JP2005029785A - High-molecular copolymer containing metal coordination compound and organic electroluminescent element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-molecular copolymer containing a metal coordination compound having blue phosphorescence emission excellent in color purity, and to provide a high-molecular copolymer containing a metal coordination compound having various color emission of from blue to red with long driving life. <P>SOLUTION: The high-molecular copolymer containing a metal coordination compound which imparts predetermined color phosphorescence emission comprises a metal coordination compound monomer unit determining energy level of the lowest excitation state, a specific (substituted) conjugated monomer unit, and a (substituted) branched monomer unit, wherein each monomer unit is connected by a specific bonding group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel metal coordination compound-containing polymer and an organic electroluminescence (EL) device using the same.

  In recent years, electroluminescent devices have attracted attention for use as large-area solid-state light sources as an alternative to incandescent lamps and gas-filled lamps, for example. On the other hand, it is also drawing attention as the most powerful self-luminous display that can replace liquid crystal displays in the field of flat panel displays (FPD). In particular, an organic electroluminescence (EL) element in which an element material is composed of an organic material has been commercialized as a low power consumption type full color FPD. In particular, a high-molecular organic EL element in which an organic material is composed of a high-molecular material is easier to print and inkjet than a low-molecular organic EL element that requires film formation in a vacuum system. Since a film is possible, it is an indispensable element for future large-screen organic EL displays.

  Until now, high molecular organic EL devices include conjugated polymers such as poly (p-phenylene-vinylene) (see, for example, WO 90/13148) and non-conjugated polymers (see, for example, I. Sokolik et al. , J. Appl. Phys. 1993.74, 3584) have been used. However, the light emission lifetime as an element is low, which has been an obstacle to constructing a full-color display.

  In order to solve these problems, in recent years, polymer type organic EL devices using various polyfluorene type and poly (p-phenylene) type conjugated polymers have been proposed. Nothing is found to be satisfactory.

  As one means for solving this problem, an element utilizing phosphorescence from an excited triplet has been studied. If phosphorescence from an excited triplet can be used, a light emission quantum yield of at least three times in principle can be expected as compared with the case of using fluorescence from an excited singlet. Furthermore, considering the use of excitons by intersystem crossing from a singlet to a triplet in terms of energy, a luminescence quantum yield of 4 times, that is, 100% can be expected in principle.

  Examples of research so far include M.A.Baldo et al., Appl.Phys.Lett.1999.75.4. In this document, the following materials are used. Abbreviations for each material are as follows.

Alq ₃ : Aluminum-quinolinol complex (tris (8-quinolinolato) aluminum)
α-NPD: N, N'-Di-naphthalen-1-yl-N, N'-diphenyl-biphenyl-4,4'-diamine
CBP: 4,4'-N, N'-dicarbazole-biphenyl
BCP: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
Ir (ppy) ₃ : iridium-phenylpyridine complex (tris (2-phenylpyridine) iridium)

In addition, examples using triplet emission include JP-A-11-329739, JP-A-11-256148, and JP-A-8-319482.
MABaldo et al., Appl. Phys. Lett. 1999.75.4 International Publication No. 90/13148 Pamphlet JP 11-329739 A Japanese Patent Laid-Open No. 11-256148 JP-A-8-319482

  In view of the above-described conventional problems, the present invention provides a polymer copolymer containing a metal coordination compound having phosphorescence emission from blue to red with excellent color purity, and further from blue to red. An object of the present invention is to provide a polymer copolymer containing a metal coordination compound that emits light of various colors and has a long driving life.

  In addition, the present invention provides a polymer composition having phosphorescence emission from blue to red with excellent color purity, and further, a polymer having emission of various colors from blue to red and having a long driving life. An object is to provide a composition.

  Furthermore, an object of the present invention is to provide an organic electroluminescence device that emits light of various colors from blue to red and is excellent in light emission characteristics, reliability, and the like.

  As a result of intensive studies, the present inventors have found that a polymer copolymer containing a metal coordination compound into which various substituents are introduced as a ligand has an emission color ranging from blue to red and has a long driving life. The inventors have found that this is an excellent material and have completed the present invention.

（式中、ＭはＩｒ、Ｒｈ、Ｒｕ、Ｏｓ、ＰｄまたはＰｔであり、ｎは１または２である。環ＡはＭに結合した窒素原子を含む環状化合物である。Ｘ_１〜Ｘ_７およびＲはそれぞれ独立に−Ｒ^１、−ＯＲ^２、−ＳＲ^３、−ＯＣＯＲ^４、−ＣＯＯＲ^５、−ＳｉＲ^６Ｒ^７Ｒ^８、および−ＮＲ^９Ｒ^１０（ただし、Ｒ^１〜Ｒ^１０は水素原子、ハロゲン原子、シアノ基、ニトロ基、炭素数１〜２２個の直鎖、環状もしくは分岐アルキル基又はそれらの水素原子の一部もしくは全部がハロゲン原子で置換されたハロゲン置換アルキル基、炭素数６〜３０個のアリール基、炭素数２〜３０個のヘテロアリール基もしくは炭素数７〜３０個のアラルキル基又はそれらの水素原子の一部もしくは全部がハロゲン原子で置換されたハロゲン置換アリール基、ハロゲン置換ヘテロアリール基、ハロゲン置換アラルキル基を表し、Ｒ^１〜Ｒ^１０はそれぞれ同一であっても異なっていてもよい。）からなる群から選択される置換基であって、また、Ｘ_１〜Ｘ_７は同一であっても異なっていてもよく、環ＡはＸ_１〜Ｘ_７で定義される基と同様の置換基を有していてもよい。環ＣはＭに結合した化合物であって、式（１４）で表される結合基と結合する化合物である。環ＣはＸ_１〜Ｘ_７で定義される基と同様の置換基を有していてもよい。）で表されるいずれかの金属配位化合物モノマー単位と、置換又は非置換であってもよい式（１３）：

（式中、Ａｒ_１及びＡｒ_２は２価のアリーレン及び／又はヘテロアリーレンを表す。複数個のＶ、Ｒ_１及びＲ_２は、それぞれ独立に−Ｒ^１、−ＯＲ^２、−ＳＲ^３、−ＯＣＯＲ^４、−ＣＯＯＲ^５および−ＳｉＲ^６Ｒ^７Ｒ^８（ただし、Ｒ^１〜Ｒ^８は、炭素数１〜２２個の直鎖、環状もしくは分岐アルキル基、または、炭素数２〜３０個のアリール基もしくはヘテロアリール基を表す）からなる群から選択される置換基であって、それぞれは同一であっても異なっていてもよい、アリーレンもしくはヘテロアリーレン残基中の置換可能な位置に結合した置換基であり、ａ及びｂは各々独立に０以上の整数である。Ｒ_１及びＲ_２は、それぞれ独立に水素原子であってもよい。ｎ、ｍ、ｌはそれぞれ独立に０または１であり、ｎ、ｍ、ｌが同時に０となることはない。）で表される共役モノマー単位と、置換または非置換であってもよい枝分れ構造モノマー単位とを含み、前記各モノマー単位を結合する基が、式（１４）：

（式中、Ｇは−Ｏ−、−Ｒ−Ｏ−Ｒ−、−Ｓ−、−ＮＲ−、−ＣＲ_２−、−ＳｉＲ_２−、−ＳｉＲ_２−Ｏ−ＳｉＲ_２−、および−ＳｉＲ_２−Ｏ−ＳｉＲ_２−Ｏ−ＳｉＲ_２−（ここで、Ｒは、炭素数１〜２２個の直鎖、環状もしくは分岐アルキル基、または、炭素数２〜３０個のアリール基もしくはヘテロアリール基を表す）からなる群から選択される２価の基であり、ｂは０〜１の整数を表す）で表される結合基である金属配位化合物含有高分子共重合体が提供される。ここで、金属配位化合物モノマー単位のＸ_１〜Ｘ_７、ＲにおけるＲ^１〜Ｒ^１０は置換基を有していてもよく、置換基の例として、ハロゲン原子、シアノ基、アルデヒド基、アミノ基、アルキル基、アルコキシ基、アルキルチオ基、カルボキシル基、スルホン酸基、ニトロ基等を挙げることができる。これらの置換基は、さらにハロゲン原子、メチル基等によって置換されていてもよい。 That is, according to the present invention, the formulas (1) to (12):

Wherein M is Ir, Rh, Ru, Os, Pd or Pt, and n is 1 or 2. Ring A is a cyclic compound containing a nitrogen atom bonded to M. X _{1 to} X ₇ and ^-R 1 R are each ^{independently, -OR 2, -SR 3, -OCOR} 4, -COOR 5, -SiR 6 R 7 R 8, and ^-NR 9 ^{R 10} (provided ^that, R 1 ^{to R 10} is a hydrogen atom A halogen atom, a cyano group, a nitro group, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or a halogen-substituted alkyl group in which part or all of the hydrogen atoms are substituted with halogen atoms, carbon number 6 A halogen-substituted aryl in which a part or all of hydrogen atoms thereof are substituted with a halogen atom or an aryl group having 30 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms Group, a halogen-substituted heteroaryl group, a halogen-substituted aralkyl group, an R ¹ to R ¹⁰ are substituents selected from the group consisting of each may be the same or different.), Also, X _{1 to} X ₇ may be the same or different, and ring A may have a substituent similar to the group defined by X _{1 to} X _7. Ring C is bonded to M. A compound that binds to the linking group represented by formula (14), wherein ring C may have the same substituents as the groups defined by X _{1 to} X ₇ ). Any of the metal coordination compound monomer units represented and formula (13), which may be substituted or unsubstituted:

(In the formula, Ar ₁ and Ar ₂ represent a divalent arylene and / or heteroarylene. A plurality of V, R ₁ and R ₂ are each independently -R ¹ , -OR ² , -SR ³ ,- OCOR ⁴ , —COOR ⁵ and —SiR ⁶ R ⁷ R ⁸ (where R ^{1 to} R ⁸ are linear, cyclic or branched alkyl groups having 1 to 22 carbon atoms, or aryl having 2 to 30 carbon atoms) A substituent selected from the group consisting of a group or a heteroaryl group, each of which may be the same or different, and is substituted at a substitutable position in an arylene or heteroarylene residue Each of a and b is independently an integer of 0 or more, R ₁ and R ₂ may each independently be a hydrogen atom, and n, m and l are each independently 0 or 1. , N, m, Are not simultaneously 0.) and a branched monomer unit that may be substituted or unsubstituted, and a group that binds each monomer unit is represented by the formula ( 14):

(Wherein, G is -O -, - R-O- R -, - S -, - NR -, - CR 2 -, - SiR 2 -, - SiR 2 -O-SiR 2 -, and -SiR ₂ —O—SiR ₂ —O—SiR ₂ — (wherein R represents a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. A metal coordination compound-containing polymer copolymer which is a divalent group selected from the group consisting of: and a bond group represented by b represents an integer of 0 to 1. Here, X _{1 to} X ₇ of the metal coordination compound monomer unit, R ^{1 to} R ¹⁰ in R may have a substituent, and examples of the substituent include a halogen atom, a cyano group, an aldehyde group, amino Groups, alkyl groups, alkoxy groups, alkylthio groups, carboxyl groups, sulfonic acid groups, nitro groups and the like. These substituents may be further substituted with a halogen atom, a methyl group or the like.

