JP4403935B2 - Polymer complex compound and polymer light emitting device using the same - Google Patents

Description

  The present invention relates to a polymer complex compound and a polymer light emitting device (hereinafter sometimes referred to as polymer LED).

As a light-emitting material used for a light-emitting layer of a light-emitting element, an element using a metal complex that emits light from a triplet excited state (hereinafter sometimes referred to as a triplet light-emitting complex) is known.
Recently, a complex compound containing a triplet light-emitting complex structure in a polymer has been studied. For example, a metal atom of a triplet light-emitting complex structure is directly bonded to a constituent atom of a polymer main chain skeleton. There is known a polymer complex compound which is a poly (fluorene) copolymer containing a metal complex portion formed as described above.

JP 2003-73480 A

  An object of the present invention is to provide a novel polymer complex compound useful as a light-emitting material, and a polymer light-emitting device using the polymer complex compound.

〔式中、Ａｒ₁およびＡｒ₂は、それぞれ独立に、アリーレン基、２価の複素環基または２価の芳香族アミン基を表し、Ａ₁は、アリール基、１価の複素環基または１価の芳香族アミン基を表し、該Ａ₁は、下式（２）
−Ｚ―Ｔ （２）
（式中、Ｔは１価の金属錯体基を表し、Ｚは、直接結合、−ＣＲ₂₀＝ＣＲ₂₁−、−Ｃ≡Ｃ−、−Ｒ₂₂−、−Ｏ−Ｒ₂₂−、―Ｒ₂₂−Ｏ−、−Ｏ−Ｒ₂₂−Ｏ−、―Ｃ（Ｏ）―Ｏ―、―Ｏ―Ｃ（Ｏ）−、−Ｃ（Ｏ）−、−Ｏ−、−Ｎ（Ｒ₂₃）−Ｃ（Ｏ）−、−Ｃ（Ｏ）−Ｎ（Ｒ₂₃）−、−Ｎ＝ＣＨ−または−ＣＨ＝Ｎ―を表す。Ｒ₂₀およびＲ₂₁は、それぞれ独立に水素原子、アルキル基、アリール基、１価の複素環基またはシアノ基を示す。Ｒ₂₂は、アルキレン基またはアルケニレン基を表す。Ｒ₂₃は、水素原子、アルキル基、アリール基または１価の複素環基を示す。）
で示される基を有する。
Ｂ₁は、水素原子、ハロゲン原子、アルキル基、水酸基、アルコキシ基、カルボキシル基、フェノキシ基、アルキルオキシカルボニル基、アルキルカルボニルオキシ基、アミノ基、アルキルアミノ基、アリール基、１価の複素環基または１価の芳香族アミン基を表し、該Ｂ₁がアリール基、１価の複素環基または１価の芳香族アミン基である場合、これらは上式（２）で示される基を有していてもよく、Ｚ₁は、−ＣＲ₁＝ＣＲ₂−または−Ｃ≡Ｃ−を表す。Ｒ₁およびＲ₂は、それぞれ独立に水素原子、アルキル基、アリール基、１価の複素環基またはシアノ基を示す。ｎは、０または１を示す。〕 That is, the present invention provides a polymer complex compound containing a repeating unit represented by the following formula (1) and having a polystyrene-equivalent number average molecular weight of 1 × 10 ³ to 1 × 10 ⁸ .

[Wherein, Ar ₁ and Ar ₂ each independently represent an arylene group, a divalent heterocyclic group or a divalent aromatic amine group, and A ₁ represents an aryl group, a monovalent heterocyclic group or 1 Represents a divalent aromatic amine group, and A ₁ represents the following formula (2):
-ZT (2)
(Wherein T represents a monovalent metal complex group, Z represents a direct bond, —CR ₂₀ ═CR ₂₁ —, —C≡C—, —R ₂₂ —, —O—R ₂₂ —, —R _22. —O—, —O—R ₂₂ —O—, —C (O) —O—, —O—C (O) —, —C (O) —, —O—, —N (R ₂₃ ) —C (O) -, - C ( O) -N (R 23) -, - N = CH- or .R ₂₀ and R ₂₁ represents a -CH = N-are independently a hydrogen atom, an alkyl group, an aryl group A monovalent heterocyclic group or a cyano group, R ₂₂ represents an alkylene group or an alkenylene group, and R ₂₃ represents a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group.
It has the group shown by.
B ₁ is a hydrogen atom, halogen atom, alkyl group, hydroxyl group, alkoxy group, carboxyl group, phenoxy group, alkyloxycarbonyl group, alkylcarbonyloxy group, amino group, alkylamino group, aryl group, monovalent heterocyclic group Or a monovalent aromatic amine group, and when B ₁ is an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine group, these have a group represented by the above formula (2) Z ₁ represents —CR ₁ ═CR ₂ — or —C≡C—. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. n represents 0 or 1. ]

  The polymer complex compound of the present invention is useful as a light emitting material. A polymer light-emitting device using the polymer complex compound has high performance and can be used as a planar light source as a backlight, a device such as a flat panel display.

  The polymer complex compound of the present invention contains one or more types of repeating units represented by the above formula (1).

Ar ₁ and Ar ₂ in the above formula (1) each independently represent an arylene group, a divalent heterocyclic group or a divalent aromatic amine group. Here, Ar ₁ and Ar ₂ are an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, It may have a substituent such as an arylamino group, a monovalent heterocyclic group or a cyano group. When Ar ₁ and Ar ₂ have a plurality of substituents, they may be the same or different from each other.

