JPWO2009022594A1 - Blue light-emitting polymer compound, organic electroluminescence device and use thereof - Google Patents

Abstract

〔式（１）において、Ｒ¹〜Ｒ⁴およびＲ¹¹〜Ｒ¹⁴は、それぞれ独立に、水素原子、置換基または電子吸引性の置換基であり、Ｒ¹〜Ｒ⁴の内の少なくとも１つ、およびＲ¹¹〜Ｒ¹⁴の内の少なくとも１つは、それぞれ独立に該電子吸引性の置換基であり、Ｒ⁵〜Ｒ⁸およびＲ¹⁵〜Ｒ¹⁸は、それぞれ独立に、水素原子または置換基である。ただし、Ｒ¹¹〜Ｒ¹⁸の内の１つは、重合性炭素−炭素二重結合を有する置換基である。〕。An object of the present invention is to provide a light-emitting material that is thermally more stable and has high light emission efficiency and high durability when used as a blue light-emitting material of an EL element.
The blue light-emitting polymer compound of the present invention includes a structural unit derived from a compound represented by the following formula (1);

[In Formula (1), R < ¹ > -R < ⁴ > and R < ¹¹ > -R < ¹⁴ > are respectively independently a hydrogen atom, a substituent, or an electron-withdrawing substituent, and at least 1 of R < ¹ > -R < ⁴ >. And at least one of R ^{11 to} R ¹⁴ is each independently the electron-withdrawing substituent, and R ^{5 to} R ⁸ and R ^{15 to} R ¹⁸ are each independently a hydrogen atom or a substituent. It is. However, one of R ^{11 to} R ¹⁸ is a substituent having a polymerizable carbon-carbon double bond. ].

Description

  The present invention relates to a blue light-emitting polymer compound, and more particularly, to a phosphorescent polymer compound that emits blue light, an organic electroluminescence device using the compound, a production method thereof, and a use thereof.

  In recent years, in order to expand the use of organic electroluminescent elements (also referred to as “organic EL elements” in this specification), phosphorescent light emitting materials having high luminous efficiency and excellent film forming properties are used as the light emitting materials. Polymer compounds, specifically, polymer compounds containing a phosphorescent iridium complex structure in the main chain or part of the side chain are being actively developed.

  Among such phosphorescent polymer compounds, as a material that emits blue light, for example, Japanese Patent Application Laid-Open No. 2003-206320 (Patent Document 1) has two phenylpyridine ligands and a picolinic acid ligand. A polymer material having an iridium complex in a side chain is disclosed. However, there was room for improvement from the viewpoint of the thermal stability of the material.

From the viewpoint of the thermal stability of the material, there is a report that an iridium complex having three phenylpyridine rings is superior to an iridium complex having two phenylpyridine rings (Non-Patent Documents 1 and 2). ). JP-A No. 2003-119179 (Patent Document 2) and JP-A No. 2006-8996 (Patent Document 3) disclose iridium complexes having three phenylpyridine rings. It is not disclosed.
JP 2003-206320 A JP 2003-119179 A JP 2006-8996 A A. Tsuboyama et al, J. Am. Chem. Soc. 125, 12971 (2003) Shinjiro Okada, “Organic EL Material Technology”, CM Publishing, 2004, pp.206-214

  The present invention has been made in view of such conventional technology, and provides a light-emitting material that is thermally more stable and has high luminous efficiency and high durability when used as a blue light-emitting material of an EL element. The purpose is to do. Another object of the present invention is to provide an organic EL device that emits blue light, has high luminous efficiency, and high durability.

The inventor has intensively studied to solve the above-mentioned problems, and completed the present invention. The present invention relates to the following [1] to [13], for example.
[1] A blue light-emitting polymer compound comprising a structural unit derived from a compound represented by the following formula (1):

In [Equation ^(1), R 1 ~R ⁴ and R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon atoms 7-40 An aralkyl group, an amino group optionally substituted by an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a silyl group optionally substituted by an alkyl group having 1 to 30 carbon atoms, or An electron-withdrawing substituent,
The electron-withdrawing substituent is a halogen atom, a fluorine-substituted C 1-10 alkyl group, a fluorine-substituted C 1-10 alkoxy group, a cyano group, an aldehyde group, or a C 2-10 carbon atom. An acyl group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aminocarbonyl group having 1 to 10 carbon atoms, a thiocyanate group, and a sulfonyl group having 1 to 10 carbon atoms;
At least one of R ^{1 to} R ⁴ and at least one of R ^{11 to} R ¹⁴ are each independently the electron-withdrawing substituent;
R ^{5 to} R ⁸ and R ^{15 to} R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 40 carbon atoms, or 1 carbon atom. It is the silyl group which may be substituted by the amino group which may be substituted by the -30 alkyl group, the C1-C30 alkoxy group, or the C1-C30 alkyl group.

However, one of R ^{11 to} R ¹⁸ is a substituent having a polymerizable carbon-carbon double bond. ].
[2] The electron-withdrawing substituent is a fluorine atom, a fluorine-substituted C 1-10 alkyl group, a fluorine-substituted C 1-10 alkoxy group, or a cyano group. The blue light-emitting polymer compound according to [1].

[3] In the formula (1), R ¹ , R ³ , R ¹¹ and R ¹³ are hydrogen atoms, and R ² , R ⁴ , R ¹² and R ¹⁴ are fluorine atoms. The blue light-emitting polymer compound according to [1] or [2].

[4] In the above formula (1), R ¹ , R ³ , R ⁴ , R ¹¹ , R ¹³ and R ¹⁴ are hydrogen atoms, and R ² and R ¹² are fluorine atoms. The blue light-emitting polymer compound according to [1] or [2].

  [5] The structure according to any one of [1] to [4], further comprising a structural unit derived from a hole transport polymerizable compound and / or an electron transport polymerizable compound. Blue light emitting polymer compound.

[6] An organic electroluminescence device comprising a substrate, a pair of electrodes formed on the substrate, and one or more organic layers including a light emitting layer between the pair of electrodes,
An organic electroluminescent device, wherein the light emitting layer contains a blue light emitting non-conjugated polymer compound having a structural unit derived from a blue light emitting compound represented by the following formula (1);

In [Equation ^(1), R 1 ~R ⁴ and R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon atoms 7-40 An aralkyl group, an amino group optionally substituted by an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a silyl group optionally substituted by an alkyl group having 1 to 30 carbon atoms, or An electron-withdrawing substituent,
The electron-withdrawing substituent is a halogen atom, a fluorine-substituted C 1-10 alkyl group, a fluorine-substituted C 1-10 alkoxy group, a cyano group, an aldehyde group, or a C 2-10 carbon atom. An acyl group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aminocarbonyl group having 1 to 10 carbon atoms, a thiocyanate group, and a sulfonyl group having 1 to 10 carbon atoms;
At least one of R ^{1 to} R ⁴ and at least one of R ^{11 to} R ¹⁴ are each independently the electron-withdrawing substituent;
R ^{5 to} R ⁸ and R ^{15 to} R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 40 carbon atoms, or 1 carbon atom. It is the silyl group which may be substituted by the amino group which may be substituted by the -30 alkyl group, the C1-C30 alkoxy group, or the C1-C30 alkyl group.

However, one of R ^{11 to} R ¹⁸ is a substituent having a polymerizable carbon-carbon double bond. ].
[7] The electron-withdrawing substituent is a fluorine atom, a fluorine-substituted C 1-10 alkyl group, a fluorine-substituted C 1-10 alkoxy group, or a cyano group. The organic electroluminescence device according to [6].

[8] In the above formula (1), R ¹ , R ³ , R ¹¹ and R ¹³ are hydrogen atoms, and R ² , R ⁴ , R ¹² and R ¹⁴ are fluorine atoms. [6] The organic electroluminescence device according to [7].

[9] In the above formula (1), R ¹ , R ³ , R ⁴ , R ¹¹ , R ¹³ and R ¹⁴ are hydrogen atoms, and R ² and R ¹² are fluorine atoms. [6] The organic electroluminescence device according to [7].

  [10] The above-mentioned [6], wherein the blue light-emitting non-conjugated polymer compound further comprises a structural unit derived from a hole-transporting polymerizable compound and / or an electron-transporting polymerizable compound. -The organic electroluminescent element in any one of [9].

  [11] A step of forming at least one organic compound layer containing the polymer compound according to any one of [1] to [5] on the anode, and a step of forming a cathode on the organic compound layer The manufacturing method of the organic electroluminescent element characterized by including these.

[12] An image display device comprising the organic electroluminescence element according to any one of [6] to [10].
[13] A surface-emitting light source comprising the organic electroluminescence element according to any one of [6] to [10].

According to the present invention, there is provided a blue light-emitting material that is more thermally stable and has high light emission efficiency and high durability when used as a light-emitting material for an EL element.
In addition, according to the present invention, an organic EL element that emits blue light, has high luminous efficiency, and high durability is provided.

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

Explanation of symbols

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

Hereinafter, the present invention will be described in more detail.
In the present invention, “blue light emission” is not necessarily limited, but refers to light emission with a wavelength giving a maximum light emission intensity of 480 nm or less, preferably 475 nm or less, for example, in an emission spectrum.

[Blue light-emitting polymer compound]
The blue light-emitting polymer compound according to the present invention, more specifically, the phosphorescent polymer compound that emits blue light (hereinafter also referred to as “polymer compound of the present invention”) is a compound represented by the following formula (1). (Hereinafter also referred to as “compound 1”).

In [Equation ^(1), R 1 ~R ⁴ and R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon atoms 7-40 An aralkyl group, an amino group optionally substituted by an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or a silyl group optionally substituted by an alkyl group having 1 to 30 carbon atoms, Or a halogen atom, a fluorine-substituted C1-C10 alkyl group, a fluorine-substituted C1-C10 alkoxy group, a cyano group, an aldehyde group, a C2-C10 acyl group, a C2-C10 An electron-withdrawing substituent selected from an alkoxycarbonyl group, an aminocarbonyl group having 1 to 10 carbon atoms, a thiocyanate group, and a sulfonyl group having 1 to 10 carbon atoms,
At least one of R ^{1 to} R ⁴ and at least one of R ^{11 to} R ¹⁴ are each independently the electron-withdrawing substituent;
R ^{5 to} R ⁸ and R ^{15 to} R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 40 carbon atoms, or 1 carbon atom. It is the silyl group which may be substituted by the amino group which may be substituted by the -30 alkyl group, the C1-C30 alkoxy group, or the C1-C30 alkyl group.

