosphorescent unit emitting blue or green and a phosphorescent compound having a phosphorescent unit emitting yellow or red are blended, Since it emits white as a whole, a suitable phosphorescent composition can be provided.

  The invention described in (21) is characterized by comprising the phosphorescent compound or phosphorescent composition according to any one of (1) to (20) and a carrier transporting polymer compound. A phosphorescent composition.

  According to the invention described in (21), the phosphorescent composition comprises the phosphorescent compound or phosphorescent composition according to any one of (1) to (20) and the carrier transporting polymer compound. Since it is blended, it is stable and has a long life. Further, by changing the ratio of the phosphorescent compound and the carrier transporting polymer compound, a phosphorescent composition having a good carrier balance and high emission efficiency can be provided.

  The invention described in (22) is the phosphorescent composition according to (21), wherein the carrier transporting polymer compound is a hole transporting polymer compound.

  According to the invention described in (22), since the carrier transporting polymer compound is a hole transporting polymer compound, it is stable and has a long life. Further, by changing the ratio of the phosphorescent compound and the hole transporting polymer compound, it is possible to provide a phosphorescent composition having a good carrier balance and high luminous efficiency.

  The invention described in (23) is the phosphorescent composition according to (21), wherein the carrier transporting polymer compound is an electron transporting polymer compound.

  According to the invention described in (23), since the carrier transporting polymer compound is an electron transporting polymer compound, it is stable and has a long life. Further, by changing the ratio of the phosphorescent compound and the electron transporting polymer compound, a phosphorescent composition having a good carrier balance and high emission efficiency can be provided.

  (24) The phosphorescent composition comprising the phosphorescent compound according to any one of (1) to (20) and a carrier transporting low molecular weight compound. It is.

  According to the invention described in (24), the phosphorescent composition comprises the phosphorescent compound according to any one of (1) to (20) and a carrier transporting low molecular weight compound. Stable and long life. Further, by changing the ratio of the phosphorescent compound and the carrier transporting low molecular weight compound, a phosphorescent composition having a good carrier balance and high emission efficiency can be provided.

  The invention described in (25) is characterized in that, in the phosphorescent composition described in (24), the carrier transporting low molecular weight compound is a hole transporting low molecular weight compound.

  According to the invention described in (25), since the carrier transporting low molecular weight compound is a hole transporting low molecular weight compound, it is stable and has a long life. In addition, by changing the ratio of the phosphorescent compound and the low transporting low molecular weight compound, a phosphorescent composition having a good carrier balance and high emission efficiency can be provided.

  The invention described in (26) is characterized in that, in the phosphorescent composition according to (24), the carrier transporting low molecular weight compound is an electron transporting low molecular weight compound.

  According to the invention described in (26), since the carrier transporting low molecular weight compound is an electron transporting low molecular weight compound, it is stable and has a long life. Further, by changing the ratio of the phosphorescent compound and the electron transporting low molecular weight compound, a phosphorescent composition having a good carrier balance and high emission efficiency can be provided.

  The invention described in (27) is an organic light-emitting device including one or more organic polymer layers sandwiched between an anode and a cathode, wherein at least one of the organic polymer layers is any one of (1) to (26) It contains the phosphorescent compound or phosphorescent composition as described in any one of the above.

  According to the invention described in (27), at least one layer of the organic polymer layer contains the phosphorescent compound or the phosphorescent composition according to any one of (1) to (26). An organic light-emitting element that emits stable and ultra-high-efficiency phosphorescence can be provided.

  The invention described in (28) is an organic light-emitting device including one or more organic polymer layers sandwiched between an anode and a cathode, and a color filter is disposed between the anode and a transparent substrate on which the anode is provided. At least one layer of the organic polymer layer contains the phosphorescent compound described in (15) or (16) or the phosphorescent composition described in (19) or (20).

  According to the invention described in (28), the color filter is disposed between the anode and the transparent substrate on which the anode is provided, and at least one of the organic polymer layers is described in (15) or (16). Since the phosphorescent compound or the phosphorescent composition described in (19) or (20) is included, an organic light-emitting device that emits stable and ultrahigh-efficiency color light can be provided.

  The invention described in (29) is characterized in that in the organic light emitting device described in (27) or (28), the anode is formed on a plastic substrate.

  According to the invention described in (29), since the anode is formed on the plastic substrate, a flexible organic light emitting device can be provided.

  The invention described in (30) is characterized in that in the organic light emitting device described in (27) to (29), the organic polymer layer is formed by an inkjet method or a printing method.

  According to the invention described in (30), since the organic polymer layer is formed by an inkjet method or a printing method, a large-area organic polymer layer can be easily produced.

  (31) In the display device having a display screen, each pixel of the display screen includes the organic light-emitting element according to any one of (27) to (30), Driven by two or more transistors.

  According to the invention described in (31), each pixel of the display screen includes the organic light-emitting element described in any one of (27) to (30), and each pixel includes two or more transistors. Therefore, an active matrix display device can be provided.

  According to the present invention, there is provided a phosphorescent compound of an organic polymer that is used as a material for an organic light-emitting device and emits stable and ultrahigh-efficiency phosphorescence. The present invention also provides an organic light emitting device using the organic polymer phosphorescent compound.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 illustrates a typical structure of an organic polymer phosphorescent compound according to the present invention. It is a figure explaining the laminated structure of the organic light emitting element of this invention. It is a figure which shows the emission spectrum of the organic light emitting element produced in Example 6-3. It is a figure which shows the emission spectrum of the organic light emitting element produced in Example 7-2.

  Next, embodiments of the present invention will be described with reference to the drawings.

  The present invention is an invention of an organic polymer phosphorescent compound used as a material of an organic light emitting device, and transports a repeating unit that emits phosphorescence (referred to as a phosphorescent unit) and carriers such as electrons and holes. Repeating units (referred to as carrier transporting units). The organic polymer phosphorescent compound of the present invention may be a random copolymer in which phosphorescent units and carrier transporting units are randomly arranged in a polymer chain, and is nonionic, That is, it is a neutral polymer. In the phosphorescent compound of the present invention, the phosphorescent unit and the carrier transport unit are linked to the polymer chain, and aggregation of the phosphorescent unit is suppressed. In addition, since it has a phosphorescent unit, ultra-high efficiency light emission can be realized.

  As shown in FIG. 1, the structure of the phosphorescent compound of the present invention typically includes (a) a phosphorescent moiety depending on the type of monomer that forms the phosphorescent unit and the carrier transporting unit. When the carrier transporting site is in the main chain of the polymer, (b) the phosphorescent site is in the side chain of the polymer, and the carrier transporting site is in the main chain of the polymer (c ) When the phosphorescent site is in the main chain of the polymer and the carrier transporting site is in the side chain of the polymer, (d) both the phosphorescent site and the carrier transporting site are in the polymer side chain. If there are, there are four ways. However, the phosphorescent site indicates a part having a function of emitting phosphorescence in the phosphorescent unit, and the carrier transporting part indicates a part having a function of transporting carriers in the carrier transporting unit.

  Here, it is desirable that at least one of the phosphorescent site and the carrier transporting site be bonded as a side chain to the polymer main chain of the phosphorescent compound (FIGS. 1B to 1D). . In this case, it is easy to synthesize a phosphorescent compound, and a phosphorescent compound that is easily dissolved in an organic solvent can be obtained.

  Further, in order to obtain a phosphorescent moiety having high phosphorescence emission efficiency, the phosphorescent moiety is preferably a monovalent group or a divalent group of a transition metal or rare earth metal complex.

  Specific examples of phosphorescent sites

に示す群から選択される配位子を含む、遷移金属錯体の一価基若しくは二価基又は希土類金属錯体の一価基若しくは二価基がある。上記の遷移金属錯体に使用される遷移金属は、周期表の第一遷移元素系列すなわち原子番号２１のＳｃから３０のＺｎまで、第二遷移元素系列すなわち原子番号３９のＹから４８のＣｄまで、第三遷移元素系列すなわち原子番号７２のＨｆから８０のＨｇまで、を含む。また上記の希土類金属錯体に使用される希土類金属は、周期表のランタノイド系列すなわち原子番号５７のＬａから７１のＬｕまでを含む。なお配位子は、上記の配位子と異なる配位子であってもよい。

Or a monovalent or divalent group of a transition metal complex or a monovalent or divalent group of a rare earth metal complex containing a ligand selected from the group shown in FIG. The transition metal used in the above transition metal complex includes the first transition element series of the periodic table, that is, Sc of atomic number 21 to Zn of 30, the second transition element series, that is, Y of atomic number 39 to Cd of 48, The third transition element series, that is, Hf of atomic number 72 to Hg of 80 is included. The rare earth metal used in the above rare earth metal complex includes the lanthanoid series of the periodic table, that is, La from atomic number 57 to 71 Lu. The ligand may be a ligand different from the above ligand.

  Specific examples of the carrier transporting portion having high performance for transporting carriers differ depending on whether the organic polymer phosphorescent compound of the present invention is a hole transporting polymer or an electron transporting polymer.

  In the case of hole transporting polymers,

に示す、第３級アミンであるカルバゾール（ＨＴ−１）、トリフェニルアミン（ＨＴ−２）、それらの多量体（ＨＴ−３）などの一価基が代表的であり、これらの一価基は、置換基で置換されていてもよい。

The monovalent groups such as carbazole (HT-1), triphenylamine (HT-2), and their multimers (HT-3), which are tertiary amines, are representative, and these monovalent groups May be substituted with a substituent.

  In the case of electron transporting polymers,

に示すオキサジアゾール誘導体（ＥＴ−１、２）、トリアゾール誘導体（ＥＴ−４）、又はイミダゾール誘導体（ＥＴ−３）の一価基が挙げられる。これら誘導体の一価基の芳香環は、置換基で置換されていてもよい。また、

The monovalent group of the oxadiazole derivative (ET-1, 2), triazole derivative (ET-4), or imidazole derivative (ET-3) shown in FIG. The monovalent aromatic ring of these derivatives may be substituted with a substituent. Also,

に示すような、蛍光性高分子においてホールの輸送能力を有し主鎖が共役系となる高分子を形成する、置換基で置換された、チオフェンの二価基（ＴＦ）、ベンゼンの二価基（ＰＰ）、スチレンの二価基（ＰＶ）、又はフルオレンの二価基（ＦＯ）を用いてもよい。ここで置換基Ｒは、アルキル基又はアルコキシ基を表す。本発明の燐光発光性化合物において、これらの二価基は燐光発光性部位として、高分子の主鎖に組み込まれる。

As shown in FIG. 1, a thiophene divalent group (TF) substituted with a substituent, a benzene divalent group that forms a polymer having a hole transport capability in a fluorescent polymer and a main chain as a conjugated system. A group (PP), a divalent group of styrene (PV), or a divalent group of fluorene (FO) may be used. Here, the substituent R represents an alkyl group or an alkoxy group. In the phosphorescent compound of the present invention, these divalent groups are incorporated into the main chain of the polymer as phosphorescent moieties.

  As an example of the copolymer polymer containing the above repeating unit,

に示すような、主鎖であるビニル構造の側鎖に、燐光発光性部位のイリジウム錯体又は白金錯体の一価基と、ホール（キャリア）輸送性部位としてのカルバゾール、又はその誘導体の一価基とを有する高分子（Ｐ１、Ｐ３、Ｐ４）があり、また電子（キャリア）輸送性部位として、側鎖にオキサジアゾール誘導体の一価基を使用した高分子（Ｐ２）がある。これら共重合高分子は、ビニル化合物から反応開始剤を使ったラジカル共重合で合成できる。イリジウム錯体の配位子の一つをビニル基で置換した単量体は

The side chain of the vinyl structure as the main chain has a monovalent group of an iridium complex or a platinum complex as a phosphorescent moiety and a monovalent group of carbazole as a hole (carrier) transport moiety or a derivative thereof. There are polymers (P1, P3, and P4) having the following structure, and there are polymers (P2) that use a monovalent group of an oxadiazole derivative in the side chain as an electron (carrier) transporting site. These copolymerized polymers can be synthesized from a vinyl compound by radical copolymerization using a reaction initiator. A monomer in which one of the ligands of the iridium complex is replaced with a vinyl group

のように、イリジウム錯体の配位子置換反応の途中で、ビニル基で置換されたフェニルピリジンを反応させて生成し単離する。

In the middle of the ligand substitution reaction of the iridium complex, phenylpyridine substituted with a vinyl group is reacted to produce and isolate.

  further,

に示すような、イリジウム錯体の配位子の一つがアセチルアセトン又はピコリン酸であって、このアセチルアセトン等を介してイリジウム錯体が高分子の主鎖に結合した構造の共重合高分子もある。ここで、化学式中の＊印は、高分子の化学式中に示した置換基Ｒに接続する部分（結合）であることを示す。

There is also a copolymer polymer having a structure in which one of the ligands of the iridium complex is acetylacetone or picolinic acid and the iridium complex is bonded to the main chain of the polymer via the acetylacetone or the like as shown in FIG. Here, the * mark in the chemical formula indicates a portion (bond) connected to the substituent R shown in the chemical formula of the polymer.

  In addition, when the transition metal complex part such as an iridium complex or a rare earth metal complex part as a phosphorescent moiety is bonded as a side chain to the main chain of the polymer as in the above copolymerized polymer, It is preferable to interpose a spacer portion between the monovalent group of the metal complex or rare earth metal complex and the main chain of the polymer.

  The spacer part is a polyvalent atom to which a substitutable atom in a polymer compound constituting the main chain is bonded, and a polyvalent atom to which a substitutable atom in a low molecular compound that is a source of a phosphorescent light emitting site is bonded. This is the part that bonds with an atom. Such a spacer portion preferably has a structure containing an organic group having 1 to 30 carbon atoms which may have a hetero atom or an inorganic group having 1 to 10 hetero atoms which does not have a carbon atom.

  As the spacer portion, for example, an alkylene group having 1 to 20 carbon atoms,

に示す、（Ｓ−１）から（Ｓ−１５）のような連結基などを挙げることができるが、これらに限定されるものではない。

(S-1) to (S-15), and the like, which are shown below, can be mentioned, but are not limited thereto.

In (S-1) to (S-15), R ₁ , R ₂ and R ₃ each independently represents a methylene group or a substituted or unsubstituted phenylene group, and k, m and n are each independently 0 1 or 2.