In said Formula (1), an arylene group is the remaining atomic group remove | excluding two hydrogen atoms from aromatic hydrocarbon, and carbon number is about 6-60 normally. The carbon number does not include the carbon number of the substituent. Here, the aromatic hydrocarbon includes those having a condensed ring and those having two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene.
Examples of the arylene group include a phenylene group (for example, Formulas 1 to 3 in the following diagram), a naphthalenediyl group (Formulas 4 to 13 in the diagram below), an anthracenylene group (Formulas 14 to 19 in the diagram below), and a biphenylene group (Formulas 20 to 25 in the diagram below). ), A triphenylene group (formulas 26 to 28 in the following figure), a condensed ring compound group (formulas 29 to 38 in the following figure), stilbene-diyl (lower figures A to D), a distilben-diyl (lower figures E and F), and the like. .
Of these, a phenylene group, a biphenylene group, a fluorene-diyl group (formulas 36 to 38 in the following figure), a stilbene-diyl (lower figures A to D), and a distilbene-diyl (lower figures E and F) are preferable.

  In the above formulas 1 to 38 and A to F, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group. A group, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group; In the above example, one structural formula has a plurality of Rs, but they may be the same or different.

  Here, the alkyl group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, methyl group, ethyl group, propyl group, i-propyl group, butyl group , I-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, etc. Pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, and 3,7-dimethyloctyl group are preferable.

  The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, the methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group Lauryloxy group, and the like, and pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, and 3,7-dimethyloctyloxy group are preferable.

  The alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, methylthio group, ethylthio group, propylthio group, i-propylthio group, butylthio group, i- Examples include butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, etc. A pentylthio group, a hexylthio group, an octylthio group, a 2-ethylhexylthio group, a decylthio group, and a 3,7-dimethyloctylthio group are preferred.

  The alkylsilyl group may be linear, branched or cyclic, and usually has about 1 to 60 carbon atoms. Specifically, methylsilyl group, ethylsilyl group, propylsilyl group, i-propylsilyl group, butylsilyl group I-butylsilyl group, t-butylsilyl group, pentylsilyl group, hexylsilyl group, cyclohexylsilyl group, heptylsilyl group, octylsilyl group, 2-ethylhexylsilyl group, nonylsilyl group, decylsilyl group, 3,7-dimethyloctylsilyl Group, laurylsilyl group, trimethylsilyl group, ethyldimethylsilyl group, propyldimethylsilyl group, i-propyldimethylsilyl group, butyldimethylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethyl Cyril Group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, etc., pentylsilyl group, hexyl Silyl group, octylsilyl group, 2-ethylhexylsilyl group, decylsilyl group, 3,7-dimethyloctylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, decyldimethyl A silyl group and a 3,7-dimethyloctyl-dimethylsilyl group are preferred.

  The alkylamino group may be linear, branched or cyclic, and may be a monoalkylamino group or a dialkylamino group, and usually has about 1 to 40 carbon atoms. Specifically, a methylamino group or a dimethylamino group , Ethylamino group, diethylamino group, propylamino group, i-propylamino group, butylamino group, i-butylamino group, t-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, Examples include octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, pentylamino group, hexylamino group, octylamino group, 2-ethylhexylamino group , Decylamino group, 3,7-dimethyloctyla A mino group is preferred.

The aryl group usually has about 6 to 60 carbon atoms, and specifically includes a phenyl group and a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ have ₁ to ₁₂ carbon atoms). The same shall apply hereinafter.), C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl group, 2-naphthyl group and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ alkylphenyl group are preferred. .

The aryloxy group usually has about 6 to 60 carbon atoms, and specifically includes a phenoxy group, a C _{1 to} C ₁₂ alkoxyphenoxy group, a C _{1 to} C ₁₂ alkylphenoxy group, a 1-naphthyloxy group, 2- naphthyloxy group and the like, C ₁ -C ₁₂ alkoxy phenoxy group, a C ₁ -C ₁₂ alkylphenoxy group are preferable.

Arylalkyl group has a carbon number of usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ ~ C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl group, 1-naphthyl-C ₁ -C ₁₂ alkyl group, 2-naphthyl-C ₁ -C ₁₂ alkyl group and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group are preferable.

Arylalkoxy group has a carbon number of usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkyloxy phenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl -C ₁ -C ₁₂ alkoxy groups, 2-naphthyl -C ₁ -C ₁₂ alkoxy groups and the like, C ₁ -C ₁₂ alkoxyphenyl - C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy group are preferable.

The arylalkenyl group has a carbon number of usually about 8 to 60, specifically, a phenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl group, 1-naphthyl -C ₂ -C ₁₂ alkenyl group, 2-naphthyl -C ₂ -C ₁₂ alkenyl groups and the like, C ₁ -C ₁₂ alkyloxy phenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl groups are preferred.

The arylalkynyl group has a carbon number of usually about 8 to 60, specifically, a phenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group, 1-naphthyl -C ₂ -C ₁₂ alkynyl group, 2-naphthyl -C ₂ -C ₁₂ alkynyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl - C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferable.

Arylamino group has a carbon number of usually about 6 to 60, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, a 2-naphthylamino group and the like, C ₁ -C ₁₂ alkylphenyl group, di (C ₁ -C ₁₂ alkylphenyl) amino group are preferable .

The monovalent heterocyclic group usually has about 4 to 60 carbon atoms, and specifically includes thienyl group, C _{1 to} C ₁₂ alkyl thienyl group, pyrrolyl group, furyl group, pyridyl group, C _{1 to} C _12. alkyl and pyridyl groups are thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable. The monovalent heterocyclic group refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound.

When the substituent is a group containing an alkyl chain, the alkyl chain may be interrupted by a hetero atom or a group containing a hetero atom. Here, examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the hetero atom or the group containing a hetero atom include the following groups.

  Here, examples of R ′ include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, and a monovalent heterocyclic group having 4 to 60 carbon atoms.

In order to enhance the solubility of the polymer complex compound of the present invention in a solvent, it is preferable that the symmetry of the shape of the repeating unit is small, and one or more of R include a cyclic or branched alkyl chain. It is preferable. A plurality of R may be connected to form a ring. In R, in the substituent containing an alkyl chain, they may be linear, branched or cyclic, or a combination thereof. If not straight, for example, an isoamyl group, 2-ethylhexyl group, 3,7-dimethyl octyl group, a cyclohexyl group, etc. 4-C ₁ ~C ₁₂ alkyl cyclohexyl groups.