However, one of R ^{11 to} R ¹⁸ is a substituent having a polymerizable carbon-carbon double bond. ].
In R ^{1 to} R ⁸ and R ^{11 to} R ¹⁸ , examples of the alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t -Butyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, cyclopentyl group, cyclohexyl group, adamantyl group and the like, methyl group, ethyl group, propyl group, Isopropyl, butyl, isobutyl, sec-butyl, t-butyl, amyl, hexyl and octyl are preferred.

  Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, anthryl group, pyridyl group and the like, and phenyl group, tolyl group, xylyl group and mesityl group are preferable. .

  Examples of the aralkyl group having 7 to 40 carbon atoms include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 2- (1-phenyl) propyl group, and 3,3-diphenylpropyl group. Groups are preferred.

  Examples of the amino group that may be substituted with the alkyl group having 1 to 30 carbon atoms include an amino group, a dimethylamino group, a diethylamino group, and a dibutylamino group, and a dimethylamino group is preferable.

  Examples of the alkoxy group having 1 to 30 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, hexyloxy group, octyloxy group, 2 -An ethylhexyloxy group, a decyloxy group, etc. are mentioned, A methoxy group is preferable.

  Examples of the silyl group that may be substituted with the alkyl group having 1 to 30 carbon atoms include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and a trimethoxysilyl group, and a trimethylsilyl group is preferable.

In R ^{1 to} R ⁴ and R ^{11 to} R ¹⁴ , examples of the electron-withdrawing substituent include a halogen atom, a fluorine-substituted C 1-10 alkyl group, and a fluorine-substituted C 1-10. Alkoxy group, cyano group, aldehyde group, acyl group having 2 to 10 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aminocarbonyl group having 1 to 10 carbon atoms, thiocyanate group, and sulfonyl group having 1 to 10 carbon atoms Is mentioned.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
Examples of the fluorine-substituted alkyl group having 1 to 10 carbon atoms include a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group, and a trifluoromethyl group is preferable.

  Examples of the fluorine-substituted alkoxy group having 1 to 10 carbon atoms include fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, 1,1,2,2-tetrafluoroethoxy group, 1,1,2,2, 2-pentafluoroethoxy group etc. are mentioned, A trifluoromethoxy group is preferable.

As said C2-C10 acyl group, an acetyl group, a propionyl group, a benzoyl group etc. are mentioned, An acetyl group is preferable.
Examples of the alkoxycarbonyl group having 2 to 10 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a propyloxycarbonyl group, a t-butyloxycarbonyl group, a benzyloxycarbonyl group, a phenoxycarbonyl group, and the like. A t-butyloxycarbonyl group and a benzyloxycarbonyl group are preferred.

  Examples of the aminocarbonyl group having 1 to 10 carbon atoms include an aminocarbonyl group, a dimethylaminocarbonyl group, a diethylaminocarbonyl group, and a dibutylaminocarbonyl group, and a dimethylaminocarbonyl group is preferable.

  Examples of the sulfonyl group having 1 to 10 carbon atoms include a methylsulfonyl group, an ethylsulfonyl group, and a phenylsulfonyl group, and a methylsulfonyl group and a phenylsulfonyl group are preferable.

  As the electron-withdrawing substituent, among these substituents, the emission wavelength from the iridium complex is shorter, the emission color is blue with high color purity, and the emission quantum yield is high. A fluorine-substituted alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms and a cyano group are preferable, and a fluorine atom is particularly preferable.

In the compound 1 of the present invention, since at least one of R ^{1 to} R ⁴ and at least one of R ^{11 to} R ¹⁴ are the electron-withdrawing substituent, only at least one of R ^{1 to} R ⁴ , or R Only at least one of ^{11 to} R ¹⁴ emits blue light with higher color purity than when the electron-withdrawing substituent is used.

  Examples of the substituent having a polymerizable carbon-carbon double bond (hereinafter also referred to as “polymerizable substituent”) include an allyl group, an alkenyl group (such as a vinyl group and a 2-propenyl group), and styryl as a polymerizable functional group. And a substituent having a group, an acryloyloxy group, a methacryloyloxy group, an acrylamide group, a methacrylamide group and a maleimide group (preferably a vinyl group, a styryl group, an acryloyloxy group and a methacryloyloxy group).

The polymerizable substituent may have a divalent group (hereinafter referred to as “spacer”) so as to be located between the carbon atom of the phenylpyridine ring coordinated to iridium and the polymerizable functional group. Examples of the spacer include a linear or branched saturated hydrocarbon chain and a hydrocarbon chain containing a hetero atom. Here, the hydrocarbon chain containing a hetero atom means that one or two or more non-adjacent methylene groups in a saturated hydrocarbon chain are —O—, —CO—, —CO—O—, —O—CO. -, - O-CO-O -, - CO-NH -, - NH-CO -, - O-CO-NH -, - NH-CO-O -, - NH -, - N (CH 3) -, A saturated hydrocarbon chain substituted with —N (C ₆ H ₅ ) —, —S—, —SO—, —SO ₂ —, —CH═CH—, —C≡C—, —C═N—, etc. means. From the viewpoint of constraining the ligand close to the polymer main chain, the number of atoms contained in the longest chain of the spacer is preferably 1 to 5. Examples of the polymerizable substituent include groups represented by the following chemical formulas (a1) to (a41). Among these polymerizable substituents, (a1), (a6), (a9) to (a19) or (a24) to (a30) have high luminous efficiency of the organic electroluminescence device and a long luminance half time. The group represented by (a1), (a12)-(a19), (a24), (a25), (a28), (a29) or (a30) is particularly preferred.

When the polymerizable substituent is bonded to the phenyl group of the phenylpyridine ring, steric hindrance occurs between the polymerizable substituent and the electron-withdrawing substituent, and the polymerizability of the compound (1) is increased. In some cases, a polymer having a sufficient molecular weight cannot be synthesized. From the above, the compound (1) is preferably a compound in which one of R ^{15 to} R ¹⁸ is the polymerizable substituent. When R ¹⁵ is the polymerizable substituent, steric hindrance occurs between the polymerizable substituent and the phenyl group of the phenylpyridine ring of the compound (1), and R ¹⁸ is the polymerizable substituent. When the group is a group, the steric hindrance between the polymerizable substituent and the iridium atom may cause a decrease in the polymerizability. Therefore, a compound in which R ¹⁶ or R ¹⁷ is the polymerizable substituent is obtained. Particularly preferred.

As the compound (1), R ¹ , R ³ , R ¹¹ and R ¹³ are hydrogen atoms because the emission wavelength is shorter, the emission color is blue with high color purity, and the emission quantum yield is high. , R ² , R ⁴ , R ¹² and R ¹⁴ are preferably fluorine atoms (compounds represented by the following formula (2) (hereinafter also referred to as “compound (2)”)).

Among these compounds (2), R ⁶ is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms because the emission wavelength is shorter and the emission color is blue with higher color purity. Is preferred.

Since the compound (1) has a high emission quantum yield, R ¹ , R ³ , R ⁴ , R ¹¹ , R ¹³ and R ¹⁴ are hydrogen atoms, and R ² and R ¹² are fluorine atoms. A compound (compound represented by the following formula (3) (hereinafter also referred to as “compound (3)”)) is also preferable.

Among these compounds (3), R ⁶ is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms because the emission wavelength is shorter and the emission color is blue with higher color purity. Is preferred.

In addition, the said compound (1) can be used individually by 1 type or in combination of 2 or more types.
(Production method of compound (1))
The compound (1) can be produced, for example, by the following method.

  First, a phenylpyridine derivative (1-1) is obtained by reacting a phenylboronic acid derivative and a 2-halogenated pyridine derivative using a normal Suzuki coupling reaction as shown in the following figure. Commercially available reagents can be used as the phenylboronic acid derivative and the 2-halogenated pyridine derivative. The 2-halogenated pyridine derivative can also be obtained by halogenating a commercially available pyridine derivative according to a conventional method.

  Next, iridium (III) chloride trihydrate and the following phenylpyridine derivative (1-1)

Is reacted in a mixed solvent of alcohol and water by heating to 50 to 150 ° C. to thereby produce the following iridium binuclear complex (1-2)

Get. In addition, R < ¹ > -R < ⁸ > in Formula (1-1) and (1-2) is synonymous with R < ¹ > -R < ⁸ > in Formula (1), respectively. Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol, 1,2-propanediol, 1 , 3-propanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, diethylene glycol monomethyl ether and the like. The ratio of alcohol to water (alcohol: water (volume ratio)) in the mixed solvent is, for example, 1 to 99: 1. Specific examples of the mixed solvent include a mixed solvent of 2-ethoxyethanol and water (2-ethoxyethanol: water = 3: 1 (volume ratio)). The reaction time is, for example, 30 minutes to 120 hours.

  Next, the following phenylpyridine derivative (1-3) having a substituent having this binuclear complex and a polymerizable carbon-carbon double bond

Is reacted in a solvent such as toluene or mesitylene in the presence of a base and / or silver salt by heating to 50 to 200 ° C. to obtain compound (1). Incidentally, R ¹¹ to R ¹⁸ in the formula (1-3) has the same meaning as R ¹¹ to R ¹⁸ each formula (1). Examples of the base include inorganic base compounds such as sodium carbonate and potassium carbonate, and organic bases such as tributylamine and lutidine. Examples of the silver salt include silver oxide (I), silver sulfide (I), silver sulfate (I), silver nitrate (I), silver phosphate (I), silver acetate (I), silver trifluoroacetate ( I), silver p-toluenesulfonate (I), silver methanesulfonate (I), silver trifluoromethanesulfonate (I) and the like. The reaction time is, for example, 10 minutes to 48 hours.

(Structural units derived from charge-transporting polymerizable compounds)
The polymer compound of the present invention may further contain a structural unit derived from a hole transporting polymerizable compound and / or an electron transporting polymerizable compound. In the present invention, the hole transport polymerizable compound and the electron transport polymerizable compound are also referred to as a charge transport polymerizable compound.