In the metal coordination compound-containing polymer copolymer of the present invention, in the formulas (1) to (12), the ring A has the same substituent as the group defined by X _{1 to} X _7. Preference is given to pyridine, quinoline, benzoxazole, benzothiazole, benzimidazole, benzotriazole, imidazole, pyrazole, oxazole, thiazole, triazole, benzopyrazole triazine or isoquinoline.

（式中、複数個のＹは、−Ｒ^１、−ＯＲ^２、−ＳＲ^３、−ＯＣＯＲ^４、−ＣＯＯＲ^５および−ＳｉＲ^６Ｒ^７Ｒ^８（ただし、Ｒ^１〜Ｒ^８は、炭素数１〜２２個の直鎖、環状もしくは分岐アルキル基、または、炭素数２〜３０個のアリール基もしくはヘテロアリール基を表す）からなる群から選択される置換基であって、それぞれは同一であっても異なっていてもよく、枝分れ構造骨格のベンゼン環の置換可能な位置に結合した置換基であり、ｐは０〜４の整数を表す。）からなる群から選択される枝分れ構造モノマー単位であることが好ましい。 A branched monomer unit which may be substituted or unsubstituted, which is one of the constituent monomer units of the metal coordination compound-containing polymer, has the formula (15):

(In the formula, plural Ys represent -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ^5, and -SiR ⁶ R ⁷ R ⁸ (wherein R ^{1 to} R ⁸ have 1 carbon atom) A substituent selected from the group consisting of ˜22 linear, cyclic or branched alkyl groups, or an aryl group or heteroaryl group having 2 to 30 carbon atoms, each being the same And a branched structure selected from the group consisting of a substituent bonded to a substitutable position of the benzene ring of the branched structure skeleton, and p represents an integer of 0 to 4. A monomer unit is preferred.

  Another object of the present invention is to provide an organic electroluminescent device produced using the polymer composition containing a metal coordination compound-containing polymer copolymer or a conjugated or non-conjugated polymer. To do.

  Moreover, this invention can provide the organic electroluminescent element produced using the polymer composition mixed with the said metal coordination compound containing polymer copolymer or the conjugated or nonconjugated polymer.

  The metal coordination compound-containing polymer copolymer of the present invention is suitable as a material for an organic EL device, for example. These exhibit good film-forming ability because of good color purity and stability of light emission and easy film formation. Accordingly, the organic EL device of the present invention using the same exhibits good light emission color purity and stability, and is excellent in productivity.

  In organic EL, in order to obtain phosphorescence emission from blue to red, it is necessary to change the energy level of the lowest excited state. In general, the lifetime of the excited triplet state is longer than that of the excited singlet state, and the molecule stays in a high energy state for a long time, causing reactions with surrounding substances, structural changes in the molecule itself, reactions between excitons, etc. Therefore, it is considered that the conventional phosphorescent light emitting device has a short driving life.

  Accordingly, the present inventors have conducted various studies, and the polymer copolymer containing the metal coordination compound monomer units represented by the following formulas (1) to (12) has phosphorescence emission from blue to red. The present inventors have found that the phosphorescent material has a long driving life.

（式中、ＭはＩｒ、Ｒｈ、Ｒｕ、Ｏｓ、ＰｄまたはＰｔであり、ｎは１または２である。環ＡはＭに結合した窒素原子を含む環状化合物である。Ｘ_１〜Ｘ_７およびＲはそれぞれ独立に−Ｒ^１、−ＯＲ^２、−ＳＲ^３、−ＯＣＯＲ^４、−ＣＯＯＲ^５、−ＳｉＲ^６Ｒ^７Ｒ^８、および−ＮＲ^９Ｒ^１０（ただし、Ｒ^１〜Ｒ^１０は水素原子、ハロゲン原子、シアノ基、ニトロ基、炭素数１〜２２個の直鎖、環状もしくは分岐アルキル基又はそれらの水素原子の一部もしくは全部がハロゲン原子で置換されたハロゲン置換アルキル基、炭素数６〜３０個のアリール基、炭素数２〜３０個のヘテロアリール基もしくは炭素数７〜３０個のアラルキル基又はそれらの水素原子の一部もしくは全部がハロゲン原子で置換されたハロゲン置換アリール基、ハロゲン置換ヘテロアリール基、ハロゲン置換アラルキル基を表し、Ｒ^１〜Ｒ^１０はそれぞれ同一であっても異なっていてもよい。）からなる群から選択される置換基であって、また、Ｘ_１〜Ｘ_７は同一であっても異なっていてもよく、環ＡはＸ_１〜Ｘ_７で定義される基と同様の置換基を有していてもよい。環ＣはＭに結合した化合物であって、結合基と結合する化合物である。環ＣはＸ_１〜Ｘ_７で定義される基と同様の置換基を有していてもよい。）ここで、金属配位化合物モノマー単位のＸ_１〜Ｘ_７、ＲにおけるＲ^１〜Ｒ^１０は置換基を有していてもよく、置換基の例として、ハロゲン原子、シアノ基、アルデヒド基、アミノ基、アルキル基、アルコキシ基、アルキルチオ基、カルボキシル基、スルホン酸基、ニトロ基等を挙げることができる。これらの置換基は、さらにハロゲン原子、メチル基等によって置換されていてもよい。 Formulas (1) to (12):

Wherein M is Ir, Rh, Ru, Os, Pd or Pt, and n is 1 or 2. Ring A is a cyclic compound containing a nitrogen atom bonded to M. X _{1 to} X ₇ and ^-R 1 R are each ^{independently, -OR 2, -SR 3, -OCOR} 4, -COOR 5, -SiR 6 R 7 R 8, and ^-NR 9 ^{R 10} (provided ^that, R 1 ^{to R 10} is a hydrogen atom A halogen atom, a cyano group, a nitro group, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or a halogen-substituted alkyl group in which part or all of the hydrogen atoms are substituted with halogen atoms, carbon number 6 A halogen-substituted aryl in which a part or all of hydrogen atoms thereof are substituted with a halogen atom or an aryl group having 30 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms Group, a halogen-substituted heteroaryl group, a halogen-substituted aralkyl group, an R ¹ to R ¹⁰ are substituents selected from the group consisting of each may be the same or different.), Also, X _{1 to} X ₇ may be the same or different, and ring A may have a substituent similar to the group defined by X _{1 to} X _7. Ring C is bonded to M. A compound which binds to a linking group, and ring C may have the same substituent as the groups defined by X _{1 to} X _7. ) Here, metal coordination compound monomer unit X _{1 to} X ₇ , R ^{1 to} R ¹⁰ in R may have a substituent, and examples of the substituent include a halogen atom, a cyano group, an aldehyde group, an amino group, an alkyl group, an alkoxy group, and an alkylthio group. Group, carboxyl group, sulfonic acid group, nito Mention may be made of the group, and the like. These substituents may be further substituted with a halogen atom, a methyl group or the like.

Show examples of the substituent represented by X ₁ to X ₇ and R below, the invention is not limited to the following.

Examples of —R ¹ include a halogen atom such as a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a cyano group, a nitro group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, and butyl. Group, isobutyl group, tert-butyl group, cyclobutyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, cycloheptyl group, octyl group, nonyl group, decyl group, phenyl group, Tolyl, xylyl, mesityl, cumenyl, benzyl, phenethyl, methylbenzyl, diphenylmethyl, styryl, cinnamyl, biphenyl, terphenyl, naphthyl, anthryl, fluorenyl, Furan residue, thiophene residue, pyrrole residue, oxazol Residue, thiazole residue, imidazole residue, pyridine residue, pyrimidine residue, pyrazine residue, triazine residue, quinoline residue, quinoxaline residue or these are fluorine atom, chlorine atom, bromine atom, iodine atom, etc. And halogen-substituted products substituted with. Examples of —OR ² are hydroxyl group, methoxy group, ethoxy group, propoxy group, butoxy group, tert-butoxy group, octyloxy group, tert-octyloxy group, phenoxy group, 4-tert-butylphenoxy group, 1- Examples thereof include a naphthyloxy group, a 2-naphthyloxy group, and a 9-anthryloxy group. Examples of —SR ³ include a mercapto group, a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group, an octylthio group, a phenylthio group, a 2-methylphenylthio group, and a 4-tert-butylphenylthio group. it can. Examples of —OCOR ⁴ include a formyloxy group, an acetoxy group, and a benzoyloxy group. Examples of —COOR ⁵ include a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, a phenoxycarbonyl group, and a naphthyloxycarbonyl group. Examples of —SiR ⁶ R ⁷ R ⁸ include a silyl group, a trimethylsilyl group, a triethylsilyl group, and a triphenylsilyl group. Examples of —NR ⁹ R ¹⁰ include an amino group, N-methylamino group, N-ethylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-diisopropylamino group, N, Examples thereof include N-dibutylamino group, N-benzylamino group, N, N-dibenzylamino group, N-phenylamino group, and N, N-diphenylamino group.