  In addition, there is a copolymer polymer having a structure in which a phosphorescent site and a carrier transporting site are incorporated in the main chain instead of the side chain.

に示すように、置換された、チオフェン、ベンゼン、フルオレンの二価基とイリジウム錯体の二価基とが重合して主鎖を形成している。

As shown in FIG. 2, the substituted divalent groups of thiophene, benzene and fluorene and the divalent group of the iridium complex are polymerized to form a main chain.

  As mentioned above, as an example of the copolymer, a copolymer of either one of a hole transporting site or an electron transporting site and a phosphorescent light emitting site has been mentioned. It may be a copolymer of a transporting site, an electron transporting site, and a phosphorescent light emitting site. In this case, the hole transporting site, the electron transporting site, and the phosphorescent light emitting site may each independently constitute the main chain of the copolymer or may constitute the side chain.

In the present invention, when the number of repeating phosphorescent units is m and the number of repeating carrier transporting units is n, in the present invention, in order to improve the phosphorescence efficiency, the relationship of m <n, It is desirable that the number of repeats is smaller than the number of repeats of the carrier transporting unit. However, both m and n are natural numbers of 1 or more. On the other hand, in the case of m ≧ n, phosphorescence emission is suppressed by concentration quenching. In order to realize ultra-high-efficiency light emission of phosphorescence, the ratio of the number of repeating phosphorescence-emitting units is preferably 0.2 or less in the total number of phosphorescence-emitting units and carrier transporting units. On the other hand, when the ratio of the number of repeating phosphorescent units is too small, the phosphorescent light emitting unit position decreases and the luminous efficiency decreases. For this reason, the ratio of the number of repeating phosphorescent units should not be too small, and is preferably 0.0001 or more. That is,
0.0001 ≦ m / (m + n) ≦ 0.2
It is desirable that

  The phosphorescent compound of the present invention may have one kind of phosphorescent unit that emits light in one color, or two or more kinds of phosphorescent units that emit light in two or more different colors. May be.

  The phosphorescent compound of the present invention has only one phosphorescent unit emitting one color by introducing two or more types of phosphorescent units emitting two or more different colors. An emission color that cannot be obtained with a compound can be obtained.

  For example, a phosphorescent compound for white light emission can be obtained by introducing three types of phosphorescent units each emitting blue, green and red into one compound at an appropriate ratio. Here, the phosphorescent unit emitting blue, green, or red means that when one phosphorescent compound is formed by using each independently, the emission color of photoluminescence indicates blue, green, or red, respectively. Or when an organic light-emitting device described below is further produced and emitted, its emission color indicates blue, green or red, respectively.

  In addition, blue of luminescent color here means that whose peak wavelength in an emission spectrum is 400-490 nm. Similarly, green means that the peak wavelength is 490 to 570 nm, and red means that the peak wavelength is 570 to 700 nm.

  A phosphorescent compound for white light emission can also be obtained by introducing two types of phosphorescent units emitting blue, green and yellow or red, respectively, into one compound at an appropriate ratio.

  In addition, blue or green of the luminescent color here means that whose peak wavelength in the emission spectrum is 400 to 570 nm, and similarly, yellow or red means that whose peak wavelength is 570 to 700 nm.

  The phosphorescent material for white light emission is not only a single phosphorescent compound as described above, but also a plurality of phosphorescent materials having one or more types of phosphorescent units exhibiting mutually different emission colors. It can also be obtained as a composition containing a compound.

  For example, a first phosphorescent compound having two types of phosphorescent units, a phosphorescent unit emitting blue light and a phosphorescent unit emitting green light, and one kind of phosphorescent unit emitting red light are included. A phosphorescent composition containing the second phosphorescent compound, a phosphorescent composition containing three phosphorescent compounds each having one kind of phosphorescent unit emitting blue, green and red, Examples thereof include, but are not limited to, a phosphorescent composition containing two phosphorescent compounds each having one phosphorescent unit emitting blue and orange.

  It is desirable that the organic polymer phosphorescent compound of the present invention can be formed by a wet process. In the wet method, since a phosphorescent compound is used as a solution, it is necessary to be soluble in an organic solvent or water. In particular, in order to make the phosphorescent compound soluble in an organic solvent, it is desirable to use a metal complex in which the phosphorescent moiety is substituted with a relatively long carbon chain such as an alkyl group or an alkoxy group.

  The organic polymer phosphorescent compound of the present invention preferably has a polymerization degree of 5 to 5,000. When the degree of polymerization is less than 5, it becomes difficult to form a uniform film, and crystallization is likely to occur, resulting in poor film stability. An organic polymer having a degree of polymerization greater than 5000 is difficult to produce and is difficult to dissolve in an organic solvent. Therefore, by setting the polymerization degree to 5 to 5000, a uniform and stable film can be formed.

  Next, the organic light emitting device of the present invention will be described.

  In the organic light emitting device of the present invention, the organic polymer phosphorescent compound of the present invention described above can be used as a light emitting material.

  In addition, the organic light emitting device of the present invention uses a composition in which the phosphorescent compound of the present invention and a carrier transport compound are blended as a light emitting material in order to further enhance the carrier transport property of the phosphorescent compound of the present invention. be able to.

  That is, when the phosphorescent compound of the present invention is hole transporting, the electron transporting compound can be mixed, and when the phosphorescent compound of the present invention is electron transporting, the hole transporting compound is mixed. be able to. At this time, each of the electron transporting compound and the hole transporting compound may be a low molecular compound or a high molecular compound.

  As a low molecular weight hole transporting compound to be blended with the phosphorescent compound of the present invention, TPD (N, N′-diphenyl-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-methyl) Known hole transport materials such as triphenylamine derivatives such as phenylphenylamino) triphenylamine) and carbazole derivatives such as CBP (4,4′-NN′-dicarbazole-biphenyl) can be used, It is not limited to these.

  In addition, as the polymer hole transporting compound to be blended with the phosphorescent compound of the present invention, a polymer obtained by introducing a polymerizable functional group into a polyvinylcarbazole, triphenylamine-based low molecular compound, for example, A polymer compound having a triphenylamine skeleton disclosed in JP-A-8-157575 can be used, but is not limited thereto.

On the other hand, examples of the low molecular electron transporting compound to be blended with the phosphorescent compound of the present invention include quinolinol derivative metal complexes such as Alq ₃ (tris aluminum quinolinol), oxadiazole derivatives, triazole derivatives, imidazole derivatives, triazine derivatives, and the like. However, it is not limited to these.

  The polymer electron transport compound to be blended with the phosphorescent compound of the present invention is a polymer obtained by introducing a polymerizable functional group into the above low molecular electron transport compound, for example, Poly PBD etc. which are indicated by 10-1665 gazette can be used, but it is not limited to these.

  In addition, for the purpose of further improving the physical properties of the film obtained by film formation, the phosphorescent compound or phosphorescent composition of the present invention is mixed with a polymer compound that does not participate in the emission characteristics to obtain a composition. This can also be used as a light emitting material. For example, in order to impart flexibility to the film, PMMA (polymethyl methacrylate) can be mixed, but is not limited thereto.

  The present invention also provides an organic light-emitting device comprising at least one layer of the above-described organic polymer phosphorescent compound. In the organic light emitting device of the present invention, since the phosphorescent unit of the phosphorescent compound and the carrier transport unit are linked to the polymer chain, the phosphorescent property of the phosphorescent compound by continuous driving or overheating of the organic light emitting device. Aggregation of units is suppressed, a stable display device can be provided, and phosphorescence units are used instead of fluorescence, so that ultra-high efficiency light emission can be realized.

  The organic light emitting device using the phosphorescent compound of the present invention functions as a single layer structure in which the phosphorescent compound of the present invention is sandwiched between a pair of anode and cathode as shown in FIG. In order to increase the luminous efficiency, a layered structure with an electron transport layer using an electron transport polymer as shown in FIG. 2B or a hole using a hole transport polymer as shown in FIG. A laminated structure with a transport layer is desirable. As these carrier (electron, hole) transport polymers,

のような第３級アミン及びその誘導体（ＨＴＰ１、２）、オキサジアゾール誘導体（ＥＴＰ１、２）、イミダゾール誘導体（ＥＴＰ３）の基を含む高分子、ポリパラフェニレンビニレン（ＣＰ１）、ポリジアルキルフルオレン（ＣＰ２）などが挙げられる。

Tertiary amines and derivatives thereof (HTP1,2), oxadiazole derivatives (ETP1,2), polymers containing groups of imidazole derivatives (ETP3), polyparaphenylene vinylene (CP1), polydialkylfluorene ( CP2) and the like.

  In the light emitting device having the laminated structure of FIG. 2B, the organic light emitting device using the polymer P1 as the phosphorescent compound and the polymer ETP2 containing an oxadiazole derivative group as the electron transporting polymer. Now, the light emission mechanism will be briefly described. The electrons injected from the metal cathode are transported through the electron transport layer and injected into the layer of the phosphorescent compound P1, while the holes injected from the ITO anode are repeating units containing the carbazole ring of the phosphorescent compound P1. Conduct. The injected electrons recombine with holes on the carbazole ring to generate an excited state of the repeating unit of the carbazole ring, and then transfer to the repeating unit of the iridium complex. As a result, an excited triplet state is formed in the repeating unit of the iridium complex, and phosphorescence is observed by energy relaxation. However, a mechanism in which recombination of injected holes and electrons occurs on the repeating unit of the iridium complex is also conceivable.

  The anode is generally formed on a glass substrate that is a transparent substrate, and a light-transmitting material is used. ITO (indium tin oxide), indium oxide, tin oxide, or an indium zinc oxide alloy is preferable. A thin film of a metal such as gold, platinum, silver, or magnesium may be used. Conductive polymers composed of polyaniline, polythiophene, polypyrrole, and derivatives thereof can also be used.

  For the cathode, it is preferable to use an alkali metal such as Li or K having a low work function or an alkaline earth metal such as Mg or Ca from the viewpoint of electron injection efficiency. It is also desirable to use Al that is chemically stable compared to these metals. In order to achieve both electron injection efficiency and chemical stability, a layer containing two or more materials may be used. These materials are described in JP-A-2-15595, JP-A-5-121172, and the like, and a thin layer (about 0.01 to 10 μm) of an alkali metal or alkaline earth metal such as cesium, calcium, strontium, and barium. May be sandwiched under the Al layer (the cathode side is the upper side and the anode side is the lower side).

  The anode and the cathode can be formed by a known method such as vacuum deposition, sputtering, or ion plating. The patterning of the electrode (particularly, the electrode of the light-transmitting material) is preferably performed by chemical etching using photolithography, physical etching using a laser, or the like. Further, patterning may be performed by stacking masks and performing vacuum deposition, sputtering, or the like.

  In the present invention, a plastic substrate can be used in addition to a normal glass substrate as the transparent substrate. The plastic used as the substrate must be excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, workability, low air permeability and low moisture absorption. Examples of such plastic include polyethylene terephthalate, polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone, polyarylate, and polyimide. By using these flexible substrates, a flexible organic light emitting element can be provided. It is preferable to provide a moisture permeation preventive layer (gas barrier layer) on the surface of the substrate on the electrode side, the surface opposite to the electrode, or both surfaces. As a material constituting the moisture permeation preventing layer, inorganic substances such as silicon nitride and silicon oxide are preferable. The moisture permeation preventing layer can be formed by a high frequency sputtering method or the like. Moreover, you may provide a hard-coat layer and an undercoat layer as needed.

  As a method for forming an organic polymer layer such as a phosphorescent compound, an electron transporting polymer, and a hole transporting polymer, a spin coating method from a solution is generally used. Examples of the method for easily producing the layer include a printing method, an inkjet method, a spray method, a dispenser method, and the like, but are not limited thereto. As a result, in the display device in which each pixel of the display screen is composed of the organic light emitting device of the present invention, the organic polymer can be separately applied to each pixel, and the display screen of the display device can be made full color. In particular, the ink jet method can easily perform the pixel-by-pixel painting and full color display screen.

  In the display device in which each pixel of the display screen is composed of the organic light emitting device of the present invention, an active matrix display device can be provided by arranging two or more transistors for each pixel and by addressing and driving the pixels by these transistors. . Of the two required transistors, one is a driving transistor that injects current into the organic light-emitting element that constitutes the pixel, and the other one controls on / off of current injection into the driving transistor. This is a switching transistor. Further, by making these transistors organic transistors, application to plastic substrates is possible.

[Example]
Examples of the phosphorescent compound of the present invention and the synthesis method thereof will be described below. These examples are merely illustrative examples, and the present invention is not limited to these examples.

(Example 1-1) Monomer of phosphorescent compound: [2- (3-methacrylphenyl) pyridine] bis [2- (3-propionylphenyl) pyridine] iridium (III) (hereinafter referred to as Ir (MPPy)) Synthesis of (PrCOPPy) ₂ ) First, 2- (3-methoxyphenyl) pyridine (MeOPPy) was synthesized according to a conventional method of Scheme (1).

具体的には、３−ブロモアニソール８．９８ｇ（４８ｍｍｏｌ）を脱水テトラヒドロフラン（ＴＨＦ）６０ｍｌ中でＭｇを用いて３−メトキシフェニルマグネシウムブロミドを合成した。さらに、２−ブロモピリジン６．３２ｇ（４０ｍｍｏ１）、［１，２−ビス（ジフェニルホスフィノ）エタン］ジクロロニッケル（０）（Ｎｉ（ｄｐｐｅ）Ｃｌ_２）０．７４ｇを脱水ＴＨＦ４０ｍｌに溶解した溶液に、先に得られた３−メトキシフェニルマグネシウムブロミドを添加し、室温で１２時間反応させることにより無色透明の２−（３−メトキシフェニル）ピリジン（ＭｅＯＰＰｙ）を６．０３ｇ（３２．４ｍｍｏｌ）得た。同定はＣＨＮ元素分析、ＮＭＲ、ＩＲで行った。

Specifically, 3-methoxyphenylmagnesium bromide was synthesized using 8.98 g (48 mmol) of 3-bromoanisole in 60 ml of dehydrated tetrahydrofuran (THF) using Mg. Further, in a solution of 6.32 g (40 mmol) of 2-bromopyridine and 0.74 g of [1,2-bis (diphenylphosphino) ethane] dichloronickel (0) (Ni (dppe) Cl ₂ ) dissolved in 40 ml of dehydrated THF. Then, 3-methoxyphenylmagnesium bromide obtained above was added and reacted at room temperature for 12 hours to obtain 6.03 g (32.4 mmol) of colorless and transparent 2- (3-methoxyphenyl) pyridine (MeOPPy). . Identification was performed by CHN elemental analysis, NMR, and IR.