  The polymer compound of the present invention comprises a structural unit derived from one or more hole-transporting polymerizable compounds, or a structural unit derived from one or more electron-transporting polymerizable compounds. The polymer compound is preferably included. When such a polymer compound is used, the mobility of charges in the light emitting layer is high, and a homogeneous thin film can be formed by coating, so that high light emission efficiency can be obtained.

  In addition, the polymer compound of the present invention has a structure derived from a structural unit derived from one or more hole-transporting polymerizable compounds and one or more electron-transporting polymerizable compounds. A polymer compound containing a unit is more preferable. When such a polymer compound is used, the polymer compound has a hole transporting function and an electron transporting function, and thus a structural unit derived from the phosphorescent compound represented by the formula (1) In the vicinity, holes and electrons recombine more efficiently, so that higher luminous efficiency can be obtained.

  The hole-transporting polymerizable compound and the electron-transporting polymerizable compound are not particularly limited except that they have a substituent containing a radically polymerizable polymerizable functional group. Compounds can be used.

  Examples of the polymerizable functional group include urethane (meth) acryloyloxy groups such as allyl groups, alkenyl groups (vinyl groups, 2-propenyl groups, etc.), acryloyloxy groups, methacryloyloxy groups, methacryloyloxyethyl carbamate groups, and acrylamides. Groups, methacrylamide groups, vinylamide groups, maleimide groups and derivatives thereof. Of these, alkenyl groups are preferred.

  More specifically, when the polymerizable functional group is an alkenyl group, the substituents containing the radical polymerizable polymerizable functional group include substituents represented by the following general formulas (A1) to (A12). preferable. Among these, substituents represented by the following formulas (A1), (A5), (A8), and (A12) are more preferable because a polymerizable functional group can be easily introduced into a charge transporting compound.

  As the hole transport polymerizable compound, specifically, compounds represented by the following general formulas (E01) to (E09) are preferable. From the viewpoint of the luminous efficiency of the organic EL device, the following formula (E02) Or the compound represented by (E03) is more preferable.

  Specifically, the electron-transporting polymerizable compound is preferably a compound represented by the following general formulas (E10) to (E19). From the viewpoint of the luminous efficiency of the organic EL device, the following formula (E16) or The compound represented by (E19) is more preferable.

  In the formulas (E01) to (E19), compounds in which the substituent represented by the formula (A1) is replaced with the substituents represented by the general formulas (A2) to (A12) are also preferably used. However, since a functional group can be easily introduced into the polymerizable compound, a compound having a substituent represented by the formula (A1) or (A5) is particularly preferable.

  Among these, as the hole-transporting polymerizable compound, the compound represented by any one of the formulas (E02) and (E03), and the electron-transporting polymerizable compound as the (E16), ( More preferably, the compound represented by any one of E19) is used in combination. When these polymerizable compounds are used, an organic EL device having high luminous efficiency and high durability can be obtained.

(Blue light emitting polymer compound)
The blue light-emitting polymer compound of the present invention may be a so-called oligomer compound or a polymer compound. The weight average molecular weight of the polymer compound of the present invention is preferably 1,000 to 5,000,000, more preferably 2,000 to 1,000,000, and still more preferably 3,000 to 100,000. The molecular weight in this specification means the polystyrene conversion molecular weight measured using GPC (gel permeation chromatography) method. When the molecular weight is within this range, the polymer is soluble in an organic solvent, and a uniform thin film can be obtained.

  If the ratio of the compound represented by the formula (1) (iridium complex) and the charge transporting polymerizable compound (hole transporting and / or electron transporting polymerizable compound) is appropriately set, a desired value can be obtained. A blue light-emitting polymer compound is obtained, and the polymer compound may be any of a random copolymer, a block copolymer, and an alternating copolymer. In the polymer compound of the present invention, the compound 1 and any of the charge-transporting polymerizable compounds are polymerized by a polymerization reaction in the polymerizable carbon-carbon double bonds and radical polymerizable functional groups of each. Thus, each structural unit is a non-conjugated polymer compound that is non-conjugated.

  In the polymer compound of the present invention, the number of structural units derived from the compound represented by the above formula (1) (iridium complex) is m, and the number of structural units derived from the charge transporting polymerizable compound (hole transportability). When the total number of structural units derived from the polymerizable compound and / or the electron-transporting polymerizable compound is n (m, n represents an integer of 1 or more), it is derived from the iridium complex with respect to the total number of structural units. The ratio of the number of structural units, that is, the value of m / (m + n) is preferably in the range of 0.001 to 0.5, and more preferably in the range of 0.001 to 0.2. When the value of m / (m + n) is within this range, an organic EL device having high light emission efficiency with high charge mobility and low influence of concentration quenching can be obtained.

  In the case where the polymer compound of the present invention includes a structural unit derived from a hole-transporting polymerizable compound and a structural unit derived from an electron-transporting polymerizable compound, the hole-transporting polymerizable compound When the number of structural units derived is x and the number of structural units derived from the electron transport polymerizable compound is y (x and y are integers of 1 or more), between x and y and n, n = X + y relationship holds. The ratio x / n of the number of structural units derived from the hole transporting polymerizable compound to the number of structural units derived from the charge transporting polymerizable compound, and the number of structural units derived from the electron transporting polymerizable compound The optimum value of the ratio y / n is determined by the charge transportability of each structural unit, the charge transportability of the structural unit derived from the iridium complex, the concentration, and the like. When the polymer compound of the present invention is used as the only compound for forming the light emitting layer of the organic EL device, the values of x / n and y / n are preferably in the range of 0.05 to 0.95, More preferably, it is in the range of 0.20 to 0.80. Here, x / n + y / n = 1 holds.

  The polymer compound of the present invention may further contain a structural unit derived from another polymerizable compound as long as it does not contradict the object of the present invention. Examples of such a polymerizable compound include (meth) acrylic acid alkyl esters such as methyl acrylate and methyl methacrylate, and compounds having no charge transporting property such as styrene and derivatives thereof, but are not limited thereto. Is not to be done.

As a polymerization method of the polymer compound of the present invention, radical polymerization is preferable.
Therefore, as a preferable production method of the polymer compound of the present invention,
A production method of polymerizing at least the compound represented by the formula (1) in the presence of a radical polymerization initiator;
At least m mol of the compound represented by the formula (1) and x mol of the hole transport polymerizable compound and / or y mol of the electron transport polymerizable compound are used as a radical polymerization initiator. (Wherein m, x and y are each an integer of 1 or more;
The value of m / (m + x + y) is preferably 0.001 to 0.5, more preferably 0.001 to 0.2;
The values of x / (x + y) and y / (x + y) are each preferably 0.05 to 0.95, more preferably 0.20 to 0.80. )
Etc.

Examples of the radical polymerization initiator include dimethyl-2,2′-azobis (2-methylpropionate).
[Organic EL device]
An organic EL device according to the present invention is an organic electroluminescence device comprising a substrate, a pair of electrodes formed on the substrate, and one or more organic layers including a light emitting layer between the pair of electrodes. There,
The light emitting layer contains a blue light emitting non-conjugated polymer compound having a structural unit derived from a blue light emitting compound represented by the following formula (1) (that is, the above-described polymer compound of the present invention). It is said.

Details of the blue light-emitting compound represented by the above formula (1) and the polymer compound having a structural unit derived from this compound (for example, preferred embodiments) are as described above.
Further, the method for producing an organic EL device according to the present invention includes a step of forming at least one organic compound layer containing the above-described polymer compound of the present invention on an anode, and forming a cathode on the organic compound layer. And a step of performing.

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

(Light emitting layer)
Although it does not specifically limit as a formation method of the said light emitting layer, For example, it can form as follows. First, (A) a solution in which the blue light-emitting polymer compound of the present invention and a charge-transporting non-conjugated polymer compound are dissolved, or (B) a structural unit derived from a charge-transporting polymerizable compound of the present invention. A solution in which the blue light emitting polymer compound is dissolved is prepared.

  As the charge transporting non-conjugated polymer compound contained in the solution (A), a known polymer compound can be used. For example, the hole transporting polymerizable compound and / or the electron transporting compound can be used. A non-conjugated polymer compound containing a structural unit derived from a polymerizable compound can be used.

  The solvent used for the preparation of the solution is not particularly limited. For example, a chlorine solvent such as chloroform, methylene chloride, dichloroethane, an ether solvent such as tetrahydrofuran and anisole, an aromatic hydrocarbon solvent such as toluene and xylene, Ketone solvents such as acetone and methyl ethyl ketone, and ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate are used.

  Next, the solution prepared in this manner is formed on a substrate using an inkjet method, a spin coating method, a dip coating method, a printing method, or the like. The concentration of the solution depends on the compound to be used and the film forming conditions, but is preferably 0.1 to 10 wt% in the case of spin coating or dip coating, for example.

As described above, since the light emitting layer is easily formed, the manufacturing process can be simplified and the area of the device can be increased.
<Other materials>
Each of the layers may be formed by mixing a polymer material as a binder. Examples of the polymer material include polymethyl methacrylate, polycarbonate, polyester, polysulfone, polyphenylene oxide, and the like.

  In addition, materials used for the respective layers may be formed by mixing materials having different functions, for example, light emitting materials, hole transport materials, electron transport materials, and the like. The organic layer containing the polymer compound of the present invention and the non-conjugated polymer compound may further contain other hole transport materials and / or electron transport materials for the purpose of supplementing charge transport properties. Such a transport material may be a low molecular compound or a high molecular compound.

  As a hole transport material for forming the hole transport layer or a hole transport material mixed in the light emitting layer, for example, TPD (N, N′-dimethyl-N, N ′-(3-methylphenyl) -1,1 '-Biphenyl-4,4'diamine); α-NPD (4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl); m-MTDATA (4,4', 4 '' -Low molecular triphenylamine derivatives such as tris (3-methylphenylphenylamino) triphenylamine); polyvinylcarbazole; a polymer compound obtained by polymerizing by introducing a polymerizable substituent into the triphenylamine derivative; polyparaphenylene vinylene And fluorescent light-emitting polymer compounds such as polydialkylfluorene. Examples of the polymer compound include a polymer compound having a triphenylamine skeleton disclosed in JP-A-8-157575. The hole transport materials may be used singly or as a mixture of two or more kinds, or different hole transport materials may be laminated and used. The thickness of the hole transport layer depends on the conductivity of the hole transport layer and cannot be generally limited, but is preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and particularly preferably 10 nm to 500 nm. .