The metal coordination compound used in the present invention has phosphorescence emission, and the lowest excited state is a triplet MLCT (Metal-to-Ligand charge transfer) excited state or a π-π ^* excited state. Conceivable. Phosphorescent emission occurs when transitioning from these states to the ground state.

  The phosphorescent quantum yield of the luminescent material of the present invention was as high as 0.1 to 0.9, and the phosphorescence lifetime was 1 to 60 μs. The short phosphorescence lifetime is a condition for increasing the luminous efficiency when an organic EL device is used. That is, when the phosphorescence lifetime is long, the proportion of molecules in the excited triplet state increases, and the light emission efficiency is reduced based on TT anionization at a high current density. The polymer copolymer containing the metal coordination compound of the present invention is a material suitable for a light-emitting material of an organic EL device because it has high phosphorescence emission efficiency and a short emission lifetime.

  In addition, the polymer copolymer containing a metal coordination compound has a minimum excited state energy level by variously changing the substituents of the metal coordination compound monomer units represented by the formulas (1) to (12). It changes and is suitable as a light emitting material for organic EL having blue to red light emission.

  In the metal coordination compound monomer units represented by the formulas (1) to (12), M is preferably iridium.

Ring A is preferably any of the cyclic compounds having the structure shown below, and more preferably the same as the group defined by X _{1 to} X ₇ (hereinafter collectively referred to as substituent Xn). Pyridine, quinoline, benzoxazole, benzothiazole, benzoimidazole, benzotriazole, imidazole, pyrazole, oxazole, thiazole, triazole, benzopyrazole, triazine or isoquinoline, more preferably pyridine, Quinoline or isoquinoline.

(Here, Z _{1 to} Z ₆ are each independently —R ¹ , —OR ² , —SR ³ , —OCOR ⁴ , —COOR ⁵ , —SiR ⁶ R ⁷ R ⁸ , and —NR ⁹ R ¹⁰ (where R ^{1 to} R ¹⁰ are each a hydrogen atom, a halogen atom, a cyano group, a nitro group, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or a part or all of these hydrogen atoms substituted with a halogen atom. A halogen-substituted alkyl group, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a part or all of hydrogen atoms thereof is substituted with a halogen atom is halogen-substituted aryl group, halogen-substituted heteroaryl group, a halogen-substituted aralkyl group, R ¹ to R ¹⁰ may each be the same or different. A substituent selected from the group consisting of, also, Z ₁ to Z ₆ are each may be the same or different.) Here, R ¹ to R ¹⁰ is substituted Examples of the substituent include a halogen atom, a cyano group, an aldehyde group, an amino group, an alkyl group, an alkoxy group, an alkylthio group, a carboxyl group, a sulfonic acid group, and a nitro group. These substituents may be further substituted with a halogen atom, a methyl group or the like.

Further, the ring C is another ligand bound to the metal M is X ₁ to X ₇ being defined may bidentate ligand may have the same substituent groups as in the metal Combines with M to form a ring. Ring C is preferably any one of the compounds having the structures shown below.

W is a divalent to hexavalent group that reacts with other monomer units to form a polymer copolymer, and is preferably divalent or trivalent. Examples of W include the same substituents as the following X _{1 to} X _8, and examples thereof include divalent to hexavalent groups that are bonded to the bonding group represented by the formula (14).

X _{1 to} X ₈ are —R ¹ , —OR ² , —SR ³ , —OCOR ⁴ , —COOR ⁵ , —SiR ⁶ R ⁷ R ⁸ , and —NR ⁹ R ¹⁰ (where R ^{1 to} R ¹⁰ are hydrogen Atoms, halogen atoms, cyano groups, nitro groups, straight-chain, cyclic or branched alkyl groups having 1 to 22 carbon atoms, or halogen-substituted alkyl groups in which some or all of these hydrogen atoms are substituted with halogen atoms, carbon numbers A 6-30 aryl group, a heteroaryl group having 2-30 carbon atoms or an aralkyl group having 7-30 carbon atoms, or a halogen-substituted aryl group in which some or all of the hydrogen atoms are substituted with halogen atoms, halogen-substituted heteroaryl group, a halogen-substituted aralkyl group, R ¹ to R ¹⁰ is selected from the group consisting of each may be the same or different.) A substituted group, also, X ₁ to X ₈ may or may not be the same. Here, R ^{1 to} R ¹⁰ may have a substituent, and examples of the substituent include a halogen atom, a cyano group, an aldehyde group, an amino group, an alkyl group, an alkoxy group, an alkylthio group, a carboxyl group, and a sulfone. An acid group, a nitro group, etc. can be mentioned. These substituents may be further substituted with a halogen atom, a methyl group or the like.

(Detailed explanation of synthesis method of metal coordination compound monomer unit)
Hereinafter, the synthesis method of the monomer unit used in the present invention will be described in detail using specific examples.

  The metal coordination compound monomer unit used in the polymer copolymer containing the metal coordination compound of the present invention can be produced by various synthetic methods known to those skilled in the art. For example, the method described in S. Lamansky et al., J. Am. Chem. Soc. 2001. 123. can be used. An example of the synthesis route of the metal coordination compound monomer unit represented by the formulas (1) to (12) used in the present invention (when ring A is a substituted pyridine) is shown by way of an iridium coordination compound monomer unit. In addition, although what is demonstrated here is related to (2) shown in Table 1 below, other exemplary compounds can be synthesized by substantially the same method.

(Synthesis of Ligand L ₁ )

(Synthesis of iridium complex monomer unit)

Here, L ₂ is a compound bonded to the metal M (in the above case, iridium) and is a ring C compound bonded to the bonding group.

  Below, the preferable aspect of the metal coordination compound monomer unit in this invention is shown.

For example, in the metal coordination compound monomer unit represented by the above formulas (1) to (6), when obtaining a blue light emitting material, the substituent is defined as the substituent Xn or the Xn that the ring A has From the viewpoint that at least one of the groups is effective for shortening the emission wavelength, a halogen atom, a cyano group or a halogen-substituted alkyl group is preferable, and a fluorine atom, a chlorine atom, a cyano group or a trifluoromethyl group is preferable. More preferably, it is more preferably a fluorine atom or a trifluoromethyl group, and most preferably a fluorine atom. When at least one of the substituents Xn or the substituents defined in the same manner as Xn of ring A has any of the above-mentioned substituents, the other Xn is often a hydrogen atom. It may be a substituent. For example, X ₇ is preferably an alkyl group or a halogen-substituted alkyl group.

Further, for example, in the case of obtaining a green to red light emitting material in the metal coordination compound monomer units represented by the formulas (1) to (6), similarly to the substituent Xn or Xn included in the ring A It is preferable that at least one of the defined substituents is —R, —OR, or —SR from the viewpoint that the emission color from green to red can be easily controlled. When at least one of the substituents Xn or the substituents defined in the same manner as Xn of ring A has any of the above-mentioned substituents, the other Xn is often a hydrogen atom. It may be a substituent. For example, X ₇ is preferably an alkyl group, an aryl group, or a heteroaryl group.

Also, for example, in the case of obtaining a blue light emitting material in the metal coordination compound monomer units represented by the formulas (7) to (12), use a compound in which B is> C═O or> SO _2. Is preferred. Further, in the case of obtaining the emission wavelength from green to red, B is>O,> S or> is preferably CR _2. Furthermore, in the above formulas (7) to (12), at least one of the substituents defined in the same manner as the substituent Xn or Xn of the ring A is a halogen atom from the viewpoint of obtaining a blue emission color. Are preferably a cyano group or a halogen-substituted alkyl group, more preferably a fluorine atom, a chlorine atom, a cyano group or a trifluoromethyl group, still more preferably a fluorine atom or a trifluoromethyl group, and a fluorine atom. Most preferably. Or it is preferable that it is -R, -OR, or -SR from a viewpoint that control of the luminescent color from blue to red is easy. When at least one of the substituents Xn or the substituents defined in the same manner as Xn of ring A has any of the above-mentioned substituents, the other Xn is often a hydrogen atom. It may be a substituent.

  Of the metal coordination compounds represented by the formulas (1) to (6), the metal coordination compound represented by the formula (1) or (4) is preferable from the viewpoint of easy synthesis. Of the metal coordination compounds represented by the formulas (7) to (12), the metal coordination compound represented by the formula (8) or (11) is preferable from the viewpoint of easy synthesis.

Illustrative compounds are shown below as specific examples of the metal coordination compound monomer unit, but are not limited thereto.
(Examples of metal coordination compounds)

  Specific examples of the metal coordination compound monomer unit of the present invention include compounds in which ring C is replaced with the following ligand in the compounds described in Tables 1 to 3 above.

（式中、Ａｒ_１及びＡｒ_２は２価のアリーレン及び／又はヘテロアリーレンを表す。複数個のＶ、Ｒ_１及びＲ_２は、それぞれ独立に−Ｒ^１、−ＯＲ^２、−ＳＲ^３、−ＯＣＯＲ^４、−ＣＯＯＲ^５および−ＳｉＲ^６Ｒ^７Ｒ^８（ただし、Ｒ^１〜Ｒ^８は、炭素数１〜２２個の直鎖、環状もしくは分岐アルキル基、または、炭素数２〜３０個のアリール基もしくはヘテロアリール基を表す）からなる群から選択される置換基であって、それぞれは同一であっても異なっていてもよい、アリーレンもしくはヘテロアリーレン残基中の置換可能な位置に結合した置換基であり、ａ及びｂは各々独立に０以上の整数である。Ｒ_１及びＲ_２は、それぞれ独立に水素原子であってもよい。ｎ、ｍ、ｌはそれぞれ独立に０または１であり、ｎ、ｍ、ｌが同時に０となることはない。）で表される共役モノマー単位と、置換または非置換であってもよい枝分れ構造モノマー単位とを含む金属配位化合物含有高分子共重合体である。 The polymer copolymer containing the metal coordination compound of the present invention has any of the metal coordination compound monomer units represented by the formulas (1) to (12) and a formula that may be substituted or unsubstituted. (13):

(In the formula, Ar ₁ and Ar ₂ represent a divalent arylene and / or heteroarylene. A plurality of V, R ₁ and R ₂ are each independently -R ¹ , -OR ² , -SR ³ ,- OCOR ⁴ , —COOR ⁵ and —SiR ⁶ R ⁷ R ⁸ (where R ^{1 to} R ⁸ are linear, cyclic or branched alkyl groups having 1 to 22 carbon atoms, or aryl having 2 to 30 carbon atoms) A substituent selected from the group consisting of a group or a heteroaryl group, each of which may be the same or different, and is substituted at a substitutable position in an arylene or heteroarylene residue Each of a and b is independently an integer of 0 or more, R ₁ and R ₂ may each independently be a hydrogen atom, and n, m and l are each independently 0 or 1. , N, m, There is a metal coordination compound-containing polymer copolymer comprising a conjugated monomer unit represented by the same time it becomes zero will not.), A substituted or unsubstituted there are branched optionally structural monomer units.