In the formula (1), the divalent heterocyclic group means the remaining atomic group obtained by removing two hydrogen atoms from the heterocyclic compound, and usually has about 4 to 60 carbon atoms. The carbon number does not include the carbon number of the substituent.
Here, a heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, and boron in the ring. Good examples include the following:
A group containing nitrogen as a hetero atom; pyridine-diyl group (formulas 39 to 44 in the following diagram), diazaphenylene group (formulas 45 to 48 in the diagram below), quinoline diyl group (formulas 49 to 63 in the diagram below), quinoxaline diyl group (in the diagram below) Formulas 64-68), acridinediyl groups (Formulas 69-72 in the lower figure), bipyridyldiyl groups (Formulas 73-75 in the lower figure), phenanthroline diyl groups (Formulas 76-78 in the lower figure), and the like.
Groups having a fluorene structure containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a hetero atom (formulas 79 to 93 in the following figure).
5-membered ring heterocyclic groups containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a hetero atom: (formulae 94 to 98 in the following figure).
5-membered ring condensed heterocyclic groups containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a hetero atom: (Formulas 99 to 108 in the following figure).
5-membered ring heterocyclic groups containing sulfur as a heteroatom and bonded at the α-position of the heteroatom to form a dimer or oligomer (formulas 109 to 110 in the following figure).
5-membered heterocyclic groups containing silicon, nitrogen, oxygen, sulfur, selenium, etc. as heteroatoms, which are bonded to the phenyl group at the α-position of the heteroatoms: (formulas 111 to 117 in the figure below) .
Among them, a pyridine-diyl group (formulas 39 to 44 in the following figure), a quinoline diyl group (formulas 49 to 63 in the following figure), and a group having a fluorene structure containing silicon, nitrogen, oxygen, sulfur, selenium and the like as heteroatoms (formula 79 in the following figure). ~ 93) is preferred.

In the above formulas 39 to 117, R represents the same meaning as described above.

  In the formula (1), the divalent aromatic amine group means the remaining atomic group obtained by removing two hydrogen atoms from the aromatic amine, and usually has about 4 to 60 carbon atoms. The number of carbon atoms of the substituent is not included. Examples of the divalent aromatic amine group include a group represented by the following general formula (11).

—Ar ₂₀ —N (Ar ₂₁ ) —Ar ₂₂ — (11)

In the formula, Ar ₂₀ and Ar ₂₂ are each independently an arylene group which may have a substituent, a group represented by the general formula (12), or a group represented by the general formula (5). Ar ₂₁ represents an aryl group which may have a substituent, a group represented by the general formula (6), or a group represented by the general formula (7). A ring may be formed between Ar ₂₀ and Ar ₂₁ , between Ar ₂₁ and Ar ₂₂ , or between Ar ₂₀ and Ar ₂₂ .

（１２）
式中、Ａｒ₈およびＡｒ₉は、それぞれ独立に置換基を有してもよいアリーレン基を示す。Ｒ₇およびＲ₈は、それぞれ独立に水素原子、アルキル基、アリール基、１価の複素環基またはシアノ基を示す。ｌは０または１である。

(12)
In the formula, Ar ₈ and Ar ₉ each independently represent an arylene group which may have a substituent. R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. l is 0 or 1.

式中、Ａｒ₁₀およびＡｒ₁₁は、それぞれ独立に、置換基を有してもよいアリーレン基を示す。Ａｒ₁₂は、置換基を有してもよいアリール基である。また、Ａｒ₁₀とＡｒ₁₂の間、Ａｒ₁₀とＡｒ₁₁の間、またはＡｒ₁₁とＡｒ₁₂の間に環を形成していてもよい。

In the formula, Ar ₁₀ and Ar ₁₁ each independently represent an arylene group which may have a substituent. Ar ₁₂ is an aryl group which may have a substituent. Further, a ring may be formed between Ar ₁₀ and Ar ₁₂ , between Ar ₁₀ and Ar ₁₁ , or between Ar ₁₁ and Ar ₁₂ .

式中、Ａｒ₁₃は、置換基を有してもよいアリーレン基を示す。Ａｒ₁₆およびＡｒ₁₇は、それぞれ独立に、置換基を有してもよいアリール基である。また、Ａｒ₁₃とＡｒ₁₆の間、Ａｒ₁₃とＡｒ₁₇の間、またはＡｒ₁₆とＡｒ₁₇の間に環を形成していてもよい。

In the formula, Ar ₁₃ represents an arylene group which may have a substituent. Ar ₁₆ and Ar ₁₇ are each independently an aryl group which may have a substituent. A ring may be formed between Ar ₁₃ and Ar ₁₆ , between Ar ₁₃ and Ar ₁₇ , or between Ar ₁₆ and Ar ₁₇ .

式中、Ａｒ₁₄は、置換基を有してもよいアリーレン基を示す。Ａｒ₁₅は、置換基を有してもよいアリール基を示す。Ｒ₁₁およびＲ₁₂は、それぞれ独立に水素原子、アルキル基、アリール基、１価の複素環基またはシアノ基を示す。ｒは０または１である。

In the formula, Ar ₁₄ represents an arylene group which may have a substituent. Ar ₁₅ represents an aryl group which may have a substituent. R ₁₁ and R ₁₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. r is 0 or 1;

Ar _8, Ar ₉ in the formula (12), Ar ₁₄ in the formula Ar _10, Ar ₁₁ in (5), Ar ₁₃ in the formula (6), equation (7) represents an alkyl group, an alkoxy group, an alkylthio group, an alkyl Has substituents such as silyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group, monovalent heterocyclic group, cyano group, etc. It may be.
Ar _{21 in the} above formula (11), Ar _{12 in} the above formula (5), Ar ₁₆ and Ar _{17 in} the above formula (6), and Ar _{15 in the} above formula (7) are an alkyl group, an alkoxy group, an alkylthio group, an alkyl Has substituents such as silyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group, monovalent heterocyclic group, cyano group, etc. It may be.