  Examples of the electron transport material forming the electron transport layer or the electron transport material mixed in the light emitting layer include quinolinol derivative metal complexes such as Alq3 (aluminum trisquinolinolate), oxadiazole derivatives, triazole derivatives, imidazole. Low molecular compounds such as derivatives, triazine derivatives, and triarylborane derivatives; high molecular compounds obtained by polymerizing a low molecular compound by introducing a polymerizable substituent. Examples of the polymer compound include poly PBD disclosed in JP-A-10-1665. The electron transport materials may be used singly or in combination of two or more, or different electron transport materials may be laminated and used. Since the thickness of the electron transport layer depends on the conductivity of the electron transport layer and the like, it cannot be generally limited, but is preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and particularly preferably 10 nm to 500 nm. .

  Further, a hole block layer may be provided adjacent to the cathode side of the light emitting layer for the purpose of suppressing holes from passing through the light emitting layer and efficiently recombining holes and electrons in the light emitting layer. Good. In order to form the hole block layer, a known material such as a triazole derivative, an oxadiazole derivative, or a phenanthroline derivative is used.

  A hole injection layer may be provided between the anode and the light emitting layer in order to relax the injection barrier in hole injection. In order to form the hole injection layer, known materials such as copper phthalocyanine, a mixture of polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS), and fluorocarbon are used.

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

  Examples of the hole transport layer, light emitting layer, and electron transport layer forming method (film forming method) include resistance heating evaporation, electron beam evaporation, sputtering, ink jet, spin coating, printing, and spraying. A dispenser method or the like is used. In the case of a low molecular compound, resistance heating vapor deposition or electron beam vapor deposition is preferably used, and in the case of a polymer material, an ink jet method, a spin coating method, or a printing method is suitably used.

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

Examples of the formation method (film formation method) of the anode material include an electron beam evaporation method, a sputtering method, a chemical reaction method, and a coating method.
(cathode)
Examples of the cathode material include alkaline metals such as Li, Na, K, and Cs; alkaline earth metals such as Mg, Ca, and Ba; Al; MgAg alloys; Al and alkaline metals or alkaline earths such as AlLi and AlCa. Known cathode materials such as alloys with metals are used. The thickness of the cathode is preferably 10 nm to 1 μm, more preferably 50 to 500 nm. When a highly active metal such as an alkali metal or alkaline earth metal is used as the cathode, the thickness of the cathode is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm. In this case, a metal layer stable to the atmosphere is laminated on the cathode for the purpose of protecting the cathode metal. Examples of the metal forming the metal layer include Al, Ag, Au, Pt, Cu, Ni, and Cr. The thickness of the metal layer is preferably 10 nm to 1 μm, more preferably 50 to 500 nm.

Examples of the cathode material forming method (film forming method) include resistance heating vapor deposition, electron beam vapor deposition, sputtering, and ion plating.
(substrate)
As the substrate of the organic EL element according to the present invention, an insulating substrate transparent to the emission wavelength of the light emitting material is used, and transparent plastic such as PET (polyethylene terephthalate) and polycarbonate is used in addition to glass.

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

  Specifically, the organic EL device according to the present invention includes a display device such as a computer, a television, a mobile terminal, a mobile phone, a car navigation, a viewfinder of a video camera, a backlight, an electrophotography, an illumination light source, a recording light source, and an exposure. It is suitably used for light sources, reading light sources, signs, signboards, interiors, optical communications, and the like.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
<Measurement equipment, etc.>
1) ¹ H-NMR, ¹³ C-NMR
JNM EX270 270Mz manufactured by JEOL Ltd.
2) Mass spectrometry (FAB-MS)
Automass II made by JEOL Ltd.
3) Elemental analysis manufactured by RECO CHNS-932 type 4) GPC measurement (molecular weight measurement)
Shodex GPC-101
Column: Shodex GPC LF-804 × 3 Eluent: Tetrahydrofuran Temperature: 40 ° C
Detector: Differential refractive index detector 5) ICP emission analysis ICPS-8000 manufactured by Shimadzu Corporation
[Synthesis Example 1]
Synthesis of polymerizable iridium complex compound (A)

This will be described with reference to the above scheme.
<Synthesis of Compound (W)>
2- (2 ′, 4′-difluorophenyl) -4-tertiarybutylpyridine synthesized in a method described in Polyhedron 25,1167 (2006) in a 50 ml two-necked flask equipped with a Jimroth condenser and a three-way cock 371 mg, 212 mg of iridium (III) chloride trihydrate, 9 ml of 2-ethoxyethanol, and 3 ml of pure water were added, and the resulting solution was bubbled with nitrogen for 5 minutes and then refluxed with stirring for 14 hours under nitrogen. Was reacted. After the reaction, the mixture was cooled to room temperature, and 30 ml of pure water was added to precipitate the product. The precipitate was collected by filtration, washed with 50 ml of a mixed solvent of methanol / water = 7/3, and then dried under reduced pressure to obtain compound (W) as a yellow powder. The yield was 367 mg, and the yield was 85%. This powder was used in the next step without being identified.

This will be described with reference to the above scheme.
<Synthesis of Compound (A1)>
A three-necked flask equipped with a Jimroth condenser and a three-way cock was charged with 6-chloropyridine-3-carbaldehyde (1.416 g, 10.0 mmol), 2,4-difluorophenylboronic acid (1.895 g, 12.0 mmol). ), Sodium carbonate (2.12 g, 20.0 mmol), 1,2-dimethoxyentane (30 ml), and pure water (10 ml) were added and bubbled with nitrogen. Further tetrakis (triphenylphosphine) palladium (0) (231 mg, 0.2 mmol) was added, and these were reacted by refluxing with stirring for 2 hours. After the reaction, the mixture was cooled to room temperature, chloroform was added, and the organic layer was washed with an aqueous sodium chloride solution. The obtained organic layer was dried over magnesium sulfate and filtered, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: chloroform / hexane = 1/1 to chloroform gradient), then the solvent was distilled off and dried under reduced pressure to obtain compound (A1) as a white solid. . The yield was 1.730 g, and the yield was 79%. The identification result of the compound (A1) was as follows.
¹ H-NMR (270 MHz, CDCl ₃ ) ppm: 10.17 (s, 1H, -CHO), 9.15 (d, 1H, J = 2.2 Hz, 8.24 (dd, 1H, J = 8.2, 2.3 Hz, ArH), 8.16 (m, 1H, ArH), 7.97 (d, 1H, J = 8.4 Hz, ArH), 7.05 (m, 1H, ArH), 6.96 (m, 1H, ArH).
<Synthesis of Compound (A2)>
Compound (A1) (438 mg, 2.0 mmol) was added to an eggplant flask equipped with a three-way cock, and the atmosphere was replaced with nitrogen. Further, dehydrated THF (4 ml) was added, 3M methylmagnesium bromide diethyl ether solution (0.73 ml, 2.2 mmol) was slowly added, and these were stirred at room temperature for 4 days to be reacted. After the reaction, pure water was carefully added and the reaction product was extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate and filtered, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: gradient from chloroform to ethyl acetate / chloroform = 1/9), the solvent was distilled off, and the residue was dried under reduced pressure to obtain compound (A2) as a colorless liquid. It was. The yield was 465 mg, and the yield was 99%. The identification result of the compound (A2) was as follows.
¹ H-NMR (270 MHz, CDCl ₃ ) ppm: 8.69 (d, 1H, J = 1.9 Hz, ArH), 7.99 (m, 1H, ArH), 7.83-7.72 (m, 2H, ArH), 7.00 (m , 1H, ArH), 6.92 (m, 1H, ArH), 5.02 (m, 1H, CH), 1.94 (d, 1H, J = 3.8 Hz, -OH), 1.58 (d, 3H, -CH ₃ ).
<Synthesis of Iridium Complex Compound (A)>
The above compound (W) (288 mg, 0.2 mmol), potassium carbonate (138 mg, 1.0 mmol), compound (A2) (118 mg, 0.5 mmol) in a two-necked flask equipped with a Jimroth condenser and a three-way cock Was added and replaced with nitrogen. After adding mesitylene (4 ml) and silver (I) trifluoromethanesulfonate (123 mg, 0.48 mmol), the mixture was reacted under reflux with stirring for 4 hours. After the reaction, the mixture was cooled to room temperature, chloroform was added, and the mixture was filtered through celite to remove insoluble matters. The solvent of the filtrate was distilled off, and the residue was purified twice by silica gel column chromatography (eluent: chloroform / hexane = 2/8 to chloroform gradient), recrystallized from methanol / dichloromethane, and dried in vacuo. The polymerizable iridium complex compound (A) was obtained as an orange solid. The yield was 37 mg, and the yield was 10%. The identification result of the compound (A) was as follows.
¹ H-NMR (270 MHz, CDCl ₃ ) ppm: 8.31 (m, 2H, ArH), 8.23 (dd, 1H, J = 8.6, 2.6 Hz, ArH), 7.70 (d, 1H, J = 8.9 Hz, ArH ), 7.34 (m, 3H, ArH), 6.99 (dd, 1H, J = 5.9, 1.9 Hz, ArH), 6.93 (dd, 1H, J = 5.9 1.9 Hz, ArH), 6.44-6.25 (m, 7H, ArH + -CH = CH ₂ ), 5.47 (d, 1H, J = 17.8 Hz, -CH = CH ₂ ), 5.22 (d, 1H, J = 10.8 Hz, -CH = CH ₂ ), 1.35 (s, 9H , -C (CH ₃ ) ₃ ), 1.34 (s, 9H, -C (CH ₃ ) ₃ ). FAB-MS: 901 (M ⁺ ).
Elemental analysis Calcd for C ₄₃ H ₃₆ F ₆ IrN ₃ : C, 57.32; H, 4.03; F, 12.65; Ir, 21.33; N, 4.66.Found: C, 57.44; H, 3.99; N, 4.58.
[Synthesis Example 2]
Synthesis of polymerizable iridium complex compound (B)