（式中、Ｇは−Ｏ−、−Ｒ−Ｏ−Ｒ−、−Ｓ−、−ＮＲ−、−ＣＲ_２−、−ＳｉＲ_２−、−ＳｉＲ_２−Ｏ−ＳｉＲ_２−、および−ＳｉＲ_２−Ｏ−ＳｉＲ_２−Ｏ−ＳｉＲ_２−（ここで、Ｒは、炭素数１〜２２個の直鎖、環状もしくは分岐アルキル基、または、炭素数２〜３０個のアリール基もしくはヘテロアリール基を表す）からなる群から選択される２価の基であり、ｂは０〜１の整数を表す）で表される結合基であることが好ましい。 The group bonding each monomer unit is represented by the formula (14):

(Wherein, G is -O -, - R-O- R -, - S -, - NR -, - CR 2 -, - SiR 2 -, - SiR 2 -O-SiR 2 -, and -SiR ₂ —O—SiR ₂ —O—SiR ₂ — (wherein R represents a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. Is a divalent group selected from the group consisting of: and b represents an integer of 0 to 1).

  The polymer copolymer containing the metal coordination compound of the present invention only needs to contain at least each of the above monomer components, and each monomer unit is randomly contained in the copolymer like a so-called random copolymer. Alternatively, it may be a copolymer in which some specific monomer units are present locally such as a block copolymer or a graft copolymer. Each of the three types of monomer units constituting the copolymer may be a single monomer or a combination of two or more types of monomers.

で表される共役モノマー単位は、単独で、または２種類以上を組み合わせて用いることができる。 Formula (13) used in the present invention:

These conjugated monomer units can be used alone or in combination of two or more.

In the monomer unit of the formula (13) of the present invention, Ar ₁ and Ar ₂ are divalent arylene and / or heteroarylene, and a plurality of V, R ₁ and R ₂ are each independently -R ¹ ,- ^{oR 2, -SR 3, -OCOR 4} , -COOR 5 or -SiR ⁶ R ⁷ R ⁸ (provided ^that, R 1 to R ⁸ is 1 to 22 straight-chain carbon atoms, cyclic or branched alkyl group, or A substituent selected from the group consisting of an aryl group or a heteroaryl group having 2 to 30 carbon atoms, each of which may be the same or different, in the arylene or heteroarylene residue A and b are each independently an integer of 0 or more. R ₁ and R ₂ may each independently be a hydrogen atom. n, m, and l are each independently 0 or 1, and n, m, and l are not 0 at the same time. ). Ar ₁ and Ar ₂ may be the same or different, and when a plurality of substituents V are substituted, these substituents may be the same substituents. There may be different types of substituents.

In the above formula (13), Ar ₁ and Ar ₂ are arylene and / or heteroarylene, which may be substituted or unsubstituted. The arylene and / or heteroarylene which may be substituted or unsubstituted is preferably a divalent group such as benzene, biphenyl, terphenyl, naphthalene, anthracene, tetracene, fluorene, phenanthrene, pyrene, chrysene. , Pyridine, pyrazine, quinoline, isoquinoline, acridine, phenanthroline, furan, pyrrole, thiophene, oxazole, oxadiazole, thiadiazole, triazole, benzoxazole, benzooxadiazole, benzothiadiazole, benzothiophene, diphenyloxadiazole, benzothiadiazole , Diphenyldiazole, diphenylthiadiazole and the like, and Ar ₁ and Ar ₂ may be used alone or in combination.

On the other hand, R ^{1 to} R ⁸ in the substituents V, R ₁ and R ₂ are each independently a linear alkyl group having 1 to 22 carbon atoms, a cyclic alkyl group or a branched alkyl group, or 2 to 2 carbon atoms. 30 aryl groups or heteroaryl groups. Such groups include, for example, methyl, ethyl, propyl, cyclopropyl, butyl, isobutyl, cyclobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl Group, cycloheptyl group, octyl group, nonyl group, decyl group, etc., linear alkyl group having 1 to 22 carbon atoms, cyclic alkyl group or branched alkyl group, phenyl group, naphthyl group, anthracenyl group, biphenyl residue , Terphenyl residue, furan residue, thiophene residue, pyrrole residue, oxazole residue, thiazole residue, imidazole residue, pyridine residue, pyrimidine residue, pyrazine residue, triazine residue, quinoline residue, Aryl group having 2 to 30 carbon atoms such as quinoxaline residue or hetero Aryl group, and the like.

The substituents V, R ₁ and R ₂ may further have a substituent. Examples of the substituent of V, R ₁ and R ₂ include the substituent represented by the above-mentioned —R ¹ , —OR ² , —SR ³ , —OCOR ⁴ , —COOR ⁵ or —SiR ⁶ R ⁷ R ⁸ , —NR ⁹ R ¹⁰ (wherein R ⁹ and R ¹⁰ are each independently a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 20 carbon atoms) The substituent represented by this is mentioned. When a plurality of substituents are present, the plurality of substituents may be the same or different.

In the conjugated monomer unit of the formula (13) of the present invention, V, R ₁ and R ₂ are each independently an unsubstituted group, that is, a hydrogen atom or an alkyl group represented by —R ^1. In view of solubility and heat resistance, an aryl group, a heteroaryl group directly substituted, or an alkoxy group represented by -OR ² , an aryloxy group, or a heteroaryloxy group is preferred. . The number of substituents is preferably from the viewpoint of polymerization reactivity, in which a or b is 0, that is, when a or b is 1 to 3, including the case of unsubstituted. Furthermore, as an aryl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted fluorene group, etc. are preferable. Further, as the heteroaryl group, an oxadiazole group, a phenyloxadiazole group, a phenylthiadiazole group, a benzothiadiazole group, and the like are preferable.

Typical examples of Ar ₁ and Ar ₂ include those represented by the following structural formulas.

These arylene and / or heteroarylene substituents R are each independently -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ or -SiR ⁶ R ⁷ R ⁸ (where R ¹ to R ⁸ represents a substituent selected from the group consisting of a hydrogen atom, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. Each of them may be the same or different and each is a substituent bonded to a substitutable position of the arylene and / or heteroarylene skeleton.

Among these substituents, each R is independently an unsubstituted group, that is, a hydrogen atom, or a group directly substituted by an alkyl group, aryl group, or heteroaryl group represented by -R ¹ , —OR ² , a hydroxyl group, an alkoxy group, an aryloxy group, and a heteroaryloxy group are preferable from the viewpoint of polymerization reactivity and heat resistance.

で表される枝分れ構造が好ましく、これらの枝分れ構造モノマー単位は、単独であるいは２種以上を組み合わせて使用することができる。 Further, the branched structure monomer unit which may be substituted or unsubstituted used in the present invention is preferably a unit having a trivalent or higher valent branched structure, and a trivalent or tetravalent branched structure. A unit having a structure is more preferable. As the branched structure monomer unit, the formula (15):

The branched structure represented by these is preferable, and these branched structure monomer units can be used alone or in combination of two or more.

In the branched monomer unit formula (15), the substituents Y are each independently —R ¹ , —OR ² , —SR ³ , —OCOR ⁴ , —COOR ⁵ or —SiR ⁶ R ⁷ R ^8. (Wherein R ^{1 to} R ⁸ represent a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms). Each of which may be the same or different, and is a substituent bonded to a substitutable position of the benzene ring of the branched structure skeleton, and p is an integer of 0 to 4. . p is preferably 0-2.

On the other hand, R ^{1 to} R ⁸ in the substituent Y are each independently a linear alkyl group having 1 to 22 carbon atoms, a cyclic alkyl group or a branched alkyl group, or an aryl group having 2 to 30 carbon atoms, or A heteroaryl group; Such groups include, for example, methyl, ethyl, propyl, cyclopropyl, butyl, isobutyl, cyclobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl Group, cycloheptyl group, octyl group, nonyl group, decyl group, etc., linear alkyl group having 1 to 22 carbon atoms, cyclic alkyl group or branched alkyl group, phenyl group, naphthyl group, anthracenyl group, biphenyl residue , Terphenyl residue, furan residue, thiophene residue, pyrrole residue, oxazole residue, thiazole residue, imidazole residue, pyridine residue, pyrimidine residue, pyrazine residue, triazine residue, quinoline residue, Aryl group having 2 to 30 carbon atoms such as quinoxaline residue or hetero Aryl group, and the like.

The substituent Y may further have a substituent. As a substituent which Y has, the substituent represented by said -R < ¹ >, -OR < ² >, -SR < ³ >, -OCOR < ⁴ >, -COOR < ⁵ > or -SiR < ⁶ > R < ⁷ > R < ⁸ >, further -NR < ⁹ > R < ¹⁰ > ( R ⁹ and R ¹⁰ each independently represents a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 20 carbon atoms. Substituents. When a plurality of substituents are present, the plurality of substituents may be the same or different.