Next, MeOPPy obtained in scheme (1) and tris (acetylacetonato) iridium (III) (Ir (acac) ₃ ) are reacted at high temperature as shown in scheme (2), and tris (2- (3-Methoxyphenyl) pyridine) iridium (III) (Ir (MeOPPy) ₃ ) was synthesized.

具体的には、ＭｅＯＰＰｙ０．５０ｇ（２．７０ｍｍｏｌ）とＩｒ（ａｃａｃ）_３０．２０ｇ（０．４１ｍｍｏｌ）をグリセロール２０ｍｌ中、２５０℃で９時間反応させ、カラムで精製することにより、蛍光性黄色粉末としてＩｒ（ＭｅＯＰＰｙ）_３０．０２０ｇ（０．０２７ｍｍｏｌ）を得た。同定はＣＨＮ及びＩｒ元素分析、ＩＲで行った。

Specifically, 0.50 g (2.70 mmol) of MeOPPy and 0.20 g (0.41 mmol) of Ir (acac) ₃ were reacted in 20 ml of glycerol at 250 ° C. for 9 hours, and purified by a column. As a powder, 0.020 g (0.027 mmol) of Ir (MeOPPy) ₃ was obtained. Identification was performed by CHN and Ir elemental analysis and IR.

Ir (MeOPPy) ₃ obtained in scheme (2) is hydrolyzed to form an OH group by hydrolyzing the MeO group in an aqueous hydrochloric acid solution in accordance with the usual method of scheme (3) to obtain tris (2- (3-hydroxyphenyl) powder. ) Pyridine) iridium (III) (Ir (HOPPy) ₃ ).

スキーム（３）で得られたＩｒ（ＨＯＰＰｙ）_３を、スキーム（４）に従い、メタクリル酸クロリドとモル比１：１で反応させることにより、ＯＨ基の一部分をメタクリル化させＩｒ（ＭＰＰｙ）（ＨＯＰＰｙ）_２が主成分となる錯体を合成した。次いで残りのＯＨ基をプロピオン酸クロリド（ＰｒＣＯＣｌ）と反応させ、Ｉｒ（ＭＰＰｙ）（ＰｒＣＯＰＰｙ）_２が主成分となる錯体を得た。

According to scheme (4), Ir (HOPPy) ₃ obtained in scheme (3) is reacted with methacrylic acid chloride at a molar ratio of 1: 1 to methacrylate a part of the OH group to give Ir (MPPy) (HOPPy). ) A complex having ₂ as a main component was synthesized. Subsequently, the remaining OH group was reacted with propionic acid chloride (PrCOCl) to obtain a complex mainly composed of Ir (MPPy) (PrCOPPy) ₂ .

具体的には、反応容器に脱水ＴＨＦ８ｍｌ、Ｉｒ（ＨＯＰＰｙ）_３０．７０６ｇ（１ｍｍｏｌ）、脱酸剤としてトリエチルアミン０．６００ｇ（５．９ｍｍｏ１）を入れた後、メタクリル酸クロリド０．１０６ｇ（１ｍｍｏｌ）を脱水ＴＨＦ４ｍｌに溶解した溶液を３０分かけて滴下し、２０℃で５時間反応させた。この反応溶液に更にプロピオン酸クロリド０．３７０ｇ（４ｍｍｏｌ）を脱水ＴＨＦ４ｍｌに溶解した溶液を３０分かけて滴下し、２０℃で５時間反応させることにより残りのＯＨ基を反応させ、トリエチルアミンの塩酸塩を濾別した。濾液の溶媒を蒸発乾固し、得られた固形成分はクロロホルム／メタノール混合溶媒にて再結晶を２回行うことによって精製し、目的とするＩｒ（ＭＰＰｙ）（ＰｒＣＯＰＰｙ）_２０．５２３ｇ（０．５９ｍｍｏｌ）を粉末として得た。この錯体の同定はＣＨＮ及びＩｒの元素分析、ＩＲで行った。

Specifically, 8 ml of dehydrated THF, 0.706 g (1 mmol) of Ir (HOPPy) _{3 and} 0.600 g (5.9 mmol) of triethylamine as a deoxidizing agent were placed in a reaction vessel, and then 0.106 g (1 mmol) of methacrylic acid chloride. Was added dropwise over 30 minutes and reacted at 20 ° C. for 5 hours. To this reaction solution, a solution of 0.370 g (4 mmol) of propionic acid chloride dissolved in 4 ml of dehydrated THF was added dropwise over 30 minutes, and the remaining OH group was reacted by reacting at 20 ° C. for 5 hours to obtain triethylamine hydrochloride. Was filtered off. The solvent of the filtrate was evaporated to dryness, and the obtained solid component was purified by recrystallization twice with a chloroform / methanol mixed solvent, and the target Ir (MPPy) (PrCOPPy) ₂ 0.523 g (0. 59 mmol) as a powder. This complex was identified by CHN and Ir elemental analysis and IR.

(Example 1-2) Phosphorescent compound: [2- (3-methacrylphenyl) pyridine] bis [2- (3-propionylphenyl) pyridine] iridium (III) / N-vinylcarbazole copolymer (hereinafter, Synthesis of Ir (MPPy) (PrCOPPy) ₂ / VCz copolymer) According to scheme (5), 0.222 g (0.25 mmol) of Ir (MPPy) (PrCOPPy) ₂ complex synthesized in Example 1 in a reaction vessel N-vinylcarbazole (VCz) 0.918 g (4.75 mmol) (Ir (MPPy) (PrCOPPy) ₂ and VCz in a molar ratio of 5:95), 2,2′-azobis (isobutyronitrile) (AIBN) ) 0.010 g (0.061 mmol) and 10 ml of butyl acetate were added to perform nitrogen substitution, followed by reaction at 80 ° C. for 10 hours. It was.

反応後、生成物をアセトンに投入して再沈殿を行い、濾過により共重合体を回収した。回収した共重合体のクロロホルム溶液をメタノール中に投入して再沈殿させることを更に２回行うことにより精製し、沈殿回収後に真空乾燥して、目的とするＩｒ（ＭＰＰｙ）（ＰｒＣＯＰＰｙ）_２／ＶＣｚ共重合体０．９４６ｇを粉末として得た。得られた共重合体のＣＨＮ及びＩｒの元素分析は、Ｉｒ（ＭＰＰｙ）（ＰｒＣＯＰＰｙ）_２とＶＣｚが５：９５のモル比で共重合していることを支持していた。即ち燐光発光性単位の繰り返し数ｍ／キャリア輸送性単位の繰り返し数ｎ＝５／９５であると考えられる。また、共重合体のクロロホルム中のＧＰＣから、重量平均分子量はポリスチレン換算で１２０００であった（重量平均分子量から計算される平均の重合度は３７）。さらに本発明の燐光発光性化合物はクロロホルムなどの有機溶剤に可溶である。

After the reaction, the product was put into acetone for reprecipitation, and the copolymer was recovered by filtration. The recovered chloroform solution of the copolymer is put into methanol and reprecipitated twice to purify, and after the precipitate is recovered, vacuum drying is performed to obtain the target Ir (MPPy) (PrCOPPy) ₂ / VCz. 0.946 g of copolymer was obtained as a powder. Elemental analysis of CHN and Ir of the resulting copolymer supported that Ir (MPPy) (PrCOPPy) ₂ and VCz were copolymerized in a molar ratio of 5:95. That is, it is considered that the number of repeating phosphorescent units m / the number of repeating carrier transporting units n = 5/95. Moreover, from GPC in chloroform of a copolymer, the weight average molecular weight was 12000 in terms of polystyrene (the average degree of polymerization calculated from the weight average molecular weight was 37). Furthermore, the phosphorescent compound of the present invention is soluble in an organic solvent such as chloroform.

Example 1-3 Trial Manufacture of Organic Light-Emitting Element A chloroform solution of an Ir (MPPy) (PrCOPPy) ₂ / VCz copolymer and an oxadiazole derivative (tBu-PBD) as an electron transport material was prepared. The ratio was 65 weight percent for Ir (MPPy) (PrCOPPy) ₂ / VCz copolymer and 35 weight percent for tBu-PBD. This solution is spin-coated on a glass substrate with indium tin oxide (ITO), which is a transparent electrode, to form a 100 nm thick film, on which 10 nm of Ca and 100 nm of Al are vapor deposited by vacuum deposition. It was. When a positive voltage was applied to the ITO side of the organic light emitting device and a negative voltage was applied to the Al side, green light emission due to the iridium complex was observed. The emission quantum efficiency was about 4%.

(Example 2-1) Monomer of phosphorescent compound: {2- [3- (2-methacryloyloxyethyl) carbamoyloxyphenyl] pyridine} bis [2- (3-propionylphenyl) pyridine] iridium (III ) (Hereinafter, abbreviated as Ir (MiPPy) (PrCOPPy) ₂ ) The monomer intermediate Ir (HOPPy) ₃ synthesized in Example 1-1 was converted into methacryloyloxyethyl isocyanate as shown in Scheme (6). It was made to react 1: 1 with Naert (MOI, Showa Denko), and then the remaining OH group was reacted with PrCOCl to obtain a complex containing Ir (MiPPy) (PrCOPPy) ₂ as a main component.

具体的には、反応容器に脱水ＴＨＦ８ｍｌ、Ｉｒ（ＨＯＰＰｙ）_３０．７０６ｇ（１ｍｍｏｌ）、ＭＯＩ０．１０６ｇ（１ｍｍｏｌ）を入れて、２０℃で５時間反応させた。ごの反応溶液に脱酸剤としてトリエチルアミン０．６００ｇ（５．９ｍｍｏ１）を加えた後、プロピオニルクロリド０．３７０ｇ（４ｍｍｏｌ）を脱水ＴＨＦ４ｍｌに溶解させた溶液を３０分かけて滴下し、更に２０℃で５時間反応させることにより残りのＯＨ基を反応させ、トリエチルアミンの塩酸塩を濾別した。濾液の溶媒を蒸発乾固し、得られた固形成分はクロロホルム／メタノール混合溶媒で再結晶を２回行うことにより精製し、目的とするＩｒ（ＭｉＰＰｙ）（ＰｒＣＯＰＰｙ）_２０．６１３ｇ（０．６３ｍｍｏｌ）を粉末として得た。この同定はＣＨＮ及びＩｒの元素分析、ＩＲで行った。

Specifically, 8 ml of dehydrated THF, 0.706 g (1 mmol) of Ir (HOPPy) _{3 and} 0.106 g (1 mmol) of MOI were put in a reaction vessel, and reacted at 20 ° C. for 5 hours. After adding 0.600 g (5.9 mmol) of triethylamine as a deoxidizer to the reaction solution, a solution prepared by dissolving 0.370 g (4 mmol) of propionyl chloride in 4 ml of dehydrated THF was added dropwise over 30 minutes, and further 20 ° C. The remaining OH groups were reacted by reacting for 5 hours at rt and the triethylamine hydrochloride was filtered off. The solvent of the filtrate was evaporated to dryness, and the obtained solid component was purified by recrystallization twice with a chloroform / methanol mixed solvent to obtain 0.613 g (0.63 mmol) of the desired Ir (MiPPy) (PrCOPPy) _2. ) Was obtained as a powder. This identification was performed by elemental analysis of CHN and Ir and IR.

Example 2-2 Phosphorescent Compound: {2- [3- (2-Methacryloyloxyethyl) carbamoyloxyphenyl] pyridine} bis [2- (3-propionylphenyl) pyridine] iridium (III) / N— Synthesis of vinyl carbazole copolymer (hereinafter, abbreviated as Ir (MiPPy) (PrCOPPy) ₂ / VCz copolymer) Ir (MiPPy) (PrCOPPy) ₂ complex synthesized in Example 3 in a reaction vessel according to scheme (7) 0.243 g (0.25 mmol), N-vinylcarbazole (VCz) 0.918 g (4.75 mmol) (Ir (MiPPy) (PrCOPPy) ₂ and VCz in a molar ratio of 5:95), 2,2′-azobis (Isobutyronitrile) (AIBN) 0.010 g (0.061 mmol), 10 ml of butyl acetate After nitrogen substitution was was reacted at 80 ° C. 10 hours.

反応後、アセトンに投入して再沈殿を行い、濾過により共重合体を回収した。回収した共重合体のクロロホルム溶液をメタノール中に投入して再沈殿させることを更に２回行うことにより精製し、沈殿回収後に真空乾燥して、目的とするＩｒ（ＭｉＰＰｙ）（ＰｒＣＯＰＰｙ）_２／ＶＣｚ共重合体１．０５３ｇを粉末として得た。得られた共重合体のＣＨＮ及びＩｒの元素分析はＩｒ（ＭｉＰＰｙ）（ＰｒＣＯＰＰｙ）_２とＶＣｚが５：９５のモル比で共重合していることを支持していた。即ち燐光発光性単位の繰り返し数ｍ／キャリア輸送性単位の繰り返し数ｎ＝５／９５であると考えられる。また、共重合体のクロロホルム中のＧＰＣから、重量平均分子量はポリスチレン換算で２３０００であった（重量平均分子量から計算される平均の重合度は６４）。さらに本発明の燐光発光性化合物はクロロホルムなどの有機溶剤に可溶である。

After the reaction, it was poured into acetone for reprecipitation, and the copolymer was recovered by filtration. The recovered chloroform solution of the copolymer is added to methanol and reprecipitated twice to purify, and after the precipitate is recovered, vacuum drying is performed to obtain the target Ir (MiPPy) (PrCOPPy) ₂ / VCz. 1.053 g of copolymer was obtained as a powder. Elemental analysis of CHN and Ir of the resulting copolymer supported that Ir (MiPPy) (PrCOPPy) ₂ and VCz were copolymerized in a molar ratio of 5:95. That is, it is considered that the number of repeating phosphorescent units m / the number of repeating carrier transporting units n = 5/95. Moreover, from GPC in chloroform of a copolymer, the weight average molecular weight was 23000 in polystyrene conversion (the average degree of polymerization calculated from the weight average molecular weight was 64). Furthermore, the phosphorescent compound of the present invention is soluble in an organic solvent such as chloroform.