This will be described with reference to the above scheme.
<Synthesis of Compound (B1)>
4-amino-2-chloropyridine (22.08 g, 172 mmol), N, N-dimethylaminopyridine (420 mg, 3.44 mmol), and acetic anhydride (35.07 g, 343 mmol) were added to the eggplant flask at 70 ° C. The reaction was stirred for 2 hours. After the reaction, the mixture was cooled to room temperature, carefully added with methanol (20 ml) while cooling, and further added with pure water (70 ml), crystals were precipitated. The crystals were collected by filtration, washed with pure water, and dried under vacuum to obtain compound (B1) as colorless crystals. The yield was 29.20 g, and the yield was 100%. The identification result of the compound (B1) was as follows.
¹ H-NMR (270 MHz, CDCl ₃ ) ppm: 8.26 (d, 1H, J = 5.7 Hz, ArH), 7.62 (d, 1H, J = 1.6 Hz, ArH), 7.47 (br, 1H, NH), 7.34 (dd, 1H, J = 5.5, 2.0 Hz, ArH), 2.23 (s, 3H, CH ₃ ).
<Synthesis of Compound (B2)>
In a three-necked flask equipped with a Jimroth condenser and a three-way cock, compound (B1) (1.71 g, 10.0 mmol), 2,4-difluorophenylboronic acid (1.895 g, 12.0 mmol), sodium carbonate ( 2.12 g, 20.0 mmol), 1,2-dimethoxyentane (30 ml), and pure water (10 ml) were added, and nitrogen was bubbled. Further, [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) dichloromethane complex (163 mg, 0.2 mmol) was added, and the mixture was reacted by refluxing with stirring for 4 hours. After the reaction, the mixture was cooled to room temperature, ethyl acetate was added, and the mixture was washed with an aqueous sodium chloride solution. The obtained organic layer was dried over magnesium sulfate and filtered, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: ethyl acetate / chloroform = 0/1 to 1/0 gradient), the solvent was distilled off and the residue was dried under reduced pressure to give compound (B2) as a white solid Got as. The yield was 2.10 g, and the yield was 85%. The identification result of the compound (B2) was as follows.
¹ H-NMR (270 MHz, CDCl ₃ ) ppm: 8.59 (d, 1H, J = 5.7 Hz, ArH), 8.00 (m, 1H, ArH), 7.73 (s, 1H, ArH), 7.64 (dd, 1H , J = 5.7, 1.9 Hz, ArH), 7.37 (br, 1H, NH), 6.99 (m, 1H, ArH), 6.91 (m, 1H, ArH), 2.24 (s, 3H, CH ₃ ).
<Synthesis of Compound (B3)>
Compound (B2) (2.10 g, 8.46 mmol) and 10% hydrochloric acid (30 g) were added to an eggplant flask and reacted with stirring for 3 hours with stirring. After the reaction, the reaction solution was filtered with glass fiber filter paper while it was hot to remove insoluble matters, and the filtrate was cooled to precipitate hydrochloride. Sodium hydroxide was added to the filtrate containing the precipitated hydrochloride to neutralize it, and the organic matter was extracted with chloroform. The obtained organic layer was dried over magnesium sulfate and filtered, and the solvent was distilled off to obtain compound (B3) as a colorless liquid. The yield was 1.79g.

<Synthesis of Compound (B4)>
Compound (B3) (1.79 g), 30% aqueous hydrogen bromide solution (40 ml), pure water (40 ml), and copper (I) bromide (23 mg, 0.16 mmol) were added to an eggplant flask and stirred at 60 ° C. did. To this was added a 5N aqueous sodium nitrite solution (5 ml, 25 mmol), and the mixture was further stirred at 60 ° C. for 30 minutes to react. After the reaction, sodium hydroxide was added to make the reaction solution alkaline, and a gray solid precipitated. The gray solid was collected by filtration, washed with pure water, dissolved in ethyl acetate, and insolubles were removed with a membrane filter. The solvent was distilled off and recrystallized from methanol / water. The crystals were collected by filtration, washed with pure water, and dried under vacuum to obtain compound (B4) as colorless crystals. The yield was 1.55 g, and the yield based on the compound (B2) was 68%. The identification result of the compound (B4) was as follows.
¹ H-NMR (270 MHz, CDCl ₃ ) ppm: 8.52 (d, 1H, J = 5.4 Hz, ArH), 8.01 (m, 1H, ArH), 7.95 (s, 1H, ArH), 7.44 (dd, 1H , J = 5.1, 1.6 Hz, ArH), 7.01 (m, 1H, ArH), 6.93 (m, 1H, ArH).
<Synthesis of Compound (B5)>
In a three-necked flask equipped with a Jimroth condenser and a three-way cock, compound (B4) (540 mg, 2.0 mmol), sodium carbonate (424 mg, 4.0 mmol), 1.2-dimethoxyentane (6 ml), and pure Water (2 ml) was added and nitrogen bubbled. Further, vinylboronic acid dibutyl ester (529 μl, 2.4 mmol) and tetrakis (triphenylphosphine) palladium (0) (163 mg, 0.2 mmol) were added, and these were reacted by refluxing with stirring for 2.5 hours. After the reaction, the mixture was cooled to room temperature, ethyl acetate was added, and the organic layer was washed with an aqueous sodium chloride solution. The obtained organic layer was dried over magnesium sulfate and filtered, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: chloroform / hexane = 1/1 to 1/0 gradient), then the solvent was distilled off and dried under reduced pressure to give compound (B5) as a colorless liquid. Obtained. The yield was 388 mg, and the yield was 89%. The identification result of the compound (B5) was as follows.
¹ H-NMR (270 MHz, CDCl ₃ ) ppm: 8.65 (d, 1H, J = 5.4 Hz, ArH), 7.98 (m, 1H, ArH), 7.72 (s, 1H, ArH), 7.26 (dd, 1H , over wrapped w / chloroform, ArH), 7.00 (m, 1H, ArH), 6.92 (m, 1H, ArH), 6.73 (dd, 1H, J = 17.8, 10.8 Hz, -CH = CH ₂ ), 6.02 ( d, 1H, J = 17.6 Hz, -CH = CH ₂ ), 5.22 (d, 1H, J = 10.8 Hz, -CH = CH ₂ ).
<Synthesis of Iridium Complex Compound (B)>
The above compound (W) (288 mg, 0.2 mmol) and potassium carbonate (138 mg, 1.0 mmol) were added to a two-necked flask equipped with a Jimroth condenser and a three-way cock, and the atmosphere was replaced with nitrogen. Further, mesitylene (4 ml), compound (B5) (109 mg, 0.5 mmol), and silver (I) trifluoromethanesulfonate (123 mg, 0.48 mmol) were added, and these were refluxed with stirring for 3 hours to react. I let you. After the reaction, the mixture was cooled to room temperature, chloroform was added, and the mixture was filtered through celite to remove insoluble matters. The solvent of the filtrate was distilled off, and the residue was purified by silica gel column chromatography. However, due to insufficient separation, preparative HPLC (column: Shodex 5C8 20E, eluent: THF / water = 7/3, flow rate : 3 ml / min). Recrystallization from methanol / dichloromethane and vacuum drying gave a polymerizable iridium complex compound (B) as a yellow solid. The yield was 113 mg and the yield was 31%. The identification result of the compound (B) was as follows.
¹ H-NMR (270 MHz, CDCl ₃ ) ppm: 8.31 (s, 2H, ArH), 8.25 (s, 1H, ArH), 7.38 (d, 1H, J = 5.9 Hz, ArH), 7.37 (d, 1H , J = 5.9 Hz, ArH), 7.32 (d, 1H, J = 6.2 Hz, ArH), 6.94 (m, 3H, ArH), 6.70 (dd, 1H, J = 17.4, 10.9 Hz, -CH = CH ₂ ), 6.39 (m, 3H, ArH), 6.27 (m, 3H, ArH), 5.97 (d, 1H, J = 17.3 Hz, -CH = CH ₂ ), 5.51 (d, 1H, J = 10.5 Hz,- CH = CH ₂ ), 1.34 (s, 9H, -C (CH ₃ ) ₃ ), 1.34 (s, 9H, -C (CH ₃ ) ₃ ).
FAB-MS: 901 (M ⁺ ).
Elemental analysis Calcd for C ₄₃ H ₃₆ F ₆ IrN ₃ : C, 57.32; H, 4.03; F, 12.65; Ir, 21.33; N, 4.66.Found: C, 57.51; H, 4.00; N, 4.73.
[Synthesis Example 3]
Synthesis of polymerizable iridium complex compound (C)