Among these substituents, as Yp, each independently, p is 0, that is, unsubstituted, or a group in which Y is directly substituted with an alkyl group represented by -R ¹ is a polymerization reaction. From the viewpoint of heat resistance and heat resistance. In addition, the number of substituents is preferably from the viewpoint of polymerization reactivity, when it is unsubstituted, that is, when p is 1, including the case where p is 0.

（式中、Ｇは−Ｏ−、−Ｒ−Ｏ−Ｒ−、−Ｓ−、−ＮＲ−、−ＣＲ_２−、−ＳｉＲ_２−、−ＳｉＲ_２−Ｏ−ＳｉＲ_２−、および−ＳｉＲ_２−Ｏ−ＳｉＲ_２−Ｏ−ＳｉＲ_２−（ここで、Ｒは、炭素数１〜２２個の直鎖、環状もしくは分岐アルキル基、または、炭素数２〜３０個のアリール基もしくはヘテロアリール基を表す）からなる群から選択される２価の基であり、ｂは０〜１の整数を表す）で表されることが好ましい。 In the metal coordination compound-containing polymer copolymer of the present invention, the group that binds each monomer unit has the formula (14):

(Wherein, G is -O -, - R-O- R -, - S -, - NR -, - CR 2 -, - SiR 2 -, - SiR 2 -O-SiR 2 -, and -SiR ₂ —O—SiR ₂ —O—SiR ₂ — (wherein R represents a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. It is preferably a divalent group selected from the group consisting of: and b represents an integer of 0 to 1.

In the above formula (14), when b is 0, it means a single bond. Of these, as the linking group, a single bond or —O— is preferable from the viewpoint of ease of synthesis. _{-R-O-R -, -} NR -, - CR 2 -, - SiR 2 -, - SiR 2 -O-SiR 2 -, or _{-SiR 2 -O-SiR 2 -O-} SiR 2 - as R in Is preferably a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms from the viewpoint of imparting solubility, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable from the viewpoint of polymerization reactivity.

  The polymer copolymer containing the metal coordination compound of the present invention contains at least the above-described three-component monomer units, and if necessary, other monomer units may be substituted or replaced as “copolymerization monomer units”. A monomer unit having an unsubstituted triphenylamine skeleton can be contained. Examples of the monomer unit having such a triphenylamine skeleton include triphenylamine, N- (4-butylphenyl) -N, N-diphenylamine, N, N′-diphenyl-N, N′-bis (3-methyl Phenyl)-[1,1′-biphenyl] -4,4′-diamine, N, N′-bis (3-methylphenyl) -N, N′-bis (2-naphthyl)-[1,1′- Biphenyl] -4,4′-diamine and the like. Examples of groups that can be substituted on these aromatic rings include C1-C22 alkyl groups and alkoxy groups.

  The mole fraction of metal coordination compound monomer units in the total number of all monomer units in the polymer copolymer containing the metal coordination compound of the present invention is preferably 0.1 to 30%, preferably 0.5 to 20%. Is more preferable, and 1 to 10% is most preferable. If the metal coordination compound monomer unit is less than 0.1%, the emission chromaticity tends to deteriorate, and if it exceeds 30%, the emission luminance tends to decrease.

  The mole fraction of conjugated monomer units in the total number of all monomer units in the polymer copolymer containing the metal coordination compound of the present invention is preferably 50 to 99.9%, more preferably 60 to 99.5%. 75 to 99% is most preferred. If the conjugated monomer unit is less than 50%, the emission luminance tends to be low, and if it exceeds 99.9%, the emission chromaticity tends to deteriorate.

  The mole fraction of the branched monomer units which may be substituted or unsubstituted in the total number of monomer units in the polymer copolymer containing the metal coordination compound of the present invention is 0.1 to 30%. Is preferable, 0.5 to 20% is more preferable, and 1 to 10% is most preferable. If the branched monomer unit is less than 0.1%, the emission chromaticity tends to deteriorate, and if it exceeds 30%, the emission luminance tends to decrease.

  The monomer unit having a substituted or unsubstituted triphenylamine skeleton that can be copolymerized with the polymer copolymer containing the metal coordination compound of the present invention is a mole fraction in the total number of all monomer units of the polymer. 0 to 48% is preferable.

  The polymer copolymer containing the metal coordination compound of the present invention can be produced by various synthetic methods known to those skilled in the art. For example, in the absence of a group linking each monomer unit, T. Yamamoto et al. Bull. Chem. Soc. Jap., 51, 7, 2091 (1978) and M. Zembayashi Et al., Tet. Lett., 47, 4089 (1977), which is reported by Suzuki in Synthetic Communications, Vol. 11, No. 7, p. 513 (1981). Are commonly used for the production of copolymers. This reaction causes a Pd-catalyzed cross-coupling reaction (usually called “Suzuki reaction”) between an aromatic boronic acid derivative and an aromatic halide, and the corresponding aromatic ring By using for the reaction which couple | bonds together, the high molecular copolymer containing the metal coordination compound of this invention can be manufactured.

This reaction also requires soluble Pd compounds in the form of Pd (II) salts or Pd (0) complexes. Pd (OAc) ₂ and PdCl ₂ (dppf) complexes with 0.01 to 5 mole percent Pd (PPh ₃ ) ₄ , tertiary phosphine ligand, based on aromatic reactants, are generally preferred Pd sources. This reaction also requires a base, with aqueous alkaline carbonate or bicarbonate being most preferred. The reaction can also be promoted in a nonpolar solvent using a phase transfer catalyst. As the solvent, N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran or the like is used.

（式中、Ｒはメチル基、エチル基、プロピル基などの低級アルキル基、あるいは２個のＲが互いに結合して環を形成するエチレン基、プロピレン基などの低級アルキレン基であり、Ａｒ_１、Ａｒ_２、Ｒ_１、Ｒ_２、Ｖ、ａ、ｂ、ｎ、ｍ、ｌは前述のとおりのものである）で表される共役モノマー誘導体のジボロンエステル及び／又は共役モノマー誘導体のジブロモ化合物と、ジブロモ金属配位化合物誘導体モノマー、トリブロモ枝分れ構造誘導体とを、パラジウム（０）触媒存在下、水溶性塩基により共重合させて製造することができる。 In the case of the polymer of the present invention, for example, specifically,

(Wherein, R represents a lower alkylene group such as a methyl group, an ethyl group, a lower alkyl group such as propyl or two R are bonded to each other ethylene group which forms a ring, a propylene group,, Ar _1, Ar ₂ , R ₁ , R ₂ , V, a, b, n, m, and l are as described above) and a diboron ester of a conjugated monomer derivative and / or a dibromo compound of a conjugated monomer derivative , A dibromo metal coordination compound derivative monomer, and a tribromo branched structure derivative can be produced by copolymerization with a water-soluble base in the presence of a palladium (0) catalyst.

  When the group connecting each monomer unit is O, a difluoroconjugated monomer, a dihydroxy metal coordination compound derivative monomer, a trihydroxy branched structure derivative, a dibromo metal, as described in JP-A-9-136954 Coordination compound derivative monomer and tribromo branched structure derivative and dihydroxy conjugated monomer, or dibromo conjugated monomer and tribromo branched structure derivative and dihydroxy metal coordination compound derivative monomer are reacted in a polar solvent in the presence of a base. A polymer copolymer containing the metal coordination compound of the invention can be produced. In this reaction, the reaction for producing a polymer copolymer containing the metal coordination compound of the present invention is carried out in the presence of a base capable of deprotonating the dihydroxy compound. Such bases include alkali metal and alkaline earth metal carbonates and hydroxides such as potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide and the like. If the dihydroxy compound has low acidity and cannot be sufficiently deprotonated with sodium hydroxide, use a stronger base, for example, a metal hydride such as sodium hydride, or a metal amide such as butyl lithium or sodium amide. Also good. During the reaction of this base with the dihydroxy compound, water is generated. This water can be removed by azeotropic distillation.

  The polymer copolymer containing the metal coordination compound of the present invention can be further copolymerized with other monomers. Examples of other dihydroxy monomers include isopropylidenediphenol, for example. (Bisphenol A), 1,2-di (4-hydroxyphenyl) ethane, di (4-hydroxyphenyl) methane, N, N-bis (4-hydroxyphenyl) -N-phenylamine, N, N′-bis (4-hydroxyphenyl) -N, N′-bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine and the like.

  The molecular weight of the metal coordination compound-containing polymer of the present invention is preferably 10,000 to 1,000,000, more preferably 30,000 to 800,000. If it is less than 10,000, the film forming ability tends to decrease, and if it exceeds 1,000,000, the solubility tends to decrease.

  The polymer copolymer containing the metal coordination compound of the present invention can be used as an active layer material for an electroluminescent device. The active layer means that the layer can emit light when an electric field is applied (light emitting layer) or that improves charge injection or charge transfer (charge injection layer or charge transfer layer). Here, the charge means a negative or positive charge.

  The thickness of the active layer can be appropriately set in consideration of light emission efficiency and the like, and is preferably 10 to 300 nm, and more preferably 20 to 200 nm. If it is less than 10 nm, pinholes or the like tend to occur as thin film defects, and if it exceeds 300 nm, the characteristics tend to deteriorate.

  The copolymer of the present invention may be used by mixing with other materials. Moreover, the electroluminescent element using the copolymer of this invention may be laminated | stacked with the active layer containing the copolymer of this invention in the layer containing materials other than the said copolymer. As materials that may be used in combination with the copolymer of the present invention, known materials such as hole injection and / or hole transfer materials, electron injection and / or electron transfer materials, light emitting materials, binder polymers, etc. are used. it can. The material to be mixed may be a high molecular material or a low molecular material.