Specific examples of the divalent aromatic amine group include the following groups.

In the above formulas 118 to 122, R represents the same meaning as described above.

From the viewpoint of ease of synthesis, Ar ₁ and Ar ₂ are preferably the same group, and Ar ₁ and Ar ₂ are more preferably phenylene.

In the formula (1), A ₁ represents an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine group, and the A ₁ represents the following formula (2)
-ZT (2)
(Wherein T represents a monovalent metal complex group, Z represents a direct bond, —CR ₂₀ ═CR ₂₁ —, —C≡C—, —R ₂₂ —, —O—R ₂₂ —, —R _22. —O—, —O—R ₂₂ —O—, —C (O) —O—, —O—C (O) —, —C (O) —, —O—, —N (R ₂₃ ) —C (O) -, - C ( O) -N (R 23) -, - N = CH- or .R _20, R ₂₁ representing a -CH = N-are independently a hydrogen atom, an alkyl group, an aryl group A monovalent heterocyclic group or a cyano group, R ₂₂ represents an alkylene group or an alkenylene group, and R ₂₃ represents a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group.
It has the group shown by. The number of the group A ₁ has is not particularly limited, but is usually 1 to 3, preferably 1 to 2, and more preferably 1 from the viewpoint of synthesis.

Examples of the monovalent metal complex group represented by T in the formula (2) include a monovalent residue obtained by removing a hydrogen atom from a ligand of a metal complex.
Here, examples of the metal complex include a metal complex that exhibits light emission from a triplet excited state (triplet light emission complex).
Examples of the metal complex exhibiting light emission from the triplet excited state include phosphorescence emission and complexes in which fluorescence emission is observed in addition to the phosphorescence emission.

  Examples of the triplet light-emitting complex include those conventionally used as low-molecular EL light-emitting materials. These include, for example, Nature, (1998), 395, 151, Appl. Phys. Lett. (1999), 75 (1), 4, Proc. SPIE-Int. Soc. Opt. Eng. (2001), 4105 ( Organic Light-Emitting Materials and Devices IV), 119, J. Am. Chem. Soc., (2001), 123, 4304, Appl. Phys. Lett., (1997), 71 (18), 2596, Syn. Met. , (1998), 94 (1), 103, Syn. Met., (1999), 99 (2), 1361, Adv. Mater., (1999), 11 (10), 852, and the like.

  The central metal of the triplet light emitting complex is usually a metal having an atomic number of 50 or more, which has a spin-orbit interaction, and can cause intersystem crossing between the singlet state and the triplet state.

  Examples of the central metal of the triplet light-emitting complex include rhenium, iridium, osmium, scandium, yttrium, platinum, gold, and the lanthanoids europium, terbium, thulium, dysprosium, samarium, praseodymium, gadolinium, and the like. Iridium, platinum, gold and europium are preferred, iridium, platinum and gold are particularly preferred, and iridium is most preferred.

  The ligand of the triplet light-emitting complex is usually an organic ligand, and the carbon number is usually about 4 to 60.

  Examples of the ligand of the triplet light-emitting complex include 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, 2-phenyl-benzothiazole and derivatives thereof, and 2-phenyl-benzo. Examples thereof include oxazole and its derivatives, porphyrin and its derivatives.

As a triplet light emission complex, the structure shown by following formula (3) is mentioned, for example.

In the formula, M represents an atom having an atomic number of 50 or more, and a metal capable of causing an intersystem crossing between a singlet state and a triplet state in the complex by spin-orbit interaction.
Examples of M include rhenium, iridium, osmium, scandium, yttrium, platinum, gold, and lanthanoids such as europium, terbium, thulium, dysprosium, samarium, praseodymium, and gadolinium, and iridium, platinum, gold, and europium. Preferably, iridium is particularly preferred.

Ar is a ligand that binds to M at one or more of a nitrogen atom, an oxygen atom, a carbon atom, a sulfur atom, and a phosphorus atom.

  Ar is, for example, a ligand formed by bonding a heterocyclic ring such as a pyridine ring, a thiophene ring, a benzoxazole ring, or a benzene ring. Specifically, phenylpyridine, 2- (paraphenylphenyl) pyridine 7-bromobenzo [h] quinoline, 2- (4-thiophen-2-yl) pyridine, 2- (4-phenylthiophen-2-yl) pyridine, 2-phenylbenzoxazole, 2- (paraphenylphenyl) benzo Oxazole, 2-phenylbenzothiazole, 2- (paraphenylphenyl) benzothiazole, 2- (benzothiophen-2-yl) pyridine 7,8,12,13,17,18-hexakisethyl-21H, 23H-porphyrin Etc., and these may have a substituent.

  Ar substituents include halogen atoms, alkyl groups, alkenyl groups, aralkyl groups, arylthio groups, arylalkenyl groups, cyclic alkenyl groups, alkoxy groups, aryloxy groups, alkyloxycarbonyl groups, aralkyloxycarbonyl groups, aryloxycarbonyls. Groups, aryl groups, and monovalent heterocyclic groups, and the definitions and specific examples thereof are the same as those described above.

  It is desirable that M is bonded to at least one carbon atom of Ar.

  In the formula (3), Ar is preferably a tetradentate ligand bonded to M by any four atoms selected from a nitrogen atom, an oxygen atom, a carbon atom, a sulfur atom and a phosphorus atom. For example, specific examples of ligands in which four pyrrole rings are connected in a cyclic manner include 7,8,12,13,17,18-hexakisethyl-21H, 23H-porphyrin.