Example 2-3 Trial Manufacture of Organic Light-Emitting Element A chloroform solution of Ir (MiPPy) (PrCOPPy) ₂ / VCz copolymer and tBu-PBD was prepared. The ratio was 65 weight percent for Ir (MiPPy) (PrCOPPy) ₂ / VCz copolymer and 35 weight percent for tBu-PBD. This solution was spin-coated on a glass substrate with ITO to form a film having a thickness of 100 nm, and a cathode was deposited thereon by vapor deposition of 10 nm of Ca and 100 nm of Al. When a positive voltage was applied to the ITO side of the organic light emitting device and a negative voltage was applied to the Al side, green light emission due to the iridium complex was observed. The emission quantum efficiency was about 3%.

(Example 3-1) Phosphorescent compound: [2- (3-hexylphenyl) pyridine] bis (2-phenylpyridine) iridium (III) / 3-hexylthiophene copolymer (hereinafter referred to as Ir (HPPy) PPy) ₂ / HT copolymer) As shown in Scheme (8), 0.099 g (0.25 mmol) of 5-bromo-2- (4-bromo-3-hexylphenyl) pyridine (HPPyBr ₂ ) and According to a conventional method, 1.549 g (4.75 mmol) of 3-hexyl-2,5-dibromothiophene (HTBr ₂ ) ((HPPyBr ₂ ) and (HTBr ₂ ) in a molar ratio of 5:95) was added to dimethylformamide (DMF ) Copolymerized with Ni (COD) ₂ (0) (where COD represents a cyclooctadienyl group) catalyst in 10 ml, and 2- (3-hexyl Nyl) pyridine / 3-hexylthiophene copolymer (HPPy / HT copolymer) was synthesized. Next, 0.625 g (4 mmol) of this HPPy / HT copolymer and 0.099 g (0.2 mmol) of Ir (acac) ₃ were dissolved in metacresol and reacted at 250 ° C. for 10 hours. Further, 0.062 g (0.4 mmol) of phenylpyridine (PPy) was added to this solution and reacted at 250 ° C. for 10 hours.

反応後、アセトンに投入して再沈殿を行い、濾過により共重合体を回収した。回収した共重合体のＤＭＦ溶液をアセトン中に投入して再沈殿を更に２回行うことにより精製し、沈殿回収後に真空乾燥して、目的とするＩｒ（ＨＰＰｙ）ＰＰｙ_２／ＨＴ共重合体０．５６４ｇを粉末として得た。

After the reaction, it was poured into acetone for reprecipitation, and the copolymer was recovered by filtration. The recovered DMF solution of the copolymer is put into acetone and re-precipitated twice to purify it. After the precipitate is recovered, it is vacuum dried to obtain the desired Ir (HPPy) PPy ₂ / HT copolymer 0. .564 g was obtained as a powder.

  Elemental analysis of CHN and Ir in the copolymer supported the putative structure. That is, it is considered that the number of repeating phosphorescent units m / the number of repeating carrier transporting units n = 5/95. Moreover, from GPC of the copolymer in hexafluoroisopropanol, the weight average molecular weight was 18000 in polystyrene conversion (the average degree of polymerization calculated from the weight average molecular weight was 68). Furthermore, the phosphorescent compound of the present invention is soluble in an organic solvent such as DMF.

Example 3-2 Trial Manufacture of Organic Light-Emitting Element A chloroform solution of Ir (HPPy) PPy ₂ / HT copolymer and tBu-PBD was prepared. The ratio was 35 weight percent for tBu-PBD with respect to 65 weight percent for Ir (HPPy) PPy ₂ / HT copolymer. This solution was spin-coated on a glass substrate with ITO to form a film having a thickness of 100 nm, and a cathode was deposited thereon by vapor deposition of 10 nm of Ca and 100 nm of Al. When a positive voltage was applied to the ITO side of the organic light emitting device and a negative voltage was applied to the Al side, yellow light emission due to the iridium complex was observed. The emission quantum efficiency was about 1%.

(Example 4-1) Monomer of electron transport compound: 2- (4-tert-butyl-phenyl)-(4′-vinyl-biphenyl-4-yl)-[1,3,4] oxadi Synthesis of azole (hereinafter abbreviated as VPBD) VPBD was synthesized according to the method disclosed in JP-A-10-1665.

(Example 4-2) Phosphorescent compound: [2- (3-methacrylphenyl) pyridine] bis [2- (3-propionylphenyl) pyridine] iridium (III) / N-vinylcarbazole / 2- (4- tert-butyl-phenyl) -5- (4′-vinyl-biphenyl-4-yl)-[1,3,4] oxadiazole copolymer (hereinafter Ir (MPPy) (PrCOPPy) ₂ / VCz / VPBD Synthesis of abbreviated as a copolymer) According to the following scheme (9), Ir (MPPy) (PrCOPPy) ₂ complex synthesized in Example 1-1 0.222 g (0.25 mmol), VCz 0.628 g (3.25 mmol) 0.571 g (1.50 mmol) of VPBD synthesized in Example 4-1 above (molar ratio Ir (MPPy) (PrCOPPy) ₂ : VCz: VPBD = 5: 65: 30), 2,2′-azobis (isobutyronitrile) (AIBN) 0.010 g (0.061 mmol), and 10 ml of benzene were placed in a reaction vessel and purged with nitrogen. For 10 hours.

After the reaction, the product was put into acetone for reprecipitation, and the copolymer was recovered by filtration. The recovered chloroform solution of the copolymer is added to methanol and re-precipitated twice to purify, and the precipitate is recovered and vacuum dried to obtain the target Ir (MPPy) (PrCOPPy) ₂ / VCz. 0.080 g of a / VPBD copolymer was obtained as a powder.

得られた共重合体（燐光発光性化合物）のＣＨＮ及びＩｒの元素分析は、モル比がＩｒ（ＭＰＰｙ）（ＰｒＣＯＰＰｙ）_２：ＶＣｚ：ＶＰＢＤ＝５：６５：２５で共重合していることを支持していた。すなわち、（燐光発光性単位の繰り返し数：ｋ）／（キャリア輸送単位の繰り返し数ｍ＋ｎ）＝５／９０であると考えられる。また、共重合体のクロロホルム中のＧＰＣから、共重合体の重量平均分子量はポリスチレン換算で３００００であった（重量平均分子量から計算される平均の重合度は２．５）。この共重合体は、クロロホルムなどの有機溶剤に可溶である。

The elemental analysis of CHN and Ir of the obtained copolymer (phosphorescent compound) shows that the molar ratio is Ir (MPPy) (PrCOPPy) ₂ : VCz: VPBD = 5: 65: 25. I supported it. That is, it is considered that (the number of repeating phosphorescent units: k) / (the number of repeating carrier transport units m + n) = 5/90. Moreover, from GPC in chloroform of the copolymer, the weight average molecular weight of the copolymer was 30000 in terms of polystyrene (the average degree of polymerization calculated from the weight average molecular weight was 2.5). This copolymer is soluble in organic solvents such as chloroform.

(Example 4-3) Trial Production of Organic Light-Emitting Element A chloroform solution of Ir (MPPy) (PrCOPPy) ₂ / VCz / VPBD copolymer obtained in Example 4-2 was prepared. This solution is spin-coated on a glass substrate with indium tin oxide (ITO), which is a transparent electrode, to form a film with a thickness of 100 nm. Then, 10 nm of Ca and 100 nm of Al are evaporated by vacuum deposition. An organic light emitting device was obtained using a cathode. When a voltage was applied with the ITO side of the organic light-emitting element being positive and the Al side being negative, green light emission due to the iridium complex was observed. The emission quantum efficiency was about 3%.

Example 5-1 Synthesis of electron-transporting polymer compound: poly-VPBD (hereinafter abbreviated as PVPBD) PVPBD was synthesized according to the method disclosed in JP-A-10-1655.

(Example 5-2)
A chloroform solution of Ir (MPPy) (PrCOPPy) ₂ / VCz copolymer obtained in Example 1-2 and PVPBD obtained in Example 5-1 was prepared. The ratio was such that Ir (MPPy) (PrCOPPy) ₂ / VCz copolymer was 65% by weight and PVPBD was 35% by weight. This solution is spin-coated on a glass substrate with indium tin oxide (ITO), which is a transparent electrode, to form a 100 nm thick film, on which Ca is deposited by 10 nm and Al by 100 nm. An organic light emitting device was obtained using a cathode. When a voltage was applied with the ITO side of the organic light-emitting device being positive and the Al side being negative, green light emission due to the iridium complex was observed. The light emission quantum efficiency was about 4.5%.

Example 6-1 Monomer having a blue phosphorescent site: Iridium (III) bis (2- (2,4-difluorophenyl) pyridinate) (5-methacryloyloxymethylpicolinate) (hereinafter, Ir ( Synthesis of 2,4-F-ppy) ₂ (abbreviated as 5-CH ₂ MA-pic)) As shown in Scheme (10), iridium (III) bis (2- (2,4-difluorophenyl) pyridinate ) (5- (hydroxymethyl) picolinate) (hereinafter abbreviated as Ir (2,4-F-ppy) ₂ (5-CH ₂ OH-pic)). That is, [Ir (2,4-F-ppy) ₂ Cl] ₂ 121.6 mg (0.1 mmol), 5-hydroxymethylpicolinic acid 45.9 mg (0.3 mmol), sodium carbonate 106.0 mg (1.0 mmol) ) Was added with 10 ml of dehydrated N, N-dimethylformamide under an argon stream and stirred at 80 ° C. for 2 hours. 50 ml of water was added to the reaction solution, followed by extraction with ethyl acetate. The solution was dried over magnesium sulfate, concentrated and purified by column chromatography (silica gel, methanol: chloroform = 1: 19 (volume ratio)). Further, it was recrystallized from hexane / chloroform to obtain 108.7 mg of Ir (2,4-F-ppy) ₂ (5-CH ₂ OH-pic) as yellow crystals. Yield 75%. Identification was performed by ¹ H-NMR and CHN elemental analysis. ¹ H-NMR (270 MHz, DMSO-d ₆ ), ppm: 8.54 (d, 1H, J = 4.6), 8.3-8.2 (m, 2H), 8.1-8.0 (M, 4H), 7.70 (s, 1H), 7.61 (d, 1H, J = 4.9), 7.49 (dd, 1H, J = 6.6, 6.6.6), 7.32 (dd, 1H, J = 6.6, 6.6.6), 6.9-6.7 (m, 2H), 5.71 (dd, 1H, J = 8.9, 2.4) ), 5.46 (dd, 1H, J = 8.5, 2.3), 5.42 (t, 1H, J = 4.6), 4.49 (d, 2H, J = 4.6) . Anal. Found: C48.05, H2.54, N5.86. Calcd: C48.06, H2.50, N5.80.

次いで、スキーム（１１）に示すように、Ｉｒ（２，４−Ｆ−ｐｐｙ）_２（５−ＣＨ_２ＭＡ−ｐｉｃ）を合成した。即ち、Ｉｒ（２，４−Ｆ−ｐｐｙ）_２（５−ＣＨ_２ＯＨ−ｐｉｃ）７２．５ｍｇ（０．１ｍｍｏｌ）と２，６−ジ−ｔｅｒｔ−４−メチルフェノール０．２ｍｇをアルゴン気流下に脱水ジクロロメタン１０ｍｌに溶解し、トリエチルアミン１０１．２ｍｇ（１．０ｍｍｏｌ）とメタクリル酸クロライド５２．３ｍｇ（０．５ｍｍｏｌ）を加え、室温で２時間攪拌した。反応液に水５０ｍｌを加え、クロロホルムで抽出した。その溶液を硫酸マグネシウムで乾燥後、濃縮し、カラムクロマトグラフィー（シリカゲル、メタノール：クロロホルム＝３：９７（体積比））で精製した。さらにそれをヘキサン／クロロホルムより再結晶することにより黄色の結晶としてＩｒ（２，４−Ｆ−ｐｐｙ）_２（５−ＣＨ_２ＭＡ−ｐｉｃ）７０．６ｍｇを得た。収率８９％。同定は^１Ｈ−ＮＭＲとＣＨＮ元素分析で行った。^１Ｈ−ＮＭＲ（２７０ＭＨｚ，ＤＭＳＯ−ｄ_６），ｐｐｍ：８．５３（ｄ，１Ｈ，Ｊ＝５．１），８．２８（ｄ，１Ｈ，Ｊ＝８．４），８．２２（ｄ，１Ｈ，Ｊ＝８．６），８．１−８．０（ｍ，４Ｈ），７．７０（ｓ，１Ｈ），７．６６（ｄ，１Ｈ，Ｊ＝４．９），７．４８（ｄｄ，１Ｈ，Ｊ＝６．５，．６．５），７．３１（ｄｄ，１Ｈ，Ｊ＝６．５，．６．５），６．９−６．７（ｍ，２Ｈ），５．８４（ｓ，１Ｈ），５．７−５．６（ｍ，２Ｈ），５．４７（ｄｄ，１Ｈ，Ｊ＝８．８，２．６），５．２４（ｄ，２Ｈ，Ｊ＝２．７），１．７８（ｓ，３Ｈ）．Ａｎａｌ．Ｆｏｕｎｄ：Ｃ４９．９２，Ｈ２．８７，Ｎ５．２８．Ｃａｌｃｄ：Ｃ５０．００，Ｈ２．８０，Ｎ５．３０．

Next, Ir (2,4-F-ppy) ₂ (5-CH ₂ MA-pic) was synthesized as shown in Scheme (11). That is, Ir (2,4-F-ppy) ₂ (5-CH ₂ OH-pic) 72.5 mg (0.1 mmol) and 2,6-di-tert-4-methylphenol 0.2 mg were added under an argon stream. In 10 ml of dehydrated dichloromethane, 101.2 mg (1.0 mmol) of triethylamine and 52.3 mg (0.5 mmol) of methacrylic acid chloride were added and stirred at room temperature for 2 hours. 50 ml of water was added to the reaction solution and extracted with chloroform. The solution was dried over magnesium sulfate, concentrated, and purified by column chromatography (silica gel, methanol: chloroform = 3: 97 (volume ratio)). Further, it was recrystallized from hexane / chloroform to obtain 70.6 mg of Ir (2,4-F-ppy) ₂ (5-CH ₂ MA-pic) as yellow crystals. Yield 89%. Identification was performed by ¹ H-NMR and CHN elemental analysis. ¹ H-NMR (270 MHz, DMSO-d ₆ ), ppm: 8.53 (d, 1H, J = 5.1), 8.28 (d, 1H, J = 8.4), 8.22 (d , 1H, J = 8.6), 8.1-8.0 (m, 4H), 7.70 (s, 1H), 7.66 (d, 1H, J = 4.9), 7.48. (Dd, 1H, J = 6.5, 6.6.5), 7.31 (dd, 1H, J = 6.5, 6.6.5), 6.9-6.7 (m, 2H), 5.84 (s, 1H), 5.7-5.6 (m, 2H), 5.47 (dd, 1H, J = 8.8, 2.6), 5.24 (d, 2H, J = 2.7), 1.78 (s, 3H). Anal. Found: C49.92, H2.87, N5.28. Calcd: C50.00, H2.80, N5.30.