This will be described with reference to the above scheme.
<Synthesis of Compound (C1)>
To an eggplant flask, 40% sulfuric acid (50 g) and 4-amino-2-chloropyridine (3.0 g, 23.3 mmol) were added and dissolved. While stirring at 0 ° C., sodium nitrite (1.93 g, 28.0 mmol) was further added, and these were reacted by stirring at room temperature for 24 hours. After the reaction, a sodium hydroxide aqueous solution and a sodium hydrogen carbonate aqueous solution were added to neutralize the reaction solution, and the reaction product was extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate and then filtered, the solvent was distilled off, and the residue was dried under reduced pressure to obtain 2-chloro-4-hydroxypyridine (compound (C1)) as a light brown solid. The yield was 2.78 g, and the yield was 92%. The identification result of the compound (C1) was as follows.
¹ H-NMR (270 MHz, DMSO-d ₆ ) ppm: 11.20 (s, 1H, -OH), 8.09 (d, 1H, J = 5.4 Hz, ArH), 6.81 (s, 1H, ArH), 6.77 ( d, 1H, J = 2.2 Hz, ArH).
<Synthesis of Compound (C2)>
In a two-necked flask equipped with a Jimroth condenser and a three-way cock, compound (C1) (667 mg, 5.15 mmol), potassium carbonate (1.424 g, 10.3 mmol), and 3,5-ditertiarybutyl-4- Hydroxytoluene (3 mg) was added and the atmosphere was replaced with nitrogen. Further, dehydrated DMF (20 ml) and 4-vinylbenzyl chloride (1.179 g, 7.73 mmol) were added, and these were reacted by stirring at 80 ° C. for 2 hours. After the reaction, chloroform was added and the organic layer was washed twice with pure water. The obtained organic layer was dried over magnesium sulfate and filtered, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: chloroform / hexane = 1/1 to chloroform gradient), then the solvent was distilled off and dried under reduced pressure to obtain compound (C2) as a white solid. . The yield was 1.247 g, and the yield was 99%. The identification result of the compound (C2) was as follows.
¹ H-NMR (270 MHz, CDCl ₃ ) ppm: 8.20 (d, 1H, J = 5.4 Hz, ArH), 7.45 (d, 2H, J = 7.8 Hz, ArH), 7.35 (d, 2H, J = 8.4 Hz, ArH), 6.91 (d, 1H, J = 2.2 Hz, ArH), 6.81 (dd, 1H, J = 5.9, 2.4 Hz, ArH), 6.73 (dd, 1H, J = 17.8, 10.8 Hz, -CH = CH ₂ ), 5.78 (d, 1H, J = 17.6 Hz, -CH = CH ₂ ), 5.29 (d, 1H, J = 11.3 Hz, -CH = CH ₂ ), 5.09 (s, 2H, -CH ₂ O-).
<Synthesis of Compound (C3)>
In a three-necked flask equipped with a Jimroth condenser and a three-way cock, compound (C2) (1.240 g, 5.05 mmol), 2,4-difluorophenylboronic acid (956 mg, 6.06 mmol), sodium carbonate (1. 071 g, 10.1 mmol), 1,2-dimethoxyentane (15 ml), and pure water (5 ml) were added, and nitrogen was bubbled. Further tetrakis (triphenylphosphine) palladium (0) (116 mg, 0.1 mmol) was added, and these were reacted by refluxing with stirring for 3 hours. After the reaction, the reaction mixture was cooled to room temperature, pure water was added, and the reaction product was extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate and filtered, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: chloroform / hexane = 1/1 to chloroform to ethyl acetate / chloroform = 1/9 gradient), the solvent was distilled off, and the residue was dried under reduced pressure to give the compound ( C3) was obtained as a colorless liquid. The yield was 389 mg, and the yield was 24%. The identification result of the compound (C3) was as follows.
¹ H-NMR (270 MHz, CDCl ₃ ) ppm: 8.52 (d, 1H, J = 5.7 Hz, ArH), 7.99 (m, 1H, ArH), 7.45 (d, 2H, J = 8.6 Hz, ArH), 7.40 (d, 2H, J = 8.1 Hz, ArH), 7.36 (m, 1H, ArH), 7.02-6.83 (m, 3H, ArH), 6.73 (dd, 1H, J = 17.4, 10.9 Hz, -CH = CH ₂ ), 5.78 (d, 1H, J = 17.8 Hz, -CH = CH ₂ ), 5.28 (d, 1H, J = 11.1 Hz, -CH = CH ₂ ), 5.15 (s, 2H, -CH ₂ O -).
<Synthesis of polymerizable iridium complex compound (C)>
In a two-necked flask equipped with a Jimroth condenser tube and a three-way cock, the above compound (W) (288 mg, 0.2 mmol), potassium carbonate (138 mg, 1.0 mmol), compound (C3) (162 mg, 0.5 mmol) ) And 3,5-ditertiary butyl-4-hydroxytoluene (3 mg) was added, and the atmosphere was replaced with nitrogen. Further, mesitylene (4 ml) and silver (I) trifluoromethanesulfonate (123 mg, 0.48 mmol) were added, and these were reacted under reflux with stirring for 3 hours. After the reaction, the mixture was cooled to room temperature, chloroform was added, and the mixture was filtered through celite to remove insoluble matters. The solvent of the filtrate was distilled off, and the residue was purified by silica gel column chromatography (eluent: chloroform / hexane = 2/8 to chloroform gradient), recrystallized from methanol / dichloromethane, vacuum dried and polymerized. The iridium complex compound (C) was obtained as yellow microcrystals. The yield was 87 mg, and the yield was 22%. The identification result of the compound (C) was as follows.
¹ H-NMR (270 MHz, CDCl ₃ ) ppm: 8.30 (m, 2H, ArH), 7.90 (m, 1H, ArH), 7.45 (d, 2H, J = 8.4 Hz, ArH), 7.40-7.37 (m , 3H, ArH), 7.30 (d, 1H, J = 5.7 Hz, ArH), 7.23 (d, 1H, J = 6.5 Hz, ArH), 6.93 (d, 2H, J = 5.9 Hz, ArH), 6.73 ( dd, 1H, J = 17.6, 10.8 Hz, -CH = CH ₂ ), 6.51 (dd, 1H, J = 6.2, 2.7 Hz, ArH), 6.38 (m, 3H, ArH), 6.30-6.24 (m, 3H , ArH), 5.78 (d, 1H, J = 17.8 Hz, -CH = CH ₂ ), 5.29 (d, 1H, J = 10.8 Hz, -CH = CH ₂ ), 5.13 (s, 2H, -CH ₂ O -), 1.34 (s, 9H, -C (CH ₃ ) ₃ ), 1.33 (s, 9H, -C (CH ₃ ) ₃ ).
FAB-MS: 1007 (M ⁺ ).
Elemental Analysis Calcd for C ₅₀ H ₄₂ F ₆ IrN _3O : C, 59.63; H, 4.20; F, 11.32; Ir, 19.09; N, 4.17; O, 1.59. Found: C, 59.85; H, 4.12; N, 4.20 .
[Synthesis Example 4]
Synthesis of polymerizable iridium complex compound (D)

This will be described with reference to the above scheme.
<Synthesis of Compound (D1)>
Methyltriphenylphosphonium bromide (4.29 g, 12 mmol) was added to a two-necked flask equipped with a three-way cock and a dropping funnel, and the atmosphere was replaced with nitrogen. Further, dehydrated THF (100 ml) was added, and while cooling in an ice bath, 1.6 M n-butyllithium hexane solution (7.5 ml, 12 mmol) was slowly added from the dropping funnel, and these were stirred at 0 ° C. for 2 hours. . Furthermore, 3-bromo-2,4-difluorobenzaldehyde (2.21 g, 10 mmol) synthesized according to the method described in the pamphlet of International Publication No. WO9935117 was added, and these were reacted by stirring overnight at room temperature. After the reaction, pure water was carefully added, and the reaction product was extracted with chloroform. The obtained organic layer was dried over magnesium sulfate and filtered, and the solvent was distilled off. The residue is purified by silica gel column chromatography (eluent: chloroform / hexane = 1/4 to 1/1 gradient), the solvent is distilled off, and the residue is dried under reduced pressure to obtain compound (D1) as a colorless liquid. It was. The yield was 1.58 g, and the yield was 72%.

<Synthesis of Compound (D2)>
Compound (D1) (1.58 g, 7.2 mmol) and lithium chloride (916 mg, 21.6 mmol) were added to a two-necked flask equipped with a Jimroth condenser tube and a three-way cock, and the atmosphere was replaced with nitrogen. Dehydrated 1,4-dioxane (15 ml), 2- (tributyltin) pyridine (2.91 g, 7.9 mmol), tetrakis (triphenylphosphine) palladium (0) (231 mg, 0.2 mmol), and 3,5- Ditertiary butyl-4-hydroxytoluene (5 mg) was added and reacted with stirring for 2 hours under reflux. After the reaction, 10% aqueous potassium fluoride solution and ethyl acetate were further added, and the mixture was stirred at room temperature for 1 hour, and the reaction product was extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate and filtered, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: chloroform / hexane = 1 / 1-chloroform), the solvent was distilled off, and the residue was dried under reduced pressure to obtain compound (D2) as a colorless liquid. Yield 1.22g. Yield 78%.

<Synthesis of polymerizable iridium complex compound (D)>
In a two-necked flask equipped with a Jimroth condenser and a three-way cock, the above compound (W) (288 mg, 0.2 mmol) (288 mg, 0.2 mmol), potassium carbonate (138 mg, 1.0 mmol), compound (D2 ) (109 mg, 0.5 mmol) and 3,5-ditertiarybutyl-4-hydroxytoluene (3 mg) were added, and the atmosphere was replaced with nitrogen. Further, mesitylene (4 ml) and silver (I) trifluoromethanesulfonate (123 mg, 0.48 mmol) were added, and these were reacted under reflux with stirring for 4 hours. After the reaction, the mixture was cooled to room temperature, chloroform was added, and the mixture was filtered through celite to remove insoluble matters. The solvent of the filtrate was distilled off, and the residue was purified by silica gel column chromatography (eluent: chloroform / hexane = 2/8 to chloroform gradient), recrystallized from methanol / dichloromethane, vacuum dried and polymerized. The iridium complex compound (D) was obtained as yellow microcrystals. The yield was 101 mg, and the yield was 28%. The identification result of the compound (D) was as follows.
FAB-MS: 901 (M ⁺ ).
Elemental analysis Calcd for C ₄₃ H ₃₆ F ₆ IrN ₃ : C, 57.32; H, 4.03; F, 12.65; Ir, 21.33; N, 4.66.Found: C, 57.37; H, 4.19; N, 4.65.
[Synthesis Example 5]
Synthesis of polymerizable iridium complex compound (E)

This will be described with reference to the above scheme.
<Synthesis of Compound (E1)>
3-bromo-2,4-difluorophenol (2.09 g, 10 mmol), potassium carbonate (2) synthesized by the method described in International Publication WO9935117 Pamphlet in a two-necked flask equipped with a Jimroth condenser and a three-way cock .76 g, 20 mmol) and 3,5-ditertiarybutyl-4-hydroxytoluene (3 mg) were added, and the atmosphere was replaced with nitrogen. Further, dehydrated DMF (40 ml) and 4-vinylbenzyl chloride (2.29 g, 15 mmol) were added, and these were reacted by stirring at 80 ° C. for 2 hours. After the reaction, chloroform was added and washed twice with pure water. The obtained organic layer was dried over magnesium sulfate and filtered, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: chloroform / hexane = 1/1 to chloroform gradient), then the solvent was distilled off and the residue was dried under reduced pressure to obtain compound (E1) as a white solid. . The yield was 3.12 g, and the yield was 96%.