  In the above formula (3), Ar is two atoms selected from a nitrogen atom, an oxygen atom, a carbon atom, a sulfur atom and a phosphorus atom, and a bidentate ligand which forms a five-membered ring by combining with M It is more preferable that M is bonded to at least one carbon atom, and more preferable when Ar is a bidentate ligand represented by the following formula (4).

In the formula, R ^{2 to} R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an arylthio group, an arylalkenyl group, a cyclic alkenyl group, an alkoxy group, an aryloxy group, or an alkyloxycarbonyl group. , An aralkyloxycarbonyl group, an aryloxycarbonyl group, or an aryl group. At least one of R ^{2 to} R ⁹ is a bond with a polymer chain.

In the formula, L is a hydrogen atom, alkyl group, aryl group, heterocyclic ligand, carboxyl group, halogen atom, amide group, imide group, alkoxy group, alkyl mercapto group, carbonyl ligand, alkene ligand, alkyne. Ligand, amine ligand, imine ligand, nitrile ligand, isonitrile ligand, phosphine ligand, phosphine oxide ligand, phosphite ligand, ether ligand, sulfone ligand A sulfoxide ligand or a sulfide ligand. m shows the integer of 1-5. o represents an integer of 0 to 5.

In L, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group, and examples of the aryl group include a phenyl group, a tolyl group, a 1-naphthyl group, and a 2-naphthyl group. The heterocyclic ligand may be zero-valent or monovalent, and examples of the zero-valent ligand include 2,2′-bipyridyl, 1,10-phenanthroline, and 2- (4-thiophen-2-yl) pyridine. , 2- (benzothiophen-2-yl) pyridine and the like,
Examples of monovalent compounds include phenylpyridine, 2- (paraphenylphenyl) pyridine, 7-bromobenzo [h] quinoline, 2- (4-phenylthiophen-2-yl) pyridine, 2-phenylbenzoxazole, 2- Examples include (paraphenylphenyl) benzoxazole, 2-phenylbenzothiazole, 2- (paraphenylphenyl) benzothiazole and the like.

  Although it does not specifically limit as a carboxyl group, For example, an acetoxy group, a naphthenate group, or 2-ethylhexanoate group etc. are mentioned. Although it does not specifically limit as a halogen atom, For example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned. The amide group is not particularly limited. For example, dimethylamide group, diethylamide group, diisopropylamide group, dioctylamide group, didecylamide group, didodecylamide group, bis (trimethylsilyl) amide group, diphenylamide group, N -A methylanilide or anilide group etc. are mentioned. Although it does not specifically limit as an imide group, For example, a benzophenone imide etc. are mentioned. Although it does not specifically limit as an alkoxy group, For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group etc. are mentioned. The alkyl mercapto group is not particularly limited, and examples thereof include a methyl mercapto group, an ethyl mercapto group, a propyl mercapto group, a butyl mercapto group, and a phenyl mercapto group. Carbonyl ligands include ketones such as carbon monoxide, acetone and benzophenone, diketones such as acetylacetone and acenaphthoquinone, acetonate ligands such as acetylacetonate, dibenzomethylate, and tenoyltrifluoroacetonate. Illustrated. The alkene ligand is not particularly limited, and examples thereof include ethylene, propylene, butene, hexene, and decene. Although it does not specifically limit as an alkyne ligand, For example, acetylene, phenyl acetylene, diphenyl acetylene, etc. are mentioned. Although it does not specifically limit as an amine ligand, For example, a triethylamine, a tributylamine, etc. are mentioned. The imine ligand is not particularly limited, and examples thereof include benzophenone imine and methyl ethyl ketone imine. The nitrile ligand is not particularly limited, and examples thereof include acetonitrile and benzonitrile. The isonitrile ligand is not particularly limited, and examples thereof include t-butyl isonitrile and phenyl isonitrile. The phosphine ligand is not particularly limited, and examples thereof include triphenylphosphine, tolylphosphine, tricyclohexylphosphine, and tributylphosphine. Although it does not specifically limit as a phosphine oxide ligand, For example, a tributyl phosphine oxide or a triphenyl phosphine oxide etc. are mentioned. Although it does not specifically limit as a phosphite ligand, For example, a triphenyl phosphite, a tolyl phosphite, a tributyl phosphite, a triethyl phosphite etc. are mentioned. The ether ligand is not particularly limited, and examples thereof include dimethyl ether, diethyl ether, and tetrahydrofuran. The sulfone ligand is not particularly limited, and examples thereof include dimethyl sulfone and dibutyl sulfone. The sulfoxide ligand is not particularly limited, and examples thereof include dimethyl sulfoxide and dibutyl sulfoxide. The sulfide ligand is not particularly limited, and examples thereof include ethyl sulfide and butyl sulfide.

Specific examples of the triplet light-emitting complex include the following.

  Here, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, aryl A group selected from the group consisting of an alkynyl group, an arylamino group, a monovalent heterocyclic group, and a cyano group is shown. In order to improve the solubility in a solvent, an alkyl group and an alkoxy group are preferable, and it is preferable that the symmetry of the shape of the repeating unit including a substituent is small.

  From the viewpoint of ease of synthesis, the ligand of the triplet light-emitting complex is preferably 2-phenyl-pyridine and a derivative thereof, and the central metal is preferably iridium.

As described above, the monovalent metal complex group includes a monovalent residue obtained by removing a hydrogen atom from a ligand of a metal complex, and includes a group in which R in the above example is a bond.

  Examples of the monovalent metal complex group include the following groups.