（実施例６−２）緑色の燐光発光性部位を有する単量体：［６−（４−ビニルフェニル）−２，４−ヘキサンジオナート］ビス（２−フェニルピリジン）イリジウム（ＩＩＩ）（以下Ｉｒ（ｐｐｙ）_２［１−（ＳｔＭｅ）−ａｃａｃ］と略す）の合成
スキーム（１２）に示すように、アセチルアセトンと４−ビニルベンジルクロライドを反応させて６−（４−ビニルフェニル）−２，４−ヘキサジオンを合成した。即ち、水素化ナトリウム１．２３ｇ（６０％ ｉｎ ｏｉｌ）（３１ｍｍｏｌ）を窒素雰囲気下で秤量し、これに乾燥テトラヒドロフラン（以下ＴＨＦと略す）６０ｍｌを加えて氷浴で０℃に冷却した。この懸濁液にアセチルアセトン２．５ｇ（２４ｍｍｏｌ）とヘキサメチルホスホリックトリアミド１ｍｌの混合溶液を滴下すると無色の沈殿が生成した。０℃で１０分間攪拌した後、ｎ−ブチルリチウムのヘキサン溶液（１．６Ｍ）１７．５ｍｌ（２８ｍｍｏｌ）を滴下すると沈殿が溶解し、更に０℃で２０分間攪拌した。得られた薄黄色の溶液に４−ビニルベンジルクロライド４．０ｇ（２６ｍｍｏｌ）を滴下し、反応液を室温に戻して２０分間攪拌後、希塩酸を加えて水層を酸性にした。有機層を飽和塩化ナトリウム水溶液で洗浄し、硫酸マグネシウムで乾燥した後、ロータリーエバポレータで溶媒を留去した。得られた反応混合物をシリカゲルカラムに加えてヘキサン／ジクロロメタンの１：１（体積比）混合溶媒で展開し、主生成物を分取した。得られた溶液から減圧で溶媒を留去することにより、目的とする６−（４−ビニルフェニル）−２，４−ヘキサジオン３．０ｇ（１４ｍｍｏｌ）を褐色の液体として得た。収率５６％。同定はＣＨＮ元素分析、^１Ｈ−ＮＭＲで行った。^１Ｈ ＮＭＲ（ＣＤＣｌ_３）：ｅｎｏｌ；δ７．３３（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ，ａｒｏｍａｔｉｃ），７．１４（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ，ａｒｏｍａｔｉｃ），６．６８（ｄｄ，Ｊ＝８．１Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），５．７０（ｄ，Ｊ＝１７．０Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），５．４６（ｓ，１Ｈ，ｄｉｋｅｔｏｎａｔｅ−ｍｅｔｈｉｎｅ），５．２０（ｄ，Ｊ＝１１．１Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），２．９１（ｔ，Ｊ＝５．７Ｈｚ，２Ｈ，ｍｅｔｈｙｌｅｎｅ），２．５８（ｔ，Ｊ＝７．３Ｈｚ，２Ｈ，ｍｅｔｈｙｌｅｎｅ），２．０３（ｓ，３Ｈ，ｍｅｔｈｙｌ）．ｋｅｔｏ；δ７．３３（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ，ａｒｏｍａｔｉｃ），７．１４（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ，ａｒｏｍａｔｉｃ），６．６８（ｄｄ，Ｊ＝８．１Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），５．７０（ｄ，Ｊ＝１７．０Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），５．２０（ｄ，Ｊ＝１１．１Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），３．５３（ｓ，２Ｈ，Ｃ（＝Ｏ）ＣＨ_２Ｃ（＝Ｏ）），２．８９（ｍ，４Ｈ，ｅｔｈｙｌｅｎｅ），２．１９（ｓ，３Ｈ，ｍｅｔｈｙｌ）．ｅｎｏｌ：ｋｅｔｏ＝６：１．Ｅ．Ａ．：Ｃａｌｃｄ ｆｏｒ Ｃ_１４Ｈ_９Ｏ_２：Ｃ，７７．７５；Ｈ，７．４６．Ｆｏｕｎｄ：Ｃ，７７．４９；Ｈ，７．５２．

(Example 6-2) Monomer having a green phosphorescent moiety: [6- (4-vinylphenyl) -2,4-hexanedionate] bis (2-phenylpyridine) iridium (III) Synthesis of Ir (ppy) ₂ [abbreviated as 1- (StMe) -acac]) As shown in Scheme (12), acetylacetone and 4-vinylbenzyl chloride are reacted to produce 6- (4-vinylphenyl) -2, 4-hexadione was synthesized. That is, 1.23 g (60% in oil) (31 mmol) of sodium hydride 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 was added dropwise to this suspension, a colorless precipitate was formed. After stirring at 0 ° C. for 10 minutes, 17.5 ml (28 mmol) of n-butyllithium in hexane (1.6M) 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-hexadione as a brown liquid. Yield 56%. Identification was performed by CHN elemental analysis and ¹ H-NMR. ¹ H NMR (CDCl ₃ ): enol; δ 7.33 (d, J = 8.1 Hz, 2H, aromatic), 7.14 (d, J = 8.4 Hz, 2H, aromatic), 6.68 (dd, J = 8.1 Hz, 1H, vinylic), 5.70 (d, J = 17.0 Hz, 1H, vinylic), 5.46 (s, 1H, diketonate-methine), 5.20 (d, J = 11 .1 Hz, 1H, vinylic), 2.91 (t, J = 5.7 Hz, 2H, methylene), 2.58 (t, J = 7.3 Hz, 2H, methylene), 2.03 (s, 3H, methyl). keto; δ 7.33 (d, J = 8.1 Hz, 2H, aromatic), 7.14 (d, J = 8.4 Hz, 2H, aromatic), 6.68 (dd, J = 8.1 Hz, 1H, vinylic), 5.70 (d, J = 17.0 Hz, 1H, vinylic), 5.20 (d, J = 11.1 Hz, 1H, vinylic), 3.53 (s, 2H, C (= O) _{CH 2 C (= O))} , 2.89 (m, 4H, ethylene), 2.19 (s, 3H, methyl). enol: keto = 6: 1. E. A. _{: Calcd for C 14 H 9 O} 2: C, 77.75; H, 7.46. Found: C, 77.49; H, 7.52.

次いで、スキーム（１３）に示すように、この６−（４−ビニルフェニル）−２，４−ヘキサンジオンと常法に従い合成した［Ｉｒ（ｐｐｙ）_２Ｃｌ］_２を反応させてＩｒ（ｐｐｙ）_２［１−（ＳｔＭｅ）−ａｃａｃ］を合成した。即ち、［Ｉｒ（ｐｐｙ）_２Ｃｌ］_２３４２ｍｇ（０．３２ｍｍｏｌ）、炭酸ナトリウム１５８ｍｇ（１．５ｍｍｏｌ）および２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール５ｍｇ（０．０２３ｍｍｏｌ）を５ｍｌのＮ，Ｎ−ジメチルホルムアミド（以下ＤＭＦと略す）に溶解し、これに６−（４−ビニルフェニル）−２，４−ヘキサンジオン２１０ｍｇ（０．９７ｍｍｏｌ）を加えて６５℃で１時間加熱攪拌した。次に室温まで冷却した反応溶液に希塩酸水溶液を加えた後、薄黄色の成分をクロロホルムで抽出した。ロータリーエバポレータを用いて溶媒を留去後、残渣を少量のジクロロメタンに溶解し、シリカゲルカラムクロマトグラフィー（展開液：ジクロロメタン）で黄色の主生成物を分取した。この溶液を減圧乾固し、ジクロロメタン−ヘキサン混合溶液を加えて−２０℃で再結晶を行い、目的とするＩｒ（ｐｐｙ）_２［１−（ＳｔＭｅ）−ａｃａｃ］３５４ｍｇ（０．４９ｍｍｏｌ）を薄黄色結晶として得た。収率７８％。同定はＣＨＮ元素分析、^１Ｈ−ＮＭＲで行った。^１Ｈ ＮＭＲ（ＣＤＣｌ_３）：δ８．４７（ｄ，Ｊ＝５．７Ｈｚ，１Ｈ，ｐｐｙ），８．２１（ｄ，Ｊ＝５．７Ｈｚ，１Ｈ，ｐｐｙ），７．９-７．５（ｍ，６Ｈ，ｐｐｙ），７．１８（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ，ｓｔｙｌｙｌ−ａｒｏｍａｔｉｃ），７．００（ｍ，２Ｈ，ｐｐｙ），６．８９（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ，ｓｔｙｌｙｌ−ａｒｏｍａｔｉｃ），６．７５（ｍ，５Ｈ，ｐｐｙ ａｎｄ ｖｉｎｙｌｉｃ），６．２８（ｔ，Ｊ＝７．３Ｈｚ，２Ｈ，ｐｐｙ），７．６７（ｄ，Ｊ＝１７．６Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），５．１９（ｄ，Ｊ＝９．５Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），５．１７（ｓ，１Ｈ，ｄｉｋｅｔｏｎａｔｅ−ｍｅｔｈｉｎｅ），２．６０（ｔ，Ｊ＝７．３Ｈｚ，２Ｈ，ｅｔｈｙｌｅｎｅ），２．３６（ｍ，２Ｈ，ｅｔｈｙｌｅｎｅ），１．７５（ｓ，３Ｈ，ｍｅｔｈｙｌ）．Ｅ．Ａ．：Ｃａｌｃｄ ｆｏｒ Ｃ_３６Ｈ_３１ＩｒＮ_２Ｏ_２：Ｃ，６０．４０；Ｈ，４．３６；Ｎ，３．９１．Ｆｏｕｎｄ：Ｃ，６１．３５；Ｈ，４．３４；Ｎ，３．８３．

Next, as shown in Scheme (13), this 6- (4-vinylphenyl) -2,4-hexanedione was reacted with [Ir (ppy) ₂ Cl] ₂ synthesized according to a conventional method to give Ir (ppy) ₂ [1- (StMe) -acac] was synthesized. That is, [Ir (ppy) ₂ Cl] ₂ 342 mg (0.32 mmol), sodium carbonate 158 mg (1.5 mmol) and 2,6-di-tert-butyl-4-methylphenol 5 mg (0.023 mmol) Dissolved in N, N-dimethylformamide (hereinafter abbreviated as DMF), 210 mg (0.97 mmol) of 6- (4-vinylphenyl) -2,4-hexanedione was added thereto, and the mixture was heated and stirred at 65 ° C. for 1 hour. . Next, a diluted hydrochloric acid aqueous solution was added to the reaction solution cooled to room temperature, and the light yellow component was extracted with chloroform. After distilling off the solvent using a rotary evaporator, the residue was dissolved in a small amount of dichloromethane, and the yellow main product was fractionated by silica gel column chromatography (developing solution: dichloromethane). This solution was dried under reduced pressure, a dichloromethane-hexane mixed solution was added and recrystallization was performed at −20 ° C., and 354 mg (0.49 mmol) of the target Ir (ppy) ₂ [1- (StMe) -acac] was diluted. Obtained as yellow crystals. Yield 78%. Identification was performed by CHN elemental analysis and ¹ H-NMR. ¹ H NMR (CDCl ₃ ): δ 8.47 (d, J = 5.7 Hz, 1H, ppy), 8.21 (d, J = 5.7 Hz, 1H, ppy), 7.9-7.5 ( m, 6H, ppy), 7.18 (d, J = 8.1 Hz, 2H, stylly-aromatic), 7.00 (m, 2H, ppy), 6.89 (d, J = 8.1 Hz, 2H) , Stylly-aromatic), 6.75 (m, 5H, ppy and vinylic), 6.28 (t, J = 7.3 Hz, 2H, ppy), 7.67 (d, J = 17.6 Hz, 1H, vinylic), 5.19 (d, J = 9.5 Hz, 1H, vinylic), 5.17 (s, 1H, diketonate-methine), 2.60 (t, J = 7.3 Hz, 2H, ethylene), 2.36 (m, 2 , Ethylene), 1.75 (s, 3H, methyl). E. A. _{: Calcd for C 36 H 31 IrN} 2 O 2: C, 60.40; H, 4.36; N, 3.91. Found: C, 61.35; H, 4.34; N, 3.83.