  Examples of usable materials for hole injection and / or hole transfer materials include arylamine derivatives, triphenylmethane derivatives, stilbene compounds, hydrazone compounds, carbazole compounds, high molecular weight arylamines, polyanilines, polythiophenes, etc. Examples are materials and materials obtained by polymerizing them. Usable materials for electron injection and / or electron transfer materials include oxadiazole derivatives, benzoxazole derivatives, benzoquinone derivatives, quinoline derivatives, quinoxaline derivatives, thiadiazole derivatives, benzodiazole derivatives, triazole derivatives, metal chelate complex compounds, And materials obtained by polymerizing them. Examples of the light-emitting material that can be used include arylamine derivatives, oxadiazole derivatives, perylene derivatives, quinacridone derivatives, pyrazoline derivatives, anthracene derivatives, rubrene derivatives, stilbene derivatives, coumarin derivatives, naphthalene derivatives, metal chelate complexes, Ir and Pt. Examples include materials such as metal complexes containing a central metal such as, and materials obtained by polymerizing them, polyfluorene derivatives, polyphenylene vinylene derivatives, polyphenylene derivatives, polythiophene derivatives, and the like. Any material that can be used for the binder polymer can be used as long as the properties are not significantly reduced. Examples of the binder polymer include materials such as polystyrene, polycarbonate, polyaryl ether, polyacrylate, polymethacrylate, and polysiloxane.

  Among these, the metal coordination compound-containing polymer copolymer of the present invention can be used as a polymer composition mixed with a conjugated or non-conjugated polymer. Examples of the conjugated or non-conjugated polymer that can be used as the polymer composition include polyphenylene derivatives, polyfluorene derivatives, polyphenylene vinylene derivatives, polythiophene derivatives, polyquinoline derivatives, and polytriphenylamine derivatives, which may be substituted or unsubstituted. , Polyvinyl carbazole derivatives, polyaniline derivatives, polyimide derivatives, polyamideimide derivatives, polycarbonate derivatives, polyacryl derivatives, polystyrene derivatives, and the like. In addition, these conjugated or non-conjugated polymers may be substituted or unsubstituted arylene and / or heteroarylene monomer units, benzene, biphenyl, terphenyl, naphthalene, anthracene, as other monomer units as necessary. , Tetracene, fluorene, phenanthrene, pyrene, chrysene, pyridine, pyrazine, quinoline, isoquinoline, acridine, phenanthroline, furan, pyrrole, thiophene, oxazole, oxadiazole, thiadiazole, triazole, benzoxazole, benzooxadiazole, benzothiadiazole, Triphenylamine, which is a monomer unit having a substituted or unsubstituted triphenylamine skeleton such as benzothiophene, N- (4-butylphenyl) -N-di Phenylamine, N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine, N, N′-bis (3-methylphenyl) Examples thereof include those copolymerized with —N, N′-bis (2-naphthyl)-[1,1′-biphenyl] -4,4′-diamine and the like.

  In order to use the copolymer or polymer composition of the present invention as an active layer material of an electroluminescent device, a method known to those skilled in the art, for example, inkjet, cast, from a solution or onto a substrate in the form of a film. It can be achieved by laminating using spraying, dipping, printing or spin coating. Printing methods include letterpress printing, intaglio printing, offset printing, lithographic printing, letterpress reversal offset printing, screen printing, gravure printing, and the like. Such a laminating method can be carried out usually in a temperature range of -20 to + 300 ° C, preferably 10 to 100 ° C, particularly preferably 15 to 50 ° C. Moreover, drying of the laminated | stacked polymer solution can be normally implemented by normal temperature drying, heat drying by a hotplate, etc.

  As a solvent used for the solution containing the copolymer, chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, anisole, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl cellosolve acetate, and the like can be used.

  Further, the metal coordination compound-containing polymer copolymer is preferably contained in an amount of 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, based on the total weight of the solution containing the copolymer. preferable. If it is less than 0.1% by weight, pinholes or the like tend to occur as thin film defects, and if it exceeds 5% by weight, film thickness unevenness tends to occur.

  The general structure of the electroluminescent device of the present invention comprising the polymer of the present invention is described in US Pat. No. 4,539,507 and US Pat. No. 5,151,629. The polymer-containing electroluminescent element is described in, for example, International Publication No. WO 90/13148 or European Patent Publication No. 0 443 861.

  These usually comprise an electroluminescent layer (light emitting layer) between a cathode and an anode where at least one of the electrodes is transparent. Furthermore, one or more electron injection layers and / or electron transfer layers can be inserted between the electroluminescent layer (light emitting layer) and the cathode, and further one or more hole injection layers and / or A hole transport layer can be inserted between the electroluminescent layer (light emitting layer) and the anode. The cathode material is preferably a metal or metal alloy such as Li, Ca, Mg, Al, In, Cs, Mg / Ag, or LiF. As anode, use metal (eg Au) or other material with metal conductivity, eg oxide (eg ITO: indium oxide / tin oxide) on transparent substrate (eg glass or transparent polymer) You can also

  The electron injection and / or electron transfer layer includes materials such as oxadiazole derivatives, benzoxazole derivatives, benzoquinone derivatives, quinoline derivatives, quinoxaline derivatives, thiadiazole derivatives, benzodiazole derivatives, triazole derivatives, metal chelate complex compounds, etc. Layer.

  For the hole injection and / or hole transfer layer, materials such as copper phthalocyanine, triphenylamine derivative, triphenylmethane derivative, stilbene compound, hydrazone compound, carbazole compound, high molecular weight arylamine, polyaniline, polythiophene, etc. The layer containing is mentioned.

  The invention is illustrated by the following examples without however being limited thereto. In addition to the examples shown below, when the above-described various monomer units are used, an electroluminescent device excellent in color purity, reliability, and light emission characteristics can be obtained.

Example 1 Metal coordination compound Synthesis of Table 1 (1) A THF solution of 3-bromo-9-methylcarbazole (30 mmol) in a THF mixture of magnesium (1.9 g, 80 mmol) was thoroughly stirred under an argon stream. While adding gradually, a Grignard reagent was prepared. The obtained Grignard reagent was gradually added dropwise to a THF solution of trimethyl borate ester (300 mmol) at −78 ° C. over 2 hours, followed by stirring for 2 days at room temperature. The reaction mixture was poured into 5% dilute sulfuric acid containing crushed ice and stirred. When the obtained aqueous solution was extracted with toluene and the extract was concentrated, a colorless solid was obtained. The obtained solid was recrystallized from toluene / acetone (1/2) to obtain a carbazole derivative boronic acid as colorless crystals (40%). The obtained carbazole derivative boronic acid (12 mmol) and 1,2-ethanediol (30 mmol) were refluxed in toluene for 10 hours and then recrystallized from toluene / acetone (1/4). As a result, the carbazole derivative boron ester was colorless. Obtained as crystals.

To a toluene solution of 2-bromopyridine (10 mmol), a carbazole derivative boron ester (10 mmol), and Pd (0) (PPh ₃ ) ₄ (0.2 mmol), 2M K ₂ CO ₃ aqueous solution was added vigorously under an argon stream. The mixture was refluxed for 48 hours with stirring. The reaction mixture was cooled to room temperature and then poured into a large amount of methanol to precipitate a solid. The precipitated solid was filtered by suction and washed with methanol to obtain a solid of 3- (2′-pyridyl) -9-methylcarbazole.

A 200 ml three-necked flask was charged with iridium (III) chloride (1.7 mmol), 3- (2′-pyridyl) -9-methylcarbazole (7.58 mmol), 50 ml of ethoxyethanol and 20 ml of water, at room temperature under a nitrogen stream. For 30 minutes, and then refluxed for 24 hours. The reaction product was cooled to room temperature, and the precipitate was collected by filtration, washed with water, and washed successively with ethanol and acetone. The mixture was dried under reduced pressure at room temperature to obtain a light yellow powder of di-μ-chloro-tetrakis [3- (2′-pyridyl) -9-methylcarbazole-N ^{1 ′} , C ² ] diiridium (III).

In a 200 ml three-necked flask, 70 ml of ethoxyethanol, di-μ-chloro-tetrakis [3- (2′-pyridyl) -9-methylcarbazole-N ^{1 ′} , C ² ] diiridium (III) (0.7 mmol) An acetylacetone derivative (2.10 mmol) represented by the following structural formula and sodium carbonate (9.43 mmol) were added, and the mixture was stirred at room temperature under a nitrogen stream, and then stirred at reflux for 15 hours.

The reaction product was ice-cooled, and the precipitate was collected by filtration and washed with water. The precipitate was purified by silica gel column chromatography (eluent: chloroform / methanol: 30/1) and bis [3- (2′-pyridyl) -9-methylcarbazole-N ^{1 ′} , C ² ] (dibromobenzylacetyl). A pale yellow powder of acetonato) iridium (III) was obtained.

  In addition, about the obtained compound, the confirmation was performed by the NMR spectrum, IR spectrum, etc. The same applies to the compounds shown below.

Example 2 Metal Coordination Compound Synthesis of Table 2 (125) In a THF mixture of magnesium (1.9 g, 80 mmol), a THF solution of 2-hydroxy-6-bromo-9-methylcarbazole (30 mmol) was added to an argon stream. The mixture was gradually added with good stirring to prepare a Grignard reagent. The obtained Grignard reagent was gradually added dropwise to a THF solution of trimethyl borate ester (300 mmol) at −78 ° C. over 2 hours, followed by stirring for 2 days at room temperature. The reaction mixture was poured into 5% dilute sulfuric acid containing crushed ice and stirred. When the obtained aqueous solution was extracted with toluene and the extract was concentrated, a colorless solid was obtained. The obtained solid was recrystallized from toluene / acetone (1/2) to obtain a carbazole derivative boronic acid as colorless crystals (40%). The obtained carbazole derivative boronic acid (12 mmol) and 1,2-ethanediol (30 mmol) were refluxed in toluene for 10 hours and then recrystallized from toluene / acetone (1/4). As a result, the carbazole derivative boron ester was colorless. Obtained as crystals.

To a toluene solution of 2-bromopyridine (10 mmol), a carbazole derivative boron ester (10 mmol), and Pd (0) (PPh ₃ ) ₄ (0.2 mmol), 2M K ₂ CO ₃ aqueous solution was added vigorously under an argon stream. The mixture was refluxed for 48 hours with stirring. The reaction mixture was cooled to room temperature and then poured into a large amount of methanol to precipitate a solid. The precipitated solid was subjected to suction filtration and washed with methanol to obtain 2-hydroxy-6- (2′-pyridyl) -9-methylcarbazole solid.