Z in the formula (2) is a direct bond, —CR ₂₀ ═CR ₂₁ —, —C≡C—, —R ₂₂ —, —O—R ₂₂ —, —R ₂₂ —O—, —O—R ₂₂ —. O -, - C (O) -O -, - O-C (O) -, - C (O) -, - O -, - N (R 23) -C (O) -, - C (O) —N (R ₂₃ ) —, —N═CH— or —CH═N— is represented.
Among these, a direct bond, —CR ₂₀ ═CR ₂₁ —, —R ₂₂ —, —O—R ₂₂ —, —R ₂₂ —O—, and —O—R ₂₂ —O— are preferable.
Here, R ₂₀ and R ₂₁ are each independently a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group.
R ₂₂ represents an alkylene group or an alkenylene group. The alkylene group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, the methylene group, ethylene group, propylene group, i-propylene group, butylene group, i -Butylene group, pentylene group, hexylene group, cyclohexylene group, heptylene group, octylene group, 2-ethylhexylene group, nonylene group, decylene group, 3,7-dimethyloctylene group, laurylene group, etc. Group, butylene group, pentylene group, hexylene group, heptylene group, octylene group and 2-ethylhexylene group are preferable.
The alkenylene group usually has about 2 to 20 carbon atoms and includes butynylene group, pentynylene group, hexynylene group, heptynylene group, octynylene group, laurinylene group, butynylene group, pentynylene group, hexynylene group, heptynylene group, An octynylene group is preferred.
R ₂₃ is a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group.

Examples of the group represented by the above formula (2) include the groups exemplified as the monovalent metal complex group and the following groups.

A ₁ represents an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine group, and A ₁ has a group represented by the above formula (2).

A ₁ may have a substituent other than the substituent represented by the above formula (2). When A ₁ has a plurality of substituents, they may be the same or different. Examples of the substituent other than the group represented by the formula (2) include an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, and an arylalkenyl group. Arylalkynyl group, arylamino group, monovalent heterocyclic group and the like.

  Here, the aryl group usually has about 6 to 60 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, a triphenyl group, a pyrenyl group, and a fluorenyl group. Of these, a phenyl group, a naphthyl group, a biphenyl group, and a fluorenyl group are preferable.

The monovalent heterocyclic group means a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 2 to 60 carbon atoms.
Examples of the monovalent heterocyclic group include the following.
A monovalent heterocyclic group containing nitrogen as a hetero atom; pyridinyl group, diazaphenyl group, quinolinyl group, quinoxalinyl group, acridinyl group, bipyridinyl group, phenanthroline-yl group, and the like.
A group containing silicon, nitrogen, sulfur, selenium, oxygen and the like as a hetero atom and having a fluorene structure (the group having a ring represented by the above formulas 79 to 93),
5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, oxygen, etc. as a heteroatom (a group having a ring represented by the above formula, 94 to 98) As a heteroatom, silicon, nitrogen, sulfur, selenium , A 5-membered condensed heterocyclic group containing oxygen and the like (a group having a ring represented by the above formulas 99 to 108).
A 5-membered ring heterocyclic group containing sulfur or the like as a heteroatom, a group bonded to the α-position of the heteroatom to form two-bodies or an oligomer (the group having a ring represented by the above formula, 109 to 110) .
A 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, oxygen or the like as a hetero atom, and a group bonded to the phenyl group at the α-position of the hetero atom (rings represented by the above formulas, 111 to 117) A group having

  The monovalent aromatic amine group refers to the remaining atomic group obtained by removing one hydrogen atom from the aromatic amine, and usually has about 4 to 60 carbon atoms. The carbon number does not include the carbon number of the substituent. Examples of the monovalent aromatic amine group include groups represented by the following formulas 123 to 127.

上記式１２３〜１２７において、Ｒは、それぞれ独立に、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アルキルシリル基、アルキルアミノ基、アリール基、アリールオキシ基、アリールアルキル基、アリールアルコキシ基、アリールアルケニル基、アリールアルキニル基、アリールアミノ基、１価の複素環基、式（2）で示される基、またはシアノ基を示し、少なくとも1つは式（2）で示される基である。上記の例において、１つの構造式中に複数のＲを有しているが、それらは同一であってもよいし、異なる基であってもよい。

In the above formulas 123 to 127, each R independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an aryl. An alkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group, a group represented by the formula (2), or a cyano group is shown, and at least one is a group represented by the formula (2). In the above example, one structural formula has a plurality of Rs, but they may be the same or different groups.

In the formula (1), B ₁ is a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, a phenoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, an amino group, an alkylamino group, an aryl group, When the monovalent heterocyclic group or monovalent aromatic amine group is represented and B ₁ is an aryl group, monovalent heterocyclic group or monovalent aromatic amine group, these are represented by the above formula (2). You may have the group shown.

  Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, methyl group, ethyl group, propyl group, i-propyl group, butyl group, i -Butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, phenylpropyl group, phenylbutyl group, etc. Can be mentioned.
The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group I-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group , Phenylpropyloxy group, phenylbutyloxy group and the like.
Examples of the alkyloxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, i-propyloxycarbonyl group, butoxycarbonyl group, i-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl Group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, lauryloxycarbonyl group, phenylpropyloxycarbonyl group, And phenylbutyloxycarbonyl group.
Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an i-propylcarbonyloxy group, a butylcarbonyloxy group, an i-butyl group carbonyloxy, a pentylcarbonyloxy group, and a hexylcarbonyloxy group. Cyclohexylcarbonyloxy group, heptylcarbonyloxy group, octylcarbonyloxy group, 2-ethylhexylcarbonyloxy group, nonylcarbonyloxy group, decylcarbonyloxy group, 3,7-dimethyloctylcarbonyloxy group, laurylcarbonyloxy group, phenylpropyl Examples thereof include a carbonyloxy group and a phenylbutylcarbonyloxy group.
The alkylamino group may be linear, branched or cyclic, and may be a monoalkylamino group or a dialkylamino group, and usually has about 1 to 40 carbon atoms. Specifically, a methylamino group, a dimethylamino group, Group, ethylamino group, diethylamino group, propylamino group, i-propylamino group, butylamino group, i-butylamino group, t-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group Octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group and the like.
Examples of the aryl group, monovalent heterocyclic group or monovalent aromatic amine group include the same groups as those described for A ₁ .
From the viewpoint of ease of synthesis, B ₁ is more preferably a hydrogen atom or an alkyl group.