（実施例６−３）赤色の燐光発光性部位を有する単量体：［６−（４−ビニルフェニル）−２，４−ヘキサンジオナート］ビス［２−（２−ピリジル）ベンゾチエニル］イリジウム（ＩＩＩ）｛以下Ｉｒ（ｂｔｐ）_２［１−（ＳｔＭｅ）−ａｃａｃ］と略す｝の合成
スキーム（１４）に示すように、アセチルアセトンと４−ビニルベンジルクロライドを反応させて６−（４−ビニルフェニル）−２，４−ヘキサンジオンを合成した。即ち、水素化ナトリウム１．２３ｇ（６０％ ｉｎ ｏｉｌ）（３１ｍｍｏｌ）を窒素雰囲気下で秤量し、これに乾燥テトラヒドロフラン（以下ＴＨＦと略す）６０ｍｌを加えて氷浴で０℃に冷却した。この懸濁液にアセチルアセトン２．５ｇ（２４ｍｍｏｌ）とヘキサメチルホスホリックトリアミド（以下ＨＭＰＡと略す）１ｍｌの混合溶液を滴下すると無色の沈殿が生成した。０℃で１０分間撹拌した後、ｎ−ブチルリチウムのヘキサン溶液（１．６Ｍ）１７．５ｍｌ（２８ｍｏｌ）を滴下すると沈殿が溶解し、更に０℃で２０分間撹拌した。得られた薄黄色の溶液に４−ビニルベンジルクロライド４．０ｇ（２６ｍｍｏｌ）を滴下し、反応液を室温に戻して２０分間撹拌後、希塩酸を加えて水層を酸性にした。有機層を飽和塩化ナトリウム水溶液で洗浄し、硫酸マグネシウムで乾燥した後、ロータリーエバポレータで溶媒を留去した。得られた反応混合物をシリカゲルカラムに加えてヘキサン／ジクロロメタンの１：１（体積比）混合溶媒で展開し、主生成物を分取した。得られた溶液から減圧で溶媒を留去することにより、目的とする６−（４−ビニルフェニル）−２，４−ヘキサンジオン３．０ｇ（１４ｍｍｏｌ）を褐色の液体として得た。収率５６％。同定はＣＨＮ元素分析、^１Ｈ−ＮＭＲで行った。^１Ｈ ＮＭＲ：ｅｎｏｌ；δ７．３３（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ，ａｒｏｍａｔｉｃ），７．１４（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ，ａｒｏｍａｔｉｃ），６．６８（ｄｄ，Ｊ＝８．１Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），５．７０（ｄ，Ｊ＝１７．０Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），５．４６（ｓ，１Ｈ，ｅｎｏｌ−ｍｅｔｈｉｎｅ），５．２０（ｄ，Ｊ＝１１．１Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），２．９１（ｔ，Ｊ＝５．７Ｈｚ，２Ｈ，ｍｅｔｈｙｌｅｎｅ），２．５８（ｔ，Ｊ＝７．３Ｈｚ，２Ｈ，ｍｅｔｈｙｌｅｎｅ），２．０３（ｓ，３Ｈ，ｍｅｔｈｙｌ）．ｋｅｔｏ；δ７．３３（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ，ａｒｏｍａｔｉｃ），７．１４（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ，ａｒｏｍａｔｉｃ），６．６８（ｄｄ，Ｊ＝８．１Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），５．７０（ｄ，Ｊ＝１７．０Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），５．２０（ｄ，Ｊ＝１１．１Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），３．５３（ｓ，２Ｈ，Ｃ（＝Ｏ）ＣＨ_２Ｃ（＝Ｏ）），２．８９（ｍ，４Ｈ，ｅｔｈｙｌｅｎｅ），２．１９（ｓ，３Ｈ，ｍｅｔｈｙｌ）．ｅｎｏｌ：ｋｅｔｏ＝６：１．Ｅ．Ａ．：Ｃａｌｃｄ ｆｏｒ Ｃ_１４Ｈ_９Ｏ_２：Ｃ，７７．７５；Ｈ，７．４６．Ｆｏｕｎｄ：Ｃ，７７．４９；Ｈ，７．５２．

(Example 6-3) Monomer having a red phosphorescent moiety: [6- (4-vinylphenyl) -2,4-hexanedionate] bis [2- (2-pyridyl) benzothienyl] iridium Synthesis of (III) {Hereinafter Abbreviated as Ir (btp) ₂ [1- (StMe) -acac]} As shown in Scheme (14), acetylacetone and 4-vinylbenzyl chloride are reacted to produce 6- (4-vinyl Phenyl) -2,4-hexanedione was synthesized. That is, 1.23 g (60% in oil) (31 mmol) of sodium hydride 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; δ 7.33 (d, J = 8.1 Hz, 2H, aromatic), 7.14 (d, J = 8.4 Hz, 2H, aromatic), 6.68 (dd, J = 8. 1 Hz, 1H, vinylic), 5.70 (d, J = 17.0 Hz, 1H, vinylic), 5.46 (s, 1H, enol-methine), 5.20 (d, J = 11.1 Hz, 1H) , Vinylic), 2.91 (t, J = 5.7 Hz, 2H, methylene), 2.58 (t, J = 7.3 Hz, 2H, methylene), 2.03 (s, 3H, methyl). keto; δ 7.33 (d, J = 8.1 Hz, 2H, aromatic), 7.14 (d, J = 8.4 Hz, 2H, aromatic), 6.68 (dd, J = 8.1 Hz, 1H, vinylic), 5.70 (d, J = 17.0 Hz, 1H, vinylic), 5.20 (d, J = 11.1 Hz, 1H, vinylic), 3.53 (s, 2H, C (= O) _{CH 2 C (= O))} , 2.89 (m, 4H, ethylene), 2.19 (s, 3H, methyl). enol: keto = 6: 1. E. A. _{: Calcd for C 14 H 9 O} 2: C, 77.75; H, 7.46. Found: C, 77.49; H, 7.52.

次いで、スキーム（１５）に示すように、この６−（４−ビニルフェニル）−２，４−ヘキサンジオンと常法（例えばＳ．Ｌａｍａｎｓｋｙ，ｅｔ ａｌ．，Ｉｎｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ，４０，１７０４（２００１）に記載）に従い合成したジ（μ−クロロ）テトラキス（２−（２−ピリジル）ベンゾチエニル）ジイリジウム（以下、［Ｉｒ（ｂｔｐ）_２Ｃｌ］_２と略す。）を反応させてＩｒ（ｂｔｐ）_２［１−（Ｓｔ−Ｍｅ）−ａｃａｃ］を合成した。即ち、［Ｉｒ（ｂｔｐ）_２Ｃｌ］_２２５３ｍｇ（０．２０ｍｍｏｌ）を１０ｍｌのＮ，Ｎ−ジメチルホルムアミド（以下ＤＭＦと略す）に懸濁させ、１６１ｍｇの６−（４−ビニルフェニル）−２，４−ヘキサンジオン（０．７４ｍｍｏｌ）と６４ｍｇの炭酸ナトリウムおよび１．９ｍｇの２，６−ジ−ｔｅｒｔ−ブチル−４−、メチルフェノール（以下ＢＨＴと略す）（０．００８６ｍｍｏｌ）を加えて８０℃で１時間加熱撹拌した。得られた反応混合物に１００ｍｌの水と５０ｍｌのクロロホルムを加えてよく振とうし、有機層を硫酸マグネシウムで乾燥後、ロータリーエバポレータで減圧乾固した。次にジクロロメタンを溶出液として、粗精製物をシリカゲルカラムで精製し、赤褐色の溶液を得た。この溶液を減圧下で濃縮し、ヘキサンを加えて−２０℃で再結晶することによって目的とするＩｒ（ｂｔｐ）_２［１−（ＳｔＭｅ）−ａｃａｃ］１５３ｍｇ（０．１８ｍｍｏｌ）を赤褐色の固体として得た（収率４７％）。同定はＣＨＮ元素分析、^１Ｈ−ＮＭＲで行った。^１Ｈ ＮＭＲ：δ８．４０（ｄ，Ｊ＝５．４Ｈｚ，１Ｈ，ｂｔｐ），７．９７（ｄ，Ｊ＝５．４Ｈｚ，１Ｈ，ｂｔｐ），７．６５（ｍ，６Ｈ，ｂｔｐ），７．１-６．７（ｍ，１０Ｈ，ａｒｏｍａｔｉｃ），６．６３（ｄｄ，Ｊ＝１７．８，１１．１Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），６．２４（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ，ｂｔｐ），６．１６（ｄ，Ｊ＝７．８Ｈｚ，１Ｈ，ｂｔｐ），５．６５（ｄ，Ｊ＝１７．８Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），５．２２（ｓ，１Ｈ，ｄｉｋｅｔｏｎａｔｅ−ｍｅｔｈｉｎｅ），５．１８（ｄ，Ｊ＝１１．１Ｈｚ，１Ｈ，ｖｉｎｙｌｉｃ），２．５６（ｍ，２Ｈ，ｅｔｈｙｌｅｎｅ），２．３７（ｍ，２Ｈ，ｅｔｈｙｌｅｎｅ），１．７５（ｓ，３Ｈ，ｍｅｔｈｙｌ）．Ｅ．Ａ．：Ｃａｌｃｄ ｆｏｒ Ｃ_４０Ｈ_３１ＩｒＮ_２Ｏ_２Ｓ_２：Ｃ，５８．０２；Ｈ，３．７７；Ｎ，３．３８．Ｆｏｕｎｄ：Ｃ，５７．７９；Ｈ，３．８１；Ｎ，３．５５．

Next, as shown in Scheme (15), 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- (St-Me) -acac] was synthesized. That is, 253 mg (0.20 mmol) of [Ir (btp) ₂ Cl] ₂ 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), 64 mg of sodium carbonate and 1.9 mg of 2,6-di-tert-butyl-4-, methylphenol (hereinafter abbreviated as BHT) (0.0086 mmol) were added at 80 ° C. And stirred 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: δ 8.40 (d, J = 5.4 Hz, 1H, btp), 7.97 (d, J = 5.4 Hz, 1H, btp), 7.65 (m, 6H, btp), 7 1-6.7 (m, 10H, aromatic), 6.63 (dd, J = 17.8, 11.1 Hz, 1H, vinylic), 6.24 (d, J = 8.1 Hz, 1H, btp) ), 6.16 (d, J = 7.8 Hz, 1H, btp), 5.65 (d, J = 17.8 Hz, 1H, vinylic), 5.22 (s, 1H, diketonate-methine), 5 .18 (d, J = 11.1 Hz, 1H, vinylic), 2.56 (m, 2H, ethylene), 2.37 (m, 2H, ethylene), 1.75 (s, 3H, methyl). E. A. _{: 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.

（実施例６−４）白色燐光発光性化合物の合成
実施例６−１〜６−３で合成した発光機能を有する３種類の単量体及びホール輸送機能を有するＮ−ビニルカルバゾールを含有する共重合体を合成した。

(Example 6-4) Synthesis of white phosphorescent compound Compound containing three types of monomers having a light emitting function synthesized in Examples 6-1 to 6-3 and N-vinylcarbazole having a hole transport function. A polymer was synthesized.

N-vinylcarbazole 1.55 g (8.0 mmol), Ir (2,4-F-ppy) ₂ (3-ST-pic) 58.0 mg (0.08 mmol), Ir (ppy) ₂ [1- (St -Me) -acac] 1.1 mg (0.0015 mmol), Ir (btp) ₂ [1- (StMe) -acac] 1.2 mg (0.0015 mmol), AIBN 13 mg (0.08 mmol) dissolved in dehydrated toluene 40 ml And argon was blown for another 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 desired blue, green and red colors. As a result, 116.3 mg of a white phosphorescent compound having three types of phosphorescent units emitting light was obtained.

  From the result of Ir elemental analysis of the obtained copolymer (phosphorescent compound), the content of Ir complex (phosphorescent unit) was 1.07 mol%. Moreover, the weight average molecular weight was 12400 in polystyrene conversion from GPC in chloroform of a copolymer.

Example 6-5 Trial Manufacture of Organic Light-Emitting Element Example 1-3 except that the copolymer synthesized in Example 6-2 was used instead of the Ir (MPPy) (PrCOPPy) ₂ / VCz copolymer. In the same manner, an organic light-emitting device was prototyped.

  When a positive voltage was applied to the ITO side of the organic light emitting device and a negative voltage was applied to the Al side, white light emission was observed with the naked eye.

The emission spectrum of the organic light emitting device is shown in FIG. Emission peaks corresponding to three types of phosphorescent units (blue, green, red) were observed at 480 nm, 520 nm, and 620 nm, respectively. The chromaticity of the emission color was (0.32, 0.33).
(Example 7-1) Monomer having a blue phosphorescent moiety: Iridium (III) bis (2- (2,4-difluorophenyl) pyridinate) (3- (4-vinylphenyl) methoxypicolinate) Synthesis of (hereinafter abbreviated as Ir (2,4-F-ppy) ₂ (3-ST-pic)) As shown in Scheme (16), 2- (2,4-difluorophenyl) pyridine was synthesized. . That is, 8.69 g (55.0 mmol) of 2-bromopyridine was dissolved in 200 ml of dehydrated tetrahydrofuran under an argon stream, cooled to −78 ° C., and 38.7 ml (61.9 mmol) of a 1.6 M n-butyllithium hexane solution. ) Was added dropwise over 30 minutes. After dropwise addition, a solution prepared by dissolving 7.5 g (55.0 mmol) of zinc chloride in 50 ml of dehydrated tetrahydrofuran (THF) was further added dropwise over 30 minutes. After the dropwise addition, the temperature was slowly raised to 0 ° C., and 9.65 g (55.0 mmol) of 1-bromo-2,4-difluorobenzene and 2.31 g (2.0 mmol) of tetrakis (triphenylphosphine) palladium (0) were added. After stirring for 6 hours under reflux, 200 ml of saturated brine was added to the reaction solution, and the mixture was extracted with diethyl ether. The extract is dried, concentrated, and purified by column chromatography (silica gel; chloroform: hexane = 1: 1 (volume ratio)) to give 2- (2,4-difluorophenyl) pyridine as a colorless and transparent oil. Obtained. Yield 6.00 g. Yield 63%. Identification was performed by ¹ H-NMR and CHN elemental analysis. ¹ H-NMR (270 MHz, CDCl ₃ ), ppm: 8.71 (d, 1H, J = 4.6 Hz), 8.00 (td, 1H, J = 8.9, 6.5 Hz), 7.8 -7.7 (m, 2H), 7.3-7.2 (over wrapped with CHCl 3, 1H), 7.1-6.8 (m, 2H). Anal. Found: C68.98, H3.80, N7.31. Calcd: C69.11, H3.69, N7.33.