<Synthesis of Compound (E2)>
Compound (E1) (1.63 g, 5 mmol) and lithium chloride (636 mg, 15 mmol) were added to a two-necked flask equipped with a Jimroth condenser tube and a three-way cock, and the atmosphere was replaced with nitrogen. Further dehydrated 1,4-dioxane (10 ml), 2- (tributyltin) pyridine (2.02 g, 5.5 mmol), tetrakis (triphenylphosphine) palladium (0) (116 mg, 0.1 mmol), and 3,5 -Ditertiary butyl-4-hydroxytoluene (3 mg) was added, and these were reacted with stirring for 2 hours under reflux. After the reaction, 10% aqueous potassium fluoride solution and ethyl acetate were added, and the mixture was stirred at room temperature for 1 hour and extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate and filtered, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: chloroform / hexane = 1 / 1-chloroform), the solvent was distilled off, and the residue was dried under reduced pressure to obtain compound (E2) as a white solid. Yield 1.12 g. Yield 69%.

<Synthesis of polymerizable iridium complex compound (E)>
In a two-necked flask equipped with a Jimroth condenser and a three-way cock, the above compound (W) (288 mg, 0.2 mmol) (288 mg, 0.2 mmol), potassium carbonate (138 mg, 1.0 mmol), compound (D2 ) (109 mg, 0.5 mmol) and 3,5-ditertiarybutyl-4-hydroxytoluene (3 mg) were added, and the atmosphere was replaced with nitrogen. Further, mesitylene (4 ml) and silver (I) trifluoromethanesulfonate (123 mg, 0.48 mmol) were added, and these were reacted under reflux with stirring for 4 hours. After the reaction, the mixture was cooled to room temperature, chloroform was added, and the mixture was filtered through celite to remove insoluble matters. The solvent of the filtrate was distilled off, and the residue was purified by silica gel column chromatography (eluent: chloroform / hexane = 2/8 to chloroform gradient), recrystallized from methanol / dichloromethane, vacuum dried and polymerized. The iridium complex compound (E) was obtained as yellow microcrystals. The yield was 113 mg and the yield was 28%. The identification result of the compound (E) was as follows.
FAB-MS: 1007 (M ⁺ ).
Elemental Analysis Calcd for C ₅₀ H ₄₂ F ₆ IrN _3O : C, 59.63; H, 4.20; F, 11.32; Ir, 19.09; N, 4.17; O, 1.59. Found: C, 59.80; H, 4.09; N, 4.31 .
[Synthesis Example 6]
Synthesis of polymerizable iridium complex compound (F)

This will be described with reference to the above scheme.
<Synthesis of Compound (W21)>
In a three-necked flask equipped with a Jimroth condenser and a three-way cock, 2-chloro-4-picoline (1.276 g, 10.0 mmol), 4-fluorophenylboronic acid (1.679 g, 12.0 mmol), sodium carbonate (2.12 g, 20.0 mmol), 1,2-dimethoxyentane (30 ml), and pure water (10 ml) were added, and nitrogen was bubbled. Further tetrakis (triphenylphosphine) palladium (0) (231 mg, 0.2 mmol) was added, and these were reacted by refluxing with stirring for 2 hours. After the reaction, the mixture was cooled to room temperature, chloroform was added, and the organic layer was washed with an aqueous sodium chloride solution. The obtained organic layer was dried over magnesium sulfate and filtered, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: chloroform / hexane = 1/1 to chloroform gradient), then the solvent was distilled off and dried under reduced pressure to obtain compound (W21) as a colorless liquid. . The yield was 1.520 g, and the yield was 81%.

<Synthesis of Compound (W)>
In a 50 ml two-necked flask equipped with a Jimroth condenser tube and a three-way cock, compound (W21) (449 mg, 2.4 mmol), iridium (III) chloride trihydrate (353 mg, 1 mmol), 2-ethoxyethanol (15 ml) ), Pure water (5 ml) was added, and nitrogen was bubbled through the resulting solution for 5 minutes, followed by refluxing with stirring for 15 hours under nitrogen. After the reaction, the reaction mixture was cooled to room temperature, and pure water (30 ml) was added to precipitate the product. The precipitate was collected by filtration, washed with 50 ml of a mixed solvent of methanol / water = 7/3, and then dried under reduced pressure to obtain compound (W2) as a yellow powder. The yield was 504 mg and the yield was 84%. This powder was used in the next step without being identified.

<Synthesis of Compound (F1)>
In a three-necked flask equipped with a Jimroth condenser and a three-way cock, 6-chloropyridine-3-carbaldehyde (1.416 g, 10.0 mmol), 4-fluorophenylboronic acid (1.679 g, 12.0 mmol), Sodium carbonate (2.12 g, 20.0 mmol), 1,2-dimethoxyentane (30 ml), and pure water (10 ml) were added, and nitrogen was bubbled. Further tetrakis (triphenylphosphine) palladium (0) (231 mg, 0.2 mmol) was added, and these were reacted by refluxing with stirring for 2 hours. After the reaction, the mixture was cooled to room temperature, chloroform was added, and the organic layer was washed with an aqueous sodium chloride solution. The obtained organic layer was dried over magnesium sulfate and filtered, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: chloroform / hexane = 1 / 1-chloroform gradient), then the solvent was distilled off and dried under reduced pressure to obtain compound (F1) as a white solid. . The yield was 1.520 g, and the yield was 81%.

<Synthesis of Compound (F2)>
Compound (F1) (402 mg, 2.0 mmol) was added to an eggplant flask equipped with a three-way cock, and the atmosphere was replaced with nitrogen. Further, dehydrated THF (4 ml) was added, 3M methylmagnesium bromide diethyl ether solution (0.73 ml, 2.2 mmol) was slowly added, and these were stirred at room temperature for 4 days to be reacted. After the reaction, pure water was carefully added and the reaction product was extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate and filtered, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: gradient from chloroform to ethyl acetate / chloroform = 2/8), the solvent was distilled off and the residue was dried under reduced pressure to obtain compound (F2) as a colorless liquid. It was. The yield was 408 mg, and the yield was 94%.

<Synthesis of Iridium Complex Compound (F)>
The above compound (W2) (240 mg, 0.2 mmol), potassium carbonate (138 mg, 1.0 mmol), compound (F2) (109 mg, 0.5 mmol) in a two-necked flask equipped with a Jimroth condenser and a three-way cock Was added and replaced with nitrogen. After adding mesitylene (4 ml) and silver (I) trifluoromethanesulfonate (123 mg, 0.48 mmol), the mixture was reacted under reflux with stirring for 4 hours. After the reaction, the mixture was cooled to room temperature, chloroform was added, and the mixture was filtered through celite to remove insoluble matters. The solvent of the filtrate was distilled off, and the residue was purified by silica gel column chromatography (eluent: chloroform / hexane = 2/8 to chloroform gradient), recrystallized from methanol / dichloromethane, vacuum dried and polymerized. The iridium complex compound (F) was obtained as an orange solid. The yield was 51 mg and the yield was 33%. The identification result of the compound (F) was as follows.
FAB-MS: 763 (M ⁺ ).
Elemental Analysis Calcd for C ₃₇ H ₂₇ F ₃ IrN ₃ : C, 58.26; H, 3.57; F, 7.47; Ir, 25.20; N, 5.51. Found: C, 58.20; H, 3.65; N, 5.46.
[Synthesis Example 7]
<Synthesis of other polymerizable iridium complex compounds>
The polymerizable iridium complex compounds (G) to (T) shown below were synthesized according to the synthesis method of the polymerizable iridium complex compounds (A) to (F).

[Synthesis Example 8]
Synthesis of polymerizable iridium complex compound (U)

This will be described with reference to the above scheme.
<Synthesis of Iridium Complex Compound (U1)>
Into a two-necked flask equipped with a Jimroth condenser and a three-way cock, the above compound (W) (288 mg, 0.4 mmol) (576 mg, 0.4 mmol), potassium carbonate (276 mg, 2.0 mmol) and 4- ( 2-Pyridyl) benzaldehyde (183 mg, 1.0 mmol) was added and the atmosphere was replaced with nitrogen. Further, mesitylene (8 ml) and silver (I) trifluoromethanesulfonate (247 mg, 0.96 mmol) were added, and these were reacted under reflux with stirring for 3 hours. After the reaction, the mixture was cooled to room temperature, chloroform was added, and the mixture was filtered through celite to remove insoluble matters. The solvent of the filtrate was distilled off, and the residue was purified by silica gel column chromatography (eluent: chloroform chloroform), recrystallized from methanol / dichloromethane, and dried under vacuum to obtain the polymerizable iridium complex compound (U1) as yellow. Obtained as crystals. The yield was 215 mg, and the yield was 31%.

<Synthesis of polymerizable iridium complex compound (U)>
Methyltriphenylphosphonium bromide (120 mg, 0.34 mmol) was dissolved in 10 ml of THF, and 1.6 M n-butyllithium hexane solution (0.18 ml, 0.29 mmol) was added at 0 ° C. After stirring at 0 ° C. for 30 minutes, iridium complex compound (U1) (208 mg, 0.24 mmol) was added, and the mixture was reacted at room temperature for 2 hours. After the reaction, dilute hydrochloric acid was added to the reaction solution, and organic substances were extracted with chloroform. The obtained organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (eluent: chloroform / hexane = 3/1), and further recrystallized from methanol / dichloromethane to obtain a polymerizable iridium complex compound (U) as yellow crystals. The yield was 105 mg, and the yield was 51%. The identification result of the compound (U) was as follows.
FAB-MS: 865 (M ⁺ ).
Elemental analysis Calcd for C ₄₃ H ₃₈ F ₄ IrN ₃ : C, 59.71; H, 4.43; F, 8.79; Ir, 22.22; N, 4.86.
Found: C, 59.30; H, 4.40; N, 4.92.
[Example 1]
In a synthetic sealed container of a copolymer of a polymerizable iridium complex compound, a polymerizable compound (X) and a polymerizable compound (Y), 100 mg of the polymerizable iridium complex compound (A) synthesized in Synthesis Example 1 and the following polymerization 450 mg of the polymerizable compound (X) (same as the above polymerizable compound (E02)) and 450 mg of the following polymerizable compound (Y) (same as the above polymerizable compound (E19)) were put, and dehydrated toluene (9.9 ml) was added. After the addition, a toluene solution (0.1 M) of dimethyl-2,2′-azobis (2-methylpropionate) (trade name V-601 (manufactured by Wako Pure Chemical Industries, Ltd.)) which is a radical polymerization initiator. 198 μl) was added, and the freeze deaeration operation was repeated 5 times. The mixture was sealed under vacuum and reacted by stirring at 60 ° C. for 60 hours. After the reaction, the reaction solution was dropped into acetone (500 ml) to cause precipitation. Further, reprecipitation purification with toluene-acetone was repeated twice, followed by vacuum drying at 50 ° C. overnight to obtain the desired copolymer (PA). Table 1 shows the recovery rate of the obtained copolymer, the weight average molecular weight (Mw) estimated from the GPC measurement in terms of polystyrene, the copolymerization ratio in the copolymer estimated from the results of ICP emission analysis and ¹³ C-NMR measurement. Show.