In the formula (1), Z ₁ represents —CR ₁ ═CR ₂ — or —C≡C—. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. n represents 0 or 1.
From the viewpoint of light stability, n is preferably 0.

Specific examples of the formula (1) include the following units.

  The total number of repeating units represented by formula (1) is usually from 0.1 mol% to 100 mol%, preferably from 0.5 mol% to 100 mol%, preferably from 1 mol% to 100 mol. The mol% or less is more preferable.

Among the polymer complex compounds of the present invention, those containing a repeating unit represented by the following formula (10) are preferred.

− Ar ₂₃ − (Z ′) _p − (10)

Ar ₂₃ in the above formula (10) is an arylene group, a divalent heterocyclic group, or a divalent aromatic amine group. Ar ₂₃ is exemplified by the same group as Ar ₁ .
In the above formula (10), Z ′ represents —CR ₄ ═CR ₅ — or —C≡C—. R ₄ and R ₅ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. p represents 0 or 1.

Specific examples of the repeating unit represented by the formula (10) include those having structures described in the above formulas 1 to 117, the above formulas A to F, the above formulas 118 to 122, and the following formulas 128 to 133.

ここにＲは前記と同じ意味を表す。
中でも、フェニレン基（例えば、上図の式１〜３）、ナフタレンジイル基（上図の式４〜１３）、アントラセニレン基（上図の式１４〜１９）、ビフェニレン基（上図の式２０〜２５）、トリフェニレン基（上図の式２６〜２８）、縮合環化合物基（上図の式２９〜３８）、ジベンゾフランージイル基（上図の式８５〜８７）、ジベンゾチオフェンージイル基（上図の式８８〜９０）、スチルベン−ジイル基、ジスチルベン−ジイル基、２価の芳香族アミン基（上図の１１８〜１１９、１２２）、アリーレンビニレン基（下図の式１２８〜１３３）などが好ましく、中でもフェニレン基、ビフェニレン基、フルオレンージイル基（上図の式３６〜３８）、ジベンゾフランージイル基（上図の式８５〜８７）、ジベンゾチオフェンージイル基（上図の式８８〜９０）、スチルベン−ジイル基、ジスチルベン−ジイル基、２価の芳香族アミン基が特に好ましい。

Here, R represents the same meaning as described above.
Among them, a phenylene group (for example, the above formulas 1 to 3), a naphthalenediyl group (the above formulas 4 to 13), an anthracenylene group (the above formulas 14 to 19), a biphenylene group (the above formulas 20 to 20). 25), a triphenylene group (formulas 26 to 28 in the above figure), a condensed ring compound group (formulas 29 to 38 in the above figure), a dibenzofuran-diyl group (formulas 85 to 87 in the above figure), a dibenzothiophene-diyl group (above) Formulas 88 to 90), stilbene-diyl groups, distilbene-diyl groups, divalent aromatic amine groups (118 to 119 and 122 in the above figure), arylene vinylene groups (formulas 128 to 133 in the following figure) and the like are preferable. Among them, phenylene group, biphenylene group, fluorene-diyl group (formulas 36 to 38 in the above figure), dibenzofurandiyl group (formulas 85 to 87 in the above figure), dibenzothiophene-diyl group ( Formula 88-90 in FIG.), Stilbene - diyl group, distilbene - diyl group, divalent aromatic amine group is particularly preferred.

  Among the polymer complex compounds containing the repeating units represented by the formulas (1) and (10), the sum of the repeating units represented by the formulas (1) and (10) is 50 mol% or more of the total repeating units. From the viewpoint of heat resistance, the repeating unit represented by the formula (1) is 1 mol% or more and 90 mol% or less with respect to the total of the repeating units represented by the formula (1) and the formula (10). preferable.

The polymer complex compound of the present invention typically has a polystyrene-equivalent number average molecular weight of about 10 ³ to 10 ⁸ and preferably 2 × 10 ³ to 10 ⁷ .

  In addition, the terminal group of the polymer complex compound of the present invention is protected with a stable group, because if the polymerization active group remains as it is, there is a possibility that the light emission characteristics and lifetime when the device is made will be reduced. Also good. Those having a conjugated bond continuous with the conjugated structure of the main chain are preferable, and for example, a structure bonded to an aryl group or a heterocyclic group via a vinylene group may be used. Specific examples include substituents described in Chemical formula 10 of JP-A-9-45478.

  The polymer complex compound of the present invention may contain a repeating unit other than the repeating units represented by the above formulas (1) and (10) as long as the phosphorescence, fluorescence property and charge transport property are not impaired. Those consisting essentially of repeating units represented by the formula (1) and those consisting essentially of repeating units represented by the formulas (1) and (10) are preferred.

The repeating unit may be linked by vinylene or a non-conjugated part, or the vinyl unit or non-conjugated part may be contained in the repeating unit. Examples of the binding structure containing the non-conjugated moiety include those shown below, those shown below in combination with vinylene groups, and those shown below in which two or more of them are combined. Here, R is a group selected from the same substituents as described above, and Ar represents a hydrocarbon group having 6 to 60 carbon atoms.

  The polymer complex compound of the present invention may be a random, block or graft copolymer, or may be a polymer having an intermediate structure thereof, for example, a random copolymer having a block property. . From the viewpoint of obtaining a polymer complex compound having high phosphorescence and fluorescence quantum yield, a random copolymer having a block property and a block or graft copolymer are preferable to a complete random copolymer. A case in which the main chain is branched and there are three or more terminal portions and dendrimers are also included.

  When the polymer complex compound of the present invention is used as a light emitting material for a polymer LED, the polymer complex compound of the present invention has fluorescence or phosphorescence in a solid state because fluorescence or phosphorescence from a thin film is used. preferable.