次いで、スキーム（１７）に示すように、イリジウムの２核錯体、ビス（μ−クロロ）テトラキス（２−（２，４−ジフルオロフェニル）ピリジン）ジイリジウム（ＩＩＩ）（以下、［Ｉｒ（２，４−Ｆ−ｐｐｙ）_２Ｃｌ］_２と略す。）を合成した。即ち、２−（２，４−ジフルオロフェニル）ピリジン０．９６ｇ（５．０ｍｍｏｌ）とヘキサクロロイリジウム（ＩＩＩ）酸ナトリウムｎ水和物（和光純薬工業製）１．００ｇを２−エトキシエタノール：水＝３：１の混合溶媒４０ｍｌに溶解し、３０分間アルゴンガスを吹き込んだ後、還流下に５時間攪拌した。生じた沈殿をろ取し、エタノールと少量のアセトンで洗浄し、真空下で５時間乾燥することにより、［Ｉｒ（２，４−Ｆ−ｐｐｙ）_２Ｃｌ］_２を黄色粉末として得た。収量０．７９ｇ。収率８６％。同定は^１Ｈ−ＮＭＲとＣＨＮ元素分析で行った。^１Ｈ−ＮＭＲ（２７０ＭＨｚ，ＣＤＣｌ_３），ｐｐｍ：９．１２（ｄ，４Ｈ，Ｊ＝５．７Ｈｚ），８．３１（ｄ，４Ｈ，Ｊ＝８．６Ｈｚ），７．８３（ｄｄ，４Ｈ，Ｊ＝７．６，７．６Ｈｚ），６．８２（ｄｄ，４Ｈ，Ｊ＝７．３，７．３Ｈｚ），６．３４（ｄｄｄ，４Ｈ，Ｊ＝１１．６，１０．０，２．４Ｈｚ），５．２９（ｄｄ，４Ｈ，Ｊ＝９．５，２．４Ｈｚ）．Ａｎａｌ．Ｆｏｕｎｄ：Ｃ４３．６９，Ｈ３．５３，Ｎ３．５４．Ｃａｌｃｄ：Ｃ４３．８８，Ｈ３．４５，Ｎ３．５６．

Next, as shown in Scheme (17), a binuclear complex of iridium, bis (μ-chloro) tetrakis (2- (2,4-difluorophenyl) pyridine) diiridium (III) (hereinafter referred to as [Ir (2, 4-F-ppy) ₂ Cl] ₂ ) was synthesized. That is, 0.96 g (5.0 mmol) of 2- (2,4-difluorophenyl) pyridine and 1.00 g of sodium hexachloroiridium (III) sodium hydrate (manufactured by Wako Pure Chemical Industries) were mixed with 2-ethoxyethanol: water. = 3: 1 The mixture was dissolved in 40 ml of a mixed solvent, and argon gas was blown for 30 minutes, followed by stirring under reflux for 5 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 (2,4-F-ppy) ₂ Cl] ₂ as a yellow powder. Yield 0.79g. Yield 86%. Identification was performed by ¹ H-NMR and CHN elemental analysis. ¹ H-NMR (270 MHz, CDCl ₃ ), ppm: 9.12 (d, 4H, J = 5.7 Hz), 8.31 (d, 4H, J = 8.6 Hz), 7.83 (dd, 4H) , J = 7.6, 7.6 Hz), 6.82 (dd, 4H, J = 7.3, 7.3 Hz), 6.34 (ddd, 4H, J = 11.6, 10.0, 2 .4 Hz), 5.29 (dd, 4H, J = 9.5, 2.4 Hz). Anal. Found: C43.69, H3.53, N3.54. Calcd: C43.88, H3.45, N3.56.

次いで、スキーム（１８）に示すように、イリジウム（ＩＩＩ）ビス（２−（２，４−ジフルオロフェニル）ピリジナート）（３−ヒドロキシピコリナート）（以下、Ｉｒ（２，４−Ｆ−ｐｐｙ）_２（３−ＯＨ−ｐｉｃ）と略す。）を合成した。即ち、［Ｉｒ（２，４−Ｆ−ｐｐｙ）_２Ｃｌ］_２１２１．６ｍｇ（０．１ｍｍｏｌ）、３−ヒドロキシピコリン酸４１．７ｍｇ（０．３ｍｍｏｌ）、炭酸ナトリウム１０６．０ｍｇ（１．０ｍｍｏｌ）にアルゴン気流下において脱水Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）１０ｍｌを加え、８０℃で２時間攪拌した。反応液に５０ｍｌの水を加えた後、酢酸エチルで抽出した。その溶液を硫酸マグネシウムで乾燥後、濃縮し、カラムクロマトグラフィー（シリカゲル、メタノール：クロロホルム＝３：９７（体積比））で精製した。さらにそれをヘキサン／クロロホルムより再結晶することにより黄色の結晶としてＩｒ（２，４−Ｆ−ｐｐｙ）_２（３−ＯＨ−ｐｉｃ）１０１．０ｍｇを得た。収率７１％。同定は^１Ｈ−ＮＭＲとＣＨＮ元素分析で行った。^１Ｈ−ＮＭＲ（２７０ＭＨｚ，ＤＭＳＯ−ｄ_６），ｐｐｍ：１３．６（ｂｒ，１Ｈ），８．５０（ｄ，１Ｈ，Ｊ＝５．９Ｈｚ），８．２５（ｄ，２Ｈ，Ｊ＝１１．１Ｈｚ），８．１−８．０（ｍ，２Ｈ），７．６９（ｄ，１Ｈ，Ｊ＝５．７Ｈｚ），７．６２（ｄ，１Ｈ，Ｊ＝８．１Ｈｚ），７．５３（ｄ，１Ｈ，Ｊ＝４．６Ｈｚ），７．５０（ｄ，１Ｈ，Ｊ＝５．７Ｈｚ），７．３６（ｔ，１Ｈ，Ｊ＝４．５Ｈｚ），７．２４（ｄ，１Ｈ，Ｊ＝５．１Ｈｚ），６．９−６．７（ｍ，２Ｈ），５．６６（ｄｄ，１Ｈ，Ｊ＝８．６，２．４Ｈｚ），５．４８（ｄｄ，１Ｈ，Ｊ＝８．６，２．４Ｈｚ）．Ａｎａｌ．Ｆｏｕｎｄ：Ｃ４７．２９，Ｈ２．３３，Ｎ５．８６．Ｃａｌｃｄ：Ｃ４７．３２，Ｈ２．２７，Ｎ５．９１．

Next, as shown in Scheme (18), iridium (III) bis (2- (2,4-difluorophenyl) pyridinate) (3-hydroxypicolinate) (hereinafter, Ir (2,4-F-ppy) ₂ (Abbreviated as 3-OH-pic)) was synthesized. That is, [Ir (2,4-F-ppy) ₂ Cl] ₂ 121.6 mg (0.1 mmol), 3-hydroxypicolinic acid 41.7 mg (0.3 mmol), sodium carbonate 106.0 mg (1.0 mmol) Under an argon stream, 10 ml of dehydrated N, N-dimethylformamide (DMF) was added and stirred at 80 ° C. for 2 hours. 50 ml of water was added to the reaction solution, followed by extraction with ethyl acetate. The solution was dried over magnesium sulfate, concentrated, and purified by column chromatography (silica gel, methanol: chloroform = 3: 97 (volume ratio)). Further, it was recrystallized from hexane / chloroform to obtain 101.0 mg of Ir (2,4-F-ppy) ₂ (3-OH-pic) as yellow crystals. Yield 71%. Identification was performed by ¹ H-NMR and CHN elemental analysis. ¹ H-NMR (270 MHz, DMSO-d ₆ ), ppm: 13.6 (br, 1H), 8.50 (d, 1H, J = 5.9 Hz), 8.25 (d, 2H, J = 11) .1 Hz), 8.1-8.0 (m, 2H), 7.69 (d, 1H, J = 5.7 Hz), 7.62 (d, 1H, J = 8.1 Hz), 7.53 (D, 1H, J = 4.6 Hz), 7.50 (d, 1H, J = 5.7 Hz), 7.36 (t, 1H, J = 4.5 Hz), 7.24 (d, 1H, J = 5.1 Hz), 6.9-6.7 (m, 2H), 5.66 (dd, 1H, J = 8.6, 2.4 Hz), 5.48 (dd, 1H, J = 8) .6, 2.4 Hz). Anal. Found: C47.29, H2.33, N5.86. Calcd: C47.32, H2.27, N5.91.

次いで、スキーム（１９）に示すように、Ｉｒ（２，４−Ｆ−ｐｐｙ）_２（３−ＳＴ−ｐｉｃ）を合成した。即ち、Ｉｒ（２，４−Ｆ−ｐｐｙ）_２（３−ＯＨ−ｐｉｃ）１０６．５ｍｇ（０．１５ｍｍｏｌ）、炭酸カリウム２０７．３ｍｇ（１．５ｍｍｏｌ）、２，６−ジ−ｔ−ブチルヒドロキシトルエン０．３ｍｇにアルゴン気流下において脱水Ｎ，Ｎ−ジメチルホルムアミド１５ｍｌを加え、さらに４−ビニルベンジルクロライド９１．５ｍｇ（０．６ｍｍｏｌ）を加え、８０℃で４時間攪拌した。反応液に水１００ｍｌを加えて生成物を沈殿させてろ取し、カラムクロマトグラフィー（シリカゲル、メタノール：クロロホルム＝３：９７（体積比））で精製した。さらにそれをヘキサン／クロロホルムより再結晶することにより黄色の結晶としてＩｒ（２，４−Ｆ−ｐｐｙ）_２（３−ＳＴ−ｐｉｃ）７２．０ｍｇを得た。収率５８％。同定は^１Ｈ−ＮＭＲとＣＨＮ元素分析で行った。^１Ｈ−ＮＭＲ（２７０ＭＨｚ，ＤＭＳＯ−ｄ_６），ｐｐｍ：８．５９（ｄ，１Ｈ，Ｊ＝５．１Ｈｚ），８．３−８．２（ｍ，２Ｈ），８．１−８．０（ｍ，２Ｈ），７．９（ｄ，１Ｈ，Ｊ＝８．６Ｈｚ），７．６７（ｄ，１Ｈ，Ｊ＝５．１Ｈｚ），７．６−７．３（ｍ，７Ｈ），６．９−６．７（ｍ，３Ｈ），５．８５（ｄ，１Ｈ，Ｊ＝１７．８Ｈｚ），５．６７（ｄｄ，１Ｈ，Ｊ＝８．９，２．４Ｈｚ），５．４５（ｄｄ，１Ｈ，Ｊ＝８．９，２．４Ｈｚ），５．２９（ｓ，２Ｈ），５．２７（ｄ，１Ｈ，Ｊ＝１１．１Ｈｚ）．Ａｎａｌ．Ｆｏｕｎｄ：Ｃ５３．７１，Ｈ２．９０，Ｎ５．０３．Ｃａｌｃｄ：Ｃ５３．７５，Ｈ２．９３，Ｎ５．０８．

Next, Ir (2,4-F-ppy) ₂ (3-ST-pic) was synthesized as shown in Scheme (19). That is, Ir (2,4-F-ppy) ₂ (3-OH-pic) 106.5 mg (0.15 mmol), potassium carbonate 207.3 mg (1.5 mmol), 2,6-di-t-butylhydroxy Under an argon stream, 15 ml of dehydrated N, N-dimethylformamide was added to 0.3 mg of toluene, 91.5 mg (0.6 mmol) of 4-vinylbenzyl chloride was further added, and the mixture was stirred at 80 ° C. for 4 hours. 100 ml of water was added to the reaction solution to precipitate the product, which was collected by filtration and purified by column chromatography (silica gel, methanol: chloroform = 3: 97 (volume ratio)). Further, it was recrystallized from hexane / chloroform to obtain 72.0 mg of Ir (2,4-F-ppy) ₂ (3-ST-pic) as yellow crystals. Yield 58%. Identification was performed by ¹ H-NMR and CHN elemental analysis. ¹ H-NMR (270 MHz, DMSO-d ₆ ), ppm: 8.59 (d, 1H, J = 5.1 Hz), 8.3-8.2 (m, 2H), 8.1-8.0 (M, 2H), 7.9 (d, 1H, J = 8.6 Hz), 7.67 (d, 1H, J = 5.1 Hz), 7.6-7.3 (m, 7H), 6 .9-6.7 (m, 3H), 5.85 (d, 1H, J = 17.8 Hz), 5.67 (dd, 1H, J = 8.9, 2.4 Hz), 5.45 ( dd, 1H, J = 8.9, 2.4 Hz), 5.29 (s, 2H), 5.27 (d, 1H, J = 11.1 Hz). Anal. Found: C53.71, H2.90, N5.03. Calcd: C53.75, H2.93, N5.08.

（実施例７−２）青色燐光発光部位を有するＩｒ（２，４−Ｆ−ｐｐｙ）_２（３−ＳＴ−ｐｉｃ）とホール輸送性機能を有するビニルカルバゾールの共重合体（以下、Ｉｒ（２，４−Ｆ−ｐｐｙ）_２（３−ＳＴ−ｐｉｃ）／ＶＣｚ共重合体と略す。）の合成
Ｎ−ビニルカルバゾール９６６ｍｇ（５．０ｍｍｏｌ）および実施例７−１で合成したＩｒ（２，４−Ｆ−ｐｐｙ）_２（３−ＳＴ−ｐｉｃ）４１（０．０５ｍｍｏｌ）、ＡＩＢＮ８．２ｍｇ（０．０５ｍｍｏｌ）を脱水トルエン２５ｍｌに溶解させ、さらに１時間アルゴンを吹き込んだ。この溶液を８０℃まで昇温し、重合反応を開始させ、そのまま８時間攪拌した。冷却後、反応液をメタノール２５０ｍｌ中に滴下して重合物を沈殿させ、濾過により回収した。さらに、回収した重合物をクロロホルム２５ｍｌに溶解させ、この溶液をメタノール２５０ｍｌ中に滴下して再沈殿させることにより精製した後、６０℃で１２時間真空乾燥させることにより目的物であるＩｒ（２，４−Ｆ−ｐｐｙ）_２（３−ＳＴ−ｐｉｃ）／ＶＣｚ共重合体７２２ｍｇを得た。

(Example 7-2) A copolymer of Ir (2,4-F-ppy) ₂ (3-ST-pic) having a blue phosphorescent site and vinylcarbazole having a hole transporting function (hereinafter referred to as Ir (2)) , 4-F-ppy) ₂ (abbreviated as 3-ST-pic) / VCz copolymer)) 966 mg (5.0 mmol) of N-vinylcarbazole and Ir (2,4) synthesized in Example 7-1 -F-ppy) ₂ (3-ST-pic) 41 (0.05 mmol) and AIBN 8.2 mg (0.05 mmol) were dissolved in 25 ml of dehydrated toluene, and argon was blown into the mixture for another 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 Ir (2, 722 mg of 4-F-ppy) ₂ (3-ST-pic) / VCz copolymer was obtained.