A 200 ml three-necked flask was charged with iridium (III) chloride (1.7 mmol), 2-hydroxy-6- (2′-pyridyl) -9-methylcarbazole (7.58 mmol), 50 ml ethoxyethanol and 20 ml water. The mixture was stirred at room temperature for 30 minutes under a nitrogen stream and then refluxed for 24 hours. The reaction product was cooled to room temperature, and the precipitate was collected by filtration, washed with water, and washed successively with ethanol and acetone. Drying under reduced pressure at room temperature gave a pale yellow powder of di-μ-chloro-tetrakis [2-hydroxy-6- (2′-pyridyl) -9-methylcarbazole-N ^{1 ′} , C ⁷ ] diiridium (III). It was.

In a 200 ml three-necked flask, 70 ml of ethoxyethanol, di-μ-chloro-tetrakis [2-hydroxy-6- (2′-pyridyl) -9-methylcarbazole-N ^{1 ′} , C ⁷ ] diiridium (III) ( 0.7 mmol), an acetylacetone derivative (2.10 mmol) represented by the following structural formula and sodium carbonate (9.43 mmol) were added, and the mixture was stirred at room temperature under a nitrogen stream, and then stirred at reflux for 15 hours.

The reaction product was ice-cooled, and the precipitate was collected by filtration and washed with water. The precipitate was purified by silica gel column chromatography (eluent: chloroform / methanol: 30/1) and bis [2-hydroxy-6- (2′-pyridyl) -9-methylcarbazole-N ^{1 ′} , C ⁷ ]. A pale yellow powder of (dibromobenzylacetylacetonato) iridium (III) was obtained.

Example 3 Metal coordination compound Synthesis of Table 3 (253) A THF solution of 2-bromo-9-fluorenone (30 mmol) in a THF mixture of magnesium (1.9 g, 80 mmol) was stirred well under an argon stream. While adding gradually, a Grignard reagent was prepared. The obtained Grignard reagent was gradually added dropwise to a THF solution of trimethyl borate ester (300 mmol) at −78 ° C. over 2 hours, followed by stirring for 2 days at room temperature. The reaction mixture was poured into 5% dilute sulfuric acid containing crushed ice and stirred. When the obtained aqueous solution was extracted with toluene and the extract was concentrated, a colorless solid was obtained. The obtained solid was recrystallized from toluene / acetone (1/2) to obtain a fluorenone derivative boronic acid as colorless crystals (40%). The obtained fluorenone derivative boronic acid (12 mmol) and 1,2-ethanediol (30 mmol) were refluxed in toluene for 10 hours and then recrystallized from toluene / acetone (1/4). As a result, the fluorenone derivative boron ester was colorless. Obtained as crystals.

To a toluene solution of 2-bromopyridine (10 mmol), fluorenone derivative boron ester (10 mmol), and Pd (0) (PPh ₃ ) ₄ (0.2 mmol), 2M K ₂ CO ₃ aqueous solution was added vigorously under an argon stream. The mixture was refluxed for 48 hours with stirring. The reaction mixture was cooled to room temperature and then poured into a large amount of methanol to precipitate a solid. The precipitated solid was subjected to suction filtration and washed with methanol to obtain 2- (2′-pyridyl) -9-fluorenone solid.

A 200 ml three-necked flask is charged with iridium (III) chloride (1.7 mmol), 2- (2′-pyridyl) -9-fluorenone (7.58 mmol), 50 ml of ethoxyethanol and 20 ml of water at room temperature under a nitrogen stream. The mixture was stirred for 30 minutes, and then refluxed for 24 hours. The reaction product was cooled to room temperature, and the precipitate was collected by filtration, washed with water, and washed successively with ethanol and acetone. Drying under reduced pressure at room temperature gave a pale yellow powder of di-μ-chloro-tetrakis [2- (2′-pyridyl) -9-fluorenone-N ^{1 ′} , C ³ ] diiridium (III).

In a 200 ml three-necked flask, 70 ml of ethoxyethanol, di-μ-chloro-tetrakis [2- (2′-pyridyl) -9-fluorenone-N ^{1 ′} , C ³ ] diiridium (III) (0.7 mmol), An acetylacetone derivative (2.10 mmol) represented by the following structural formula and sodium carbonate (9.43 mmol) were added, stirred at room temperature under a nitrogen stream, and then refluxed for 15 hours.

The reaction product was ice-cooled, and the precipitate was collected by filtration and washed with water. The precipitate was purified by silica gel column chromatography (eluent: chloroform / methanol: 30/1) and bis [2- (2′-pyridyl) -9-fluorenone-N ^{1 ′} , C ³ ] (dibromobenzylacetylacetate). A pale yellow powder of nato) iridium (III) was obtained.

Example 4 Synthesis of dicyclohexyloxybenzene diboronic acid ester (PP-1) 2,5-dibromo-1,4-dihexyloxybenzene (30 mmol) in THF in a mixture of magnesium (1.9 g, 80 mmol) in THF Was gradually added under a stream of argon with good stirring to prepare a Grignard reagent. The obtained Grignard reagent was gradually added dropwise to a THF solution of trimethyl borate ester (300 mmol) at −78 ° C. over 2 hours, followed by stirring for 2 days at room temperature. The reaction mixture was poured into 5% dilute sulfuric acid containing crushed ice and stirred. When the obtained aqueous solution was extracted with toluene and the extract was concentrated, a colorless solid was obtained. The obtained solid was recrystallized from toluene / acetone (1/2) to obtain dicyclohexyloxybenzenediboronic acid as colorless crystals (50%). The obtained dicyclohexyloxybenzene diboronic acid (12 mmol) and 1,2-ethanediol (30 mmol) were refluxed in toluene for 10 hours and then recrystallized from toluene / acetone (1/4). The boronic ester was obtained as colorless crystals (80%).

Example 5 Synthesis of Polymer Copolymer Containing Metal Coordination Compound (P-1)
Metal coordination compound (1) (1 mmol) synthesized in Example 1, 2,5-bis (4-bromophenyl) [1,3,4] oxadiazole (8 mmol) represented by the following structural formula, To a toluene solution of the dicyclohexyloxybenzene diboronic acid ester (10 mmol) synthesized in Example 4 and a tribromo branched structure monomer (1 mmol), Pd (0) (PPh ₃ ) ₄ (0.2 mmol) under a stream of argon, 2M Of K ₂ CO ₃ was added and refluxed for 48 hours with vigorous stirring.

  The reaction mixture was cooled to room temperature and then poured into a large amount of methanol to precipitate a solid. The precipitated solid was subjected to suction filtration and washed with methanol to obtain a solid. The solid collected by filtration was dissolved in toluene and then poured into a large amount of acetone to precipitate the solid. The precipitated solid was filtered with suction and washed with acetone to obtain a solid. Further, the reprecipitation treatment with acetone was repeated twice. Next, after dissolving the obtained solid in toluene, a cation / anion exchange resin (ion exchange resin manufactured by Organo Co., Ltd.) was added and stirred for 1 hour, followed by suction filtration to recover a polymer solution. Further, the treatment with the ion exchange resin was repeated twice. The recovered polymer solution was poured into a large amount of methanol to precipitate a solid. Furthermore, the obtained solid was extracted and washed with acetone in a Soxhlet extractor for 24 hours to obtain a polymer copolymer (P-1) containing a metal coordination compound.

Example 6 Synthesis of Polymer Copolymer Containing Metal Coordination Compound (P-2)
Metal coordination compound (125) (1 mmol) synthesized in Example 2, 2,5-bis (4-bromophenyl) [1,3,4] oxadiazole (3.5 mmol) represented by the following structural formula 2- (2,5-dibromophenyl) -5-phenyl [1,3,4] oxadiazole (4 mmol), dicyclohexyloxybenzene diboronic acid ester (10 mmol) synthesized in Example 4 and tribromo branch To a toluene solution of the structural monomer (0.5 mmol) and Pd (0) (PPh ₃ ) ₄ (0.2 mmol), 2M K ₂ CO ₃ aqueous solution was added under argon stream, and the mixture was refluxed for 48 hours with vigorous stirring. .

  The reaction mixture was cooled to room temperature and then poured into a large amount of methanol to precipitate a solid. The precipitated solid was subjected to suction filtration and washed with methanol to obtain a solid. The solid collected by filtration was dissolved in toluene and then poured into a large amount of acetone to precipitate the solid. The precipitated solid was filtered with suction and washed with acetone to obtain a solid. Further, the reprecipitation treatment with acetone was repeated twice. Next, after dissolving the obtained solid in toluene, a cation / anion exchange resin (ion exchange resin manufactured by Organo Co., Ltd.) was added and stirred for 1 hour, followed by suction filtration to recover a polymer solution. Further, the treatment with the ion exchange resin was repeated twice. The recovered polymer solution was poured into a large amount of methanol to precipitate a solid. Furthermore, the obtained solid was extracted and washed with acetone in a Soxhlet extractor for 24 hours to obtain a polymer copolymer (P-2) containing a metal coordination compound.

Example 7 Synthesis of Polymer Copolymer Containing Metal Coordination Compound (P-3)
Metal coordination compound (253) (1 mmol) synthesized in Example 3, 2,5-bis (4-bromophenyl) [1,3,4] oxadiazole (8 mmol) represented by the following structural formula, 9 , 9-Dioctylfluorene-2,7-diboronic acid ester (5 mmol), dicyclohexyloxybenzene diboronic acid ester synthesized in Example 4 (5 mmol) and tribromo branched structure monomer (1 mmol), Pd (0) (PPh ₃ ) A 2M aqueous K ₂ CO ₃ solution was added to a toluene solution of ₄ (0.2 mmol) under an argon stream, and the mixture was refluxed for 48 hours with vigorous stirring.