[Examples 2 to 20, Comparative Examples 1 to 3]
A copolymer was synthesized in the same manner as in Example 1 except that the polymerizable iridium complex compound (A) was changed to the polymerizable iridium complex described in Table 1. For these copolymers, the recovery rate, weight average molecular weight (Mw), and copolymerization ratio are shown in Table 1, as in Example 1. The polymerizable iridium complex compound (V) was synthesized according to the method described in JP-A-2003-206320.

[Example 21]
Fabrication of organic EL element A substrate with ITO (Indium Tin Oxide) in which two ITO electrodes with a width of 4 mm as an anode are formed in a stripe shape on one surface of a 25 mm square glass substrate (Nippo Electric Co., Ltd.) , LTD.) To produce an organic EL device. First, poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (trade name “Vitron P”, manufactured by Bayer Co., Ltd.) is rotated on the ITO (anode) of the substrate with ITO by a spin coating method. After coating under conditions of 3500 rpm and a coating time of 40 seconds, the anode buffer layer was formed by drying at 60 ° C. for 2 hours under reduced pressure in a vacuum dryer. The film thickness of the obtained anode buffer layer was about 50 nm.

  Next, a coating solution for forming a light emitting layer was prepared. That is, 150 mg of the copolymer (PA) synthesized in Example 1 as a luminescent material was dissolved in 9850 mg of chloroform (manufactured by Wako Pure Chemical Industries, Ltd., special grade), and the resulting solution was filtered with a filter having a pore size of 0.2 μm. A coating solution was obtained. Next, the prepared coating solution is applied onto the anode buffer layer by spin coating under the conditions of a rotation speed of 3000 rpm and a coating time of 30 seconds, and dried at room temperature (25 ° C.) for 30 minutes, whereby the light emitting layer Formed. The film thickness of the obtained light emitting layer was about 100 nm. Next, the substrate on which the light emitting layer is formed is placed in a vapor deposition apparatus, barium is vapor-deposited to a thickness of 5 nm at a vapor deposition rate of 0.01 nm / s, and then aluminum is deposited as a cathode to a thickness of 150 nm at a vapor deposition rate of 1 nm / s. The organic EL element was produced by vapor deposition. The barium layer and the aluminum layer are formed in two stripes having a width of 3 mm perpendicular to the extending direction of the anode, and an organic light emitting device having a length of 4 mm and a width of 3 mm per glass substrate. Four were produced.

EL characteristic evaluation Co., Ltd., ADVANTEST Co., Ltd. Programmable DC voltage / current source TR6143 was used to apply voltage to the organic EL element to emit light, and the light emission luminance was measured using Topcon Co., Ltd. luminance meter BM-8. . Table 2 shows the emission color, emission uniformity, external quantum efficiency at 100 cd / m ² lighting, and luminance half time when driven at a constant current at an initial luminance of 100 cd / m ^2. (The values of the quantum efficiency and the luminance half time are average values of four elements formed on one substrate.) Moreover, the measurement result of the luminance half time in Table 2 is expressed as a relative value when a measured value of the element 3 described later is set to 100.

[Examples 22 to 40 and Comparative Examples 4 and 6]
A device was fabricated in the same manner as in Example 6 except that the light emitting material (copolymer) shown in Table 2 was used as the light emitting material instead of the copolymer (PA). These elements were also evaluated for EL emission characteristics in the same manner as in Example 21. The results are shown in Table 2.

[Comparative Example 5]
A device was produced in the same manner as in Example 21 except that instead of the copolymer (PA) as the light emitting material, a mixture of 135 mg of the copolymer (P) and 15 mg of the iridium complex compound (Z) was used. . With respect to this device, the EL emission characteristics were evaluated in the same manner as in Example 21. The results are shown in Table 2.

  From Table 2, the organic electroluminescent element (Examples 21-40) using the polymer light-emitting material of this invention used the polymer light-emitting material which copolymerized the conventional polymerizable iridium complex which has a picolinic acid ligand. Compared with an organic EL device (Comparative Example 4) or an organic EL device (Comparative Example 5) which is simply dispersed in a polymer without copolymerizing an iridium complex, it has a high luminous efficiency, a long lifetime, and a high maximum luminance. It is clear. Further, an organic EL device (Comparative Example 6) using a polymer light-emitting material obtained by copolymerizing a polymerizable iridium complex having no electron-withdrawing group on a phenylpyridine ligand having a polymerizable substituent emits blue-green light. did.

Claims (13)

A blue light-emitting polymer compound comprising a structural unit derived from a compound represented by the following formula (1);

In [Equation ^(1), R 1 ~R ⁴ and R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon atoms 7-40 An aralkyl group, an amino group optionally substituted by an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a silyl group optionally substituted by an alkyl group having 1 to 30 carbon atoms, or An electron-withdrawing substituent,
The electron-withdrawing substituent is a halogen atom, a fluorine-substituted C 1-10 alkyl group, a fluorine-substituted C 1-10 alkoxy group, a cyano group, an aldehyde group, or a C 2-10 carbon atom. An acyl group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aminocarbonyl group having 1 to 10 carbon atoms, a thiocyanate group, and a sulfonyl group having 1 to 10 carbon atoms;
At least one of R ^{1 to} R ⁴ and at least one of R ^{11 to} R ¹⁴ are each independently the electron-withdrawing substituent;
R ^{5 to} R ⁸ and R ^{15 to} R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 40 carbon atoms, or 1 carbon atom. It is the silyl group which may be substituted by the amino group which may be substituted by the -30 alkyl group, the C1-C30 alkoxy group, or the C1-C30 alkyl group.
However, one of R ^{11 to} R ¹⁸ is a substituent having a polymerizable carbon-carbon double bond. ].   2. The electron-withdrawing substituent is a fluorine atom, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, a fluorine-substituted carbon group having 1 to 10 carbon atoms, or a cyano group. The blue light emitting polymer compound described in 1. In the formula (1), R ¹ , R ³ , R ¹¹ and R ¹³ are hydrogen atoms, and R ² , R ⁴ , R ¹² and R ¹⁴ are fluorine atoms. The blue light emitting polymer compound described in 1. ^{3. The} formula (1), wherein R ¹ , R ³ , R ⁴ , R ¹¹ , R ¹³ and R ¹⁴ are hydrogen atoms, and R ² and R ¹² are fluorine atoms. The blue light emitting polymer compound described in 1.   The blue light-emitting polymer compound according to claim 1, further comprising a structural unit derived from a hole-transporting polymerizable compound and / or an electron-transporting polymerizable compound. . An organic electroluminescence device comprising a substrate, a pair of electrodes formed on the substrate, and one or more organic layers including a light emitting layer between the pair of electrodes,
An organic electroluminescent device, wherein the light emitting layer contains a blue light emitting non-conjugated polymer compound having a structural unit derived from a blue light emitting compound represented by the following formula (1);

In [Equation ^(1), R 1 ~R ⁴ and R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon atoms 7-40 An aralkyl group, an amino group optionally substituted by an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a silyl group optionally substituted by an alkyl group having 1 to 30 carbon atoms, or An electron-withdrawing substituent,
The electron-withdrawing substituent is a halogen atom, a fluorine-substituted C 1-10 alkyl group, a fluorine-substituted C 1-10 alkoxy group, a cyano group, an aldehyde group, or a C 2-10 carbon atom. An acyl group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aminocarbonyl group having 1 to 10 carbon atoms, a thiocyanate group, and a sulfonyl group having 1 to 10 carbon atoms;
At least one of R ^{1 to} R ⁴ and at least one of R ^{11 to} R ¹⁴ are each independently the electron-withdrawing substituent;
R ^{5 to} R ⁸ and R ^{15 to} R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 40 carbon atoms, or 1 carbon atom. It is the silyl group which may be substituted by the amino group which may be substituted by the -30 alkyl group, the C1-C30 alkoxy group, or the C1-C30 alkyl group.
However, one of R ^{11 to} R ¹⁸ is a substituent having a polymerizable carbon-carbon double bond. ].   The electron-withdrawing substituent is a fluorine atom, a fluorine-substituted C 1-10 alkyl group, a fluorine-substituted C 1-10 alkoxy group, or a cyano group. The organic electroluminescent element of description. In the formula (1), R ¹ , R ³ , R ¹¹ and R ¹³ are hydrogen atoms, and R ² , R ⁴ , R ¹² and R ¹⁴ are fluorine atoms. The organic electroluminescent element of description. In the formula (1), R ¹ , R ³ , R ⁴ , R ¹¹ , R ¹³ and R ¹⁴ are hydrogen atoms, and R ² and R ¹² are fluorine atoms. The organic electroluminescent element of description.   10. The blue light-emitting non-conjugated polymer compound further includes a structural unit derived from a hole transport polymerizable compound and / or an electron transport polymerizable compound. An organic electroluminescence device according to any one of the above.   A step of forming at least one organic compound layer containing the polymer compound according to any one of claims 1 to 5 on an anode, and a step of forming a cathode on the organic compound layer. A method for producing an organic electroluminescent element.   The image display apparatus provided with the organic electroluminescent element in any one of Claims 6-10.   The surface emitting light source provided with the organic electroluminescent element in any one of Claims 6-10.

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