  From the result of Ir elemental analysis of the obtained copolymer (phosphorescent compound), the content of Ir complex (phosphorescent unit) was 1.04 mol%. Moreover, the weight average molecular weight was 11400 in polystyrene conversion from GPC in chloroform of a copolymer.

Example 7-3 [6- (4-Vinylphenyl) -2,4-hexanedionate] bis [2- (2-pyridyl) benzothienyl] iridium (III) having a red phosphorescent site and hole transport Of vinyl carbazole copolymer having sexual function (hereinafter abbreviated as Ir (btp) ₂ [1- (StMe) -acac] / VCz copolymer) 1.55 g (8.0 mmol) of N-vinyl carbazole Ir (btp) ₂ [1- (StMe) -acac] synthesized in Example 6-3, 33.1 mg (0.04 mmol), and 13 mg (0.08 mmol) of AIBN were dissolved in 40 ml of dehydrated toluene, and argon was further added for 1 hour. Infused. 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 purified by dripping the solution into 250 ml of methanol and reprecipitating, followed by vacuum drying at 60 ° C. for 12 hours to obtain the target Ir (btp) ₂ [1- (StMe) -acac] / VCz copolymer 1.12 g was obtained.

  From the result of Ir elemental analysis of the obtained copolymer (phosphorescent compound), the content of Ir complex (phosphorescent unit) was 0.59 mol%. Moreover, the weight average molecular weight was 10800 in polystyrene conversion from GPC in chloroform of a copolymer.

(Example 7-4) Trial Production of Organic Light-Emitting Element Ir (2,4-F-ppy) ₂ (3-ST-pic) / VCz Copolymer Synthesized in Example 7-2, in Example 7-3 A synthesized Ir (btp) ₂ [1- (StMe) -acac] / VCz copolymer and a chloroform solution of tBu-PBD were prepared. The ratio is 66.85% by mass of Ir (2,4-F-ppy) ₂ (3-ST-pic) / VCz copolymer, Ir (btp) ₂ [1- (StMe) -acac] / VCz The polymer was 3.15% by mass, and tBu-PBD was 30.00% by mass.

  This solution was spin-coated on a glass substrate with ITO to form a film having a thickness of 100 nm, and a cathode was formed thereon by depositing 10 nm of Ca and 100 nm of Al by vacuum deposition.

  When a positive voltage was applied to the ITO side of the obtained organic light emitting device and a negative voltage was applied to the Al side, white light emission was observed with the naked eye.

The emission spectrum of the organic light emitting device is shown in FIG. The emission peaks corresponding to Ir (2,4-F-ppy) ₂ (3-ST-pic) / VCz copolymer and Ir (btp) ₂ [1- (StMe) -acac] / VCz copolymer are respectively shown. Observed around 480 nm and 620 nm. The chromaticity coordinates were (0.30, 0.35).

[Appendix]
Appendix (1):
A phosphorescent compound of a neutral organic polymer that is used in an organic light emitting device and emits phosphorescence,
A phosphorescent unit that is a repeating unit that emits phosphorescence; and
A carrier transporting unit which is a repeating unit for transporting a carrier;
A phosphorescent compound comprising:

Appendix (2):
The repeating number m of the phosphorescent unit and the repeating number n of the carrier transporting unit are:
m <n
The phosphorescent compound according to appendix (1), which satisfies the relationship:

Appendix (3):
The repeating number m of the phosphorescent unit and the repeating number n of the carrier transporting unit are:
0.0001 ≦ m / (m + n) ≦ 0.2
The phosphorescent compound according to appendix (2), which satisfies the relationship:

Appendix (4):
The phosphorescent compound according to any one of appendices (1) to (3), which is soluble in an organic solvent or water.

Appendix (5):
The phosphorescent compound according to any one of appendices (1) to (4), wherein the degree of polymerization is 5 to 5000.

Appendix (6):
Any one of appendices (1) to (5), wherein the phosphorescent portion of the phosphorescent unit and / or the carrier transporting portion of the carrier transport unit constitutes a side chain. The phosphorescent compound described in 1.

Appendix (7):
Any one of appendices (1) to (5), wherein the phosphorescent light emitting portion of the phosphorescent light emitting unit and / or the carrier transporting portion of the carrier transportable unit constitutes a main chain. The phosphorescent compound described in 1.

Appendix (8):
The phosphorescent compound according to any one of appendices (1) to (7), wherein the carrier transporting part of the carrier transporting unit is a hole transporting part.

Appendix (9):
The phosphorescent compound according to any one of appendices (1) to (7), wherein the carrier transporting moiety of the carrier transporting unit is an electron transporting moiety.

Appendix (10):
The phosphorescent compound according to any one of appendices (1) to (7), wherein the carrier transporting part of the carrier transporting unit comprises a hole transporting part and an electron transporting part.

Appendix (11):
The phosphorescence according to any one of appendices (1) to (10), wherein the phosphorescent site of the phosphorescent unit is a monovalent or divalent group of a transition metal or rare earth metal complex. Luminescent compound.

Appendix (12):
The monovalent group of the transition metal or rare earth metal complex binds to the main chain as a side chain via a spacer moiety,
The spacer part includes an organic group having 1 to 30 carbon atoms which may have a hetero atom or an inorganic group having 1 to 10 hetero atoms which does not have a carbon atom. Phosphorescent compound.

Appendix (13):
The carrier transporting part of the carrier transporting unit is a monovalent group of carbazole, a monovalent group of a tertiary amine, a monovalent group of an imidazole derivative, a monovalent group of a triazole derivative, a monovalent group of an oxadiazole derivative, styrene And (2) a group selected from at least one group selected from the group consisting of a divalent group and a group composed of a divalent group of fluorene and a group obtained by substituting the group with a substituent. The phosphorescent compound as described in any one of thru | or (12).

Appendix (14):
One of the supplementary notes (1) to (13), having one kind of light emitting in a predetermined color or two or more kinds of phosphorescent units emitting light in two or more different colors The phosphorescent compound described.

Appendix (15):
The phosphorescent compound according to appendix (14), wherein the phosphorescent unit is composed of two types that emit blue or green and yellow or red, and emits white as a whole.

Appendix (16):
The phosphorescent compound according to appendix (14), wherein the phosphorescent unit comprises three types that emit blue, green, and red, and emits white as a whole.

Appendix (17):
A phosphorescent composition comprising the phosphorescent compound according to any one of appendices (1) to (16).

Appendix (18):
A phosphorescent composition comprising the phosphorescent compound according to appendix (14), wherein the phosphorescent compound comprises one or more phosphorescent units that emit light of different colors.

Appendix (19):
The phosphorescent composition according to appendix (18), which emits white light as a whole.

Appendix (20):
It comprises a phosphorescent compound having a phosphorescent unit emitting blue or green and a phosphorescent compound having a phosphorescent unit emitting yellow or red, and emits white as a whole. The phosphorescent composition according to appendix (18).

Appendix (21):
A phosphorescent composition comprising the phosphorescent compound or phosphorescent composition according to any one of appendices (1) to (20) and a carrier transporting polymer compound.

Appendix (22):
The phosphorescent composition according to appendix (21), wherein the carrier transporting polymer compound is a hole transporting polymer compound.

Appendix (23):
The phosphorescent composition according to appendix (21), wherein the carrier transporting polymer compound is an electron transporting polymer compound.

Appendix (24):
A phosphorescent composition comprising the phosphorescent compound or phosphorescent composition according to any one of appendices (1) to (20) and a carrier transporting low molecular weight compound.

Appendix (25):
The phosphorescent composition according to appendix (24), wherein the carrier transporting low molecular weight compound is a hole transporting low molecular weight compound.

Appendix (26):
The phosphorescent composition according to appendix (24), wherein the carrier transporting low molecular weight compound is an electron transporting low molecular weight compound.

Appendix (27):
In an organic light emitting device comprising one or more organic polymer layers sandwiched between an anode and a cathode,
At least one layer of the organic polymer layer includes the phosphorescent compound or the phosphorescent composition according to any one of appendices (1) to (26).

Appendix (28):
In an organic light emitting device comprising one or more organic polymer layers sandwiched between an anode and a cathode,
A color filter is disposed between the anode and the transparent substrate on which the anode is provided,
At least one layer of the organic polymer layer contains the phosphorescent compound according to appendix (15) or (16) or the phosphorescent composition according to appendix (19) or (20). Light emitting element.

Appendix (29):
The organic light-emitting element according to appendix (27) or (28), wherein the anode is formed on a plastic substrate.

Appendix (30):
The organic light-emitting element according to any one of appendices (27) to (29), wherein the organic polymer layer is formed by an inkjet method or a printing method.

Appendix (31):
In a display device having a display screen,
Each pixel of the display screen is composed of the organic light emitting device according to any one of appendices (27) to (30),
Each pixel includes two or more transistors.

Claims (27)

A phosphorescent compound of a neutral organic polymer that emits phosphorescence,
The organic polymer is a phosphorescent unit that is obtained by radical polymerization of a vinyl compound and is a repeating unit that emits phosphorescence, and a repeating unit that is obtained by radical polymerization of a vinyl compound and transports carriers. Including a carrier transportable unit,
The phosphorescent site of the phosphorescent unit is a monovalent group of an iridium or platinum complex,
The monovalent group of the iridium or platinum complex is bonded as a side chain via a spacer portion to the main chain of the organic polymer,
The phosphor part is characterized in that the spacer part contains an organic group having 1 to 30 carbon atoms which may have a hetero atom or an inorganic group having 1 to 10 hetero atoms which does not have a carbon atom. . The phosphorescent compound according to claim 1,
The number m of repeating phosphorescent units and the number n of repeating carrier transporting units are:
m <n
A phosphorescent compound characterized by satisfying the relationship: The phosphorescent compound according to claim 2, wherein
The number m of repeating phosphorescent units and the number n of repeating carrier transporting units are:
0.0001 ≦ m / (m + n) ≦ 0.2
A phosphorescent compound characterized by satisfying the relationship: The phosphorescent compound according to any one of claims 1 to 3,
The phosphorescent compound, wherein the organic polymer is soluble in an organic solvent or water. The phosphorescent compound according to any one of claims 1 to 4,
A phosphorescent compound, wherein the organic polymer has a degree of polymerization of 5 to 5000. The phosphorescent compound according to any one of claims 1 to 5,
The phosphorescent compound, wherein a carrier transporting part of the carrier transporting unit is a hole transporting part. The phosphorescent compound according to any one of claims 1 to 5,
The phosphorescent compound, wherein a carrier transporting part of the carrier transporting unit is an electron transporting part. The phosphorescent compound according to any one of claims 1 to 5,
The phosphorescent compound, wherein the carrier transporting part of the carrier transporting unit comprises a hole transporting part and an electron transporting part. The phosphorescent compound according to any one of claims 1 to 8,
The carrier transporting part of the carrier transporting unit includes a monovalent group of carbazole, a monovalent group of a tertiary amine, a monovalent group of an imidazole derivative, a monovalent group of a triazole derivative, a monovalent group of an oxadiazole derivative, And at least one group selected from the group of groups in which the group is substituted with a substituent. The phosphorescent compound according to any one of claims 1 to 9,
The organic polymer has a phosphorescent compound (provided that the organic polymer has one or more phosphorescent units emitting one or more predetermined colors and emitting two or more different colors) Chemical formula

Except for the compounds represented by The phosphorescent compound according to claim 10,
The phosphorescent unit is composed of two types of phosphorescent units that emit blue or green and yellow or red,
The phosphorescent compound is characterized in that it emits white light as a whole. The phosphorescent compound according to claim 10,
The phosphorescent unit is composed of three types of phosphorescent units that emit blue, green, and red,
The phosphorescent compound is characterized in that it emits white light as a whole.   A phosphorescent composition comprising the phosphorescent compound according to any one of claims 1 to 12. A phosphorescent composition comprising a plurality of types of phosphorescent compounds according to claim 10 that emit light in different colors, wherein the chemical formula

The composition consisting of the compound represented by is excluded. ). The phosphorescent composition according to claim 14,
The phosphorescent composition is characterized in that the phosphorescent composition emits white light as a whole. The phosphorescent composition according to claim 15,
The phosphorescent composition includes the phosphorescent compound that emits blue or green light and the phosphorescent compound that emits yellow or red light.   The phosphorescent compound according to any one of claims 1 to 12, or the phosphorescent composition according to any one of claims 13 to 16 and a carrier transporting polymer compound. A phosphorescent composition. The phosphorescent composition according to claim 17,
The phosphorescent composition, wherein the carrier transporting polymer compound is a hole transporting polymer compound. The phosphorescent composition according to claim 17,
The phosphorescent composition, wherein the carrier transporting polymer compound is an electron transporting polymer compound.   A phosphorescent compound according to any one of claims 1 to 12, or a phosphorescent composition according to any one of claims 13 to 16 and a carrier transporting low molecular weight compound. A phosphorescent composition. The phosphorescent composition according to claim 20,
The phosphorescent composition, wherein the carrier transporting low molecular weight compound is a hole transporting low molecular weight compound. The phosphorescent composition according to claim 20,
The phosphorescent composition, wherein the carrier transporting low molecular weight compound is an electron transporting low molecular weight compound. In an organic light emitting device comprising one or a plurality of organic polymer layers sandwiched between an anode and a cathode,
The at least one layer of the organic polymer layer is a phosphorescent compound according to any one of claims 1 to 12, or a phosphorescent composition according to any one of claims 13 to 22. An organic light-emitting device comprising: In an organic light emitting device comprising one or a plurality of organic polymer layers sandwiched between an anode and a cathode,
While having a color filter between the anode and the transparent substrate provided with the anode,
At least one layer of the organic polymer layer includes the phosphorescent compound according to claim 11 or 12, or the phosphorescent composition according to claim 15 or 16. The organic light-emitting device according to claim 23 or 24,
The organic light-emitting device, wherein the anode is formed on a plastic substrate. In the organic light emitting element according to any one of claims 23 to 25,
The organic light emitting element, wherein the organic polymer layer is formed by an ink jet method or a printing method. In a display device having a display screen,
Each pixel of the display screen includes the organic light emitting device according to any one of claims 23 to 26, and
Each of the pixels includes two or more transistors.

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