  Examples of the good solvent for the polymer complex compound of the present invention include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, and n-butylbenzene. Although depending on the structure and molecular weight of the polymer compound, it can usually be dissolved in these solvents in an amount of 0.1% by weight or more.

  Next, the manufacturing method of the polymer complex compound of this invention is demonstrated.

The polymer complex compound of the present invention is, for example,
[1] A monomer represented by X ₁ -GX ₂ (wherein X ₁ and X ₂ each independently represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group. -G- represents a group represented by the formula (1 It can be obtained by reacting in the presence of Ni catalyst.
For example, when the polymer complex compound has a repeating unit represented by the formula (10), a monomer represented by Z ₃ -DZ ₄ (Z ₃ and Z ₄ are each independently a halogen atom, alkylsulfonyl Represents an oxy group or an arylsulfonyloxy group, -D- represents a repeating unit represented by the formula (10)).

In addition, the polymer complex compound of the present invention is Y ₁ -GY ₂ (wherein Y ₁ and Y ₂ each independently represents a boric acid group or a boric acid ester group. -G- represents the formula (1) a monomer represented by the in. showing a repeating unit represented), the monomer (Z ₅ represented by _{Z 5 -G-Z 6, Z} 6 represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group -G- represents a repeating unit represented by the formula (1)) in the presence of a Pd catalyst.

Furthermore, among the polymer complex compounds of the present invention, those having a repeating unit represented by the formula (10) are Y ₃ -GY ₄ (wherein Y ₃ and Y ₄ are each independently a boric acid group or boron). -G- represents a repeating unit represented by the formula (1)) and a monomer represented by Z ₃ -DZ ₄ (Z ₃ , Z ₄ independently represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group, and -D- represents a repeating unit represented by the formula (10)) and is obtained by reacting in the presence of a Pd catalyst. Can do.

The polymer complex compound of the present invention can be obtained by reacting [2] a polymer compound having a structure T ′ obtained by removing a metal part from a monovalent metal complex group T with a metal complex compound corresponding to the metal part. Can be manufactured.
That is, for example, 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, 2-phenyl-benzothiazole and derivatives thereof, and 2-phenyl. -After obtaining a polymer compound having benzoxazole and its derivative, porphyrin and its derivative, etc., the polymer compound can be reacted with a metal compound to obtain a polymer complex compound.

T ′ is not particularly limited as long as it corresponds to T. For example, a group that forms a ligand formed by bonding a heterocyclic ring such as a pyridine ring, a thiophene ring, a benzoxazole ring, or a benzene ring. Specifically, 4- (2-pyridyl) phenylene, 4- {4- (2-pyridyl) phenylene} phenylene, benzo [h] quinolin-2-yl, 4- (2-pyridyl) thiophene-2 -Yl, 4- {4- (2-pyridyl) phenylene} thiophen-2-yl, 4- (2-benzoxazole) phenylene, 4- {4- (2-benzoxazole) phenylene} phenylene, 4- (2 -Benzothiazole) phenylene, 4- {4- (2-benzothiazole) phenylene} phenylene, 5- (2-pyridine) benzothiophen-2-yl, 7,8,12,13,17,18-hex Kisuechiru-21H, 23H-like porphyrin over-yl and the like, may have these substituents. Examples of the substituent include a halogen atom, alkyl group, alkenyl group, aralkyl group, arylthio group, arylalkenyl group, cyclic alkenyl group, alkoxy group, aryloxy group, alkyloxycarbonyl group, aralkyloxycarbonyl group, aryloxycarbonyl group, Examples thereof include an aryl group and a monovalent heterocyclic group, and the definitions and specific examples thereof are the same as those described above.

Specific groups are shown below.

This polymer compound is, for example, X ₃ —J—X ₄ (wherein X ₃ and X ₄ each independently represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group. —J— represents the formula (1) Represents a repeating unit in which T is replaced by T ′.) And is obtained by reacting in the presence of a Ni catalyst.
The monomer represented by X ₃ -JX ₄ and Y ₃ -JY ₄ (wherein Y ₃ and Y ₄ each independently represent a boric acid group or a boric acid ester group. And the same meaning as described above) can be obtained by reacting with a monomer represented by Pd catalyst.

A metal complex compound is reacted with the polymer compound to produce a polymer complex compound.
Specifically, in the above-described polymer compound and the metal complex represented by the formula (3), the coordination ability of the ligand to the central metal is lower than the coordination ability of the coordination portion of the polymer. The polymer complex compound of the present invention can be produced by reacting a metal complex having a ligand as a structural unit and performing a ligand exchange reaction.

次に示すような金属錯体化合物を

例えば、不活性ガス雰囲気下、反応を阻害することがない溶媒、例えば、脱水グリセロール等の高沸点溶媒中、反応温度は、特に限定されないが、通常は、０から３００℃、好ましくは、６０から２５０℃、より好ましくは、７０から２００℃程度、反応時間は、特に限定されないが、通常は、０．５時間から１００時間、好ましくは、３から５０時間、より好ましくは、６から２４時間程度反応させることにより、例えば、次のような構造単位を有する、本発明の高分子錯体化合物を製造することができる。

Specifically, for example, a polymer compound having a metal complex structure portion as shown below

The metal complex compound as shown below

For example, the reaction temperature is not particularly limited in a solvent that does not inhibit the reaction under an inert gas atmosphere, for example, a high boiling point solvent such as dehydrated glycerol, but is usually 0 to 300 ° C., preferably 60 to 60 ° C. 250 ° C., more preferably about 70 to 200 ° C. The reaction time is not particularly limited, but is usually 0.5 to 100 hours, preferably 3 to 50 hours, more preferably about 6 to 24 hours. By reacting, for example, the polymer complex compound of the present invention having the following structural unit can be produced.

In this case, by adjusting the amount of the metal complex compound to be reacted with the polymer compound, a