  The reaction mixture was cooled to room temperature and then poured into a large amount of methanol to precipitate a solid. The precipitated solid was subjected to suction filtration and washed with methanol to obtain a solid. The solid collected by filtration was dissolved in toluene and then poured into a large amount of acetone to precipitate the solid. The precipitated solid was filtered with suction and washed with acetone to obtain a solid. Further, the reprecipitation treatment with acetone was repeated twice. Next, after dissolving the obtained solid in toluene, a cation / anion exchange resin (ion exchange resin manufactured by Organo Co., Ltd.) was added and stirred for 1 hour, followed by suction filtration to recover a polymer solution. Further, the treatment with the ion exchange resin was repeated twice. The recovered polymer solution was poured into a large amount of methanol to precipitate a solid. Furthermore, the obtained solid was extracted and washed with acetone in a Soxhlet extractor for 24 hours to obtain a polymer copolymer (P-3) containing a metal coordination compound.

Example 8 Production of Organic EL Element (1)
A toluene solution (1.0 wt%) of the polymer copolymer (P-1) containing the metal coordination compound obtained in Example 5 was placed on a glass substrate patterned with ITO (indium tin oxide) to a width of 2 mm. Then, a polymer light emitting layer (film thickness 70 nm) was formed by spin coating in a dry nitrogen environment. Subsequently, it was heat-dried on a hot plate at 80 ° C. for 5 minutes under a dry nitrogen environment. The obtained glass substrate was transferred into a vacuum evaporation machine, and electrodes were formed on the light emitting layer in the order of Ca (film thickness 20 nm) and Al (film thickness 100 nm). The characteristics of the organic EL element were measured at room temperature, the current-voltage characteristics were measured with a microammeter 4140B manufactured by Hewlett-Packard, and the luminance was measured with SR-3 manufactured by Topcon. When voltage was applied with ITO as the anode and Ca / Al as the cathode, blue light emission (λ = 445 nm) was observed at about 4V. This change in color tone in blue light emission was not observed even after 500 hours at 25 ° C.

Example 9 Production of Organic EL Device (2)
A toluene solution (1.0 wt%) of the polymer copolymer (P-2) containing the metal coordination compound obtained in Example 6 was patterned on a glass substrate with ITO (indium tin oxide) patterned to a width of 2 mm. Then, a polymer light emitting layer (film thickness 70 nm) was formed by spin coating in a dry nitrogen environment. Subsequently, it was heat-dried on a hot plate at 80 ° C. for 5 minutes under a dry nitrogen environment. The obtained glass substrate was transferred into a vacuum evaporation machine, and electrodes were formed on the light emitting layer in the order of LiF (film thickness 0.5 nm) and Al (film thickness 100 nm). The characteristics of the organic EL element were measured at room temperature, the current-voltage characteristics were measured with a microammeter 4140B manufactured by Hewlett-Packard, and the luminance was measured with SR-3 manufactured by Topcon. When voltage was applied using ITO as the anode and LiF / Al as the cathode, orange light emission (λ = 580 nm) was observed at about 5V. No change in color tone in this orange light emission was observed at 25 ° C. even after 500 hours.

Example 10 Production of Organic EL Device (3)
In the same manner as in Example 8, except that the polymer copolymer (P-3) containing a metal coordination compound was used instead of the polymer copolymer (P-1) containing a metal coordination compound, ITO / A polymer light emitting layer / Ca / Al element was produced. The characteristics of the organic EL element were measured at room temperature, the current-voltage characteristics were measured with a microammeter 4140B manufactured by Hewlett-Packard, and the luminance was measured with SR-3 manufactured by Topcon. When voltage was applied with ITO as the anode and Ca / Al as the cathode, blue light emission (λ = 455 nm) was observed at about 4V. This change in color tone in blue light emission was not observed even after 500 hours at 25 ° C.

Comparative Example 1
An ITO / polymer light emitting layer / Ca / Al device was produced in the same manner as in Example 8 except that polydioctylfluorene was used instead of the polymer copolymer (P-1) containing a metal coordination compound. When the obtained ITO / polymer light emitting layer / Ca / Al element was connected to a power source and a voltage was applied using ITO as an anode and Ca / Al as a cathode, blue light emission (λ = 430 nm) was observed at about 6V. However, the emission color changed from blue to yellowish green over time.

Comparative Example 2
ITO was used in the same manner as in Example 8 except that a (dioctylfluorene / benzothiazole) copolymer represented by the following structural formula was used instead of the polymer copolymer (P-1) containing a metal coordination compound. / Polymer light emitting layer / LiF / Al element was produced. When the obtained ITO / polymer light emitting layer / LiF / Al element was connected to a power source and a voltage was applied using ITO as an anode and LiF / Al as a cathode, yellow light emission (λ = 548 nm) was observed at about 8V. However, the emission color changed from yellow to yellowish white over time.

Comparative Example 3
On a glass substrate patterned with a width of 2 mm of ITO (indium tin oxide), α-NPD as a hole transport layer was formed in a thickness of 40 nm by a vacuum evaporation method using resistance heating in a vacuum chamber of 10 ⁻⁵ Pa. . On top of that, the metal coordination compound Ir (ppy) ₃ represented by the following structural formula was co-deposited with CBP so that the weight ratio was 5%.

Further, the Alq ₃ was deposited as a 30 nm thick electron transport layer. On top of this, 0.5 to 2 nm of LiF and 100 to 150 nm of Al were deposited as a cathode electrode layer. The characteristics of the organic EL element were measured at room temperature, the current-voltage characteristics were measured with a microammeter 4140B manufactured by Hewlett-Packard, and the luminance was measured with SR-3 manufactured by Topcon. When the obtained device was connected to a power source and a voltage was applied using ITO as an anode and LiF / Al as a cathode, green light emission (λ = 516 nm) was observed at about 6V. It was 100 hours when the brightness | luminance half-life when driving by a fixed electric current (50mA / cm < ² >) was measured.

Claims (7)

Formulas (1) to (12):

Wherein M is Ir, Rh, Ru, Os, Pd or Pt, and n is 1 or 2. Ring A is a cyclic compound containing a nitrogen atom bonded to M. X _{1 to} X ₇ and ^-R 1 R are each ^{independently, -OR 2, -SR 3, -OCOR} 4, -COOR 5, -SiR 6 R 7 R 8, and ^-NR 9 ^{R 10} (provided ^that, R 1 ^{to R 10} is a hydrogen atom A halogen atom, a cyano group, a nitro group, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or a halogen-substituted alkyl group in which part or all of the hydrogen atoms are substituted with halogen atoms, carbon number 6 A halogen-substituted aryl in which a part or all of hydrogen atoms thereof are substituted with a halogen atom or an aryl group having 30 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms Group, a halogen-substituted heteroaryl group, a halogen-substituted aralkyl group, an R ¹ to R ¹⁰ are substituents selected from the group consisting of each may be the same or different.), Also, X _{1 to} X ₇ may be the same or different, and ring A may have a substituent similar to the group defined by X _{1 to} X _7. Ring C is bonded to M. A compound that binds to the linking group represented by formula (14), wherein ring C may have the same substituents as the groups defined by X _{1 to} X ₇ ). Any of the metal coordination compound monomer units represented,
Formula (13), which may be substituted or unsubstituted:

(In the formula, Ar ₁ and Ar ₂ represent a divalent arylene and / or heteroarylene. A plurality of V, R ₁ and R ₂ are each independently -R ¹ , -OR ² , -SR ³ ,- OCOR ⁴ , —COOR ⁵ and —SiR ⁶ R ⁷ R ⁸ (where R ^{1 to} R ⁸ are linear, cyclic or branched alkyl groups having 1 to 22 carbon atoms, or aryl having 2 to 30 carbon atoms) A substituent selected from the group consisting of a group or a heteroaryl group, each of which may be the same or different, and is substituted at a substitutable position in an arylene or heteroarylene residue Each of a and b is independently an integer of 0 or more, R ₁ and R ₂ may each independently be a hydrogen atom, and n, m and l are each independently 0 or 1. , N, m, And a conjugated monomer units but represented by no.) Is 0 at the same time,
A branched monomer unit that may be substituted or unsubstituted,
The group bonding each monomer unit is represented by the formula (14):

(Wherein, G is -O -, - R-O- R -, - S -, - NR -, - CR 2 -, - SiR 2 -, - SiR 2 -O-SiR 2 -, and -SiR ₂ —O—SiR ₂ —O—SiR ₂ — (wherein R represents a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or an aryl group or heteroaryl group having 2 to 30 carbon atoms. A divalent group selected from the group consisting of: and b represents an integer of 0 to 1,
A metal coordination compound-containing polymer copolymer. In the formulas (1) to (12), ring A may have the same substituent as the group defined by X _{1 to} X ₇ , pyridine, quinoline, benzoxazole, benzothiazole, benzimidazole, The metal coordination compound-containing polymer copolymer according to claim 1, which is benzotriazole, imidazole, pyrazole, oxazole, thiazole, triazole, benzopyrazole triazine or isoquinoline. In the formulas (1) to (12), at least one of the substituents defined in the same manner as X _{1 to} X ₇ or X _{1 to} X ₇ of the ring A is a fluorine atom or a trifluoromethyl group. The metal coordination compound-containing polymer copolymer according to claim 1 or 2.   In said Formula (1)-(12), M is iridium, The metal coordination compound containing high molecular copolymer in any one of Claims 1-3. A branched monomer unit, which may be substituted or unsubstituted, has the formula (15):

(In the formula, plural Ys represent -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ^5, and -SiR ⁶ R ⁷ R ⁸ (wherein R ^{1 to} R ⁸ have 1 carbon atom) A substituent selected from the group consisting of ˜22 linear, cyclic or branched alkyl groups, or an aryl group or heteroaryl group having 2 to 30 carbon atoms, each being the same And a branched structure selected from the group consisting of a substituent bonded to a substitutable position of the benzene ring of the branched structure skeleton, and p represents an integer of 0 to 4. It is a monomer unit, The metal coordination compound containing high molecular copolymer in any one of Claims 1-4.   A polymer composition obtained by mixing the metal coordination compound-containing polymer copolymer according to any one of claims 1 to 5 with a conjugated or non-conjugated polymer. The organic electroluminescent element produced using the metal coordination compound containing high molecular copolymer in any one of Claims 1-5, or the polymer composition of Claim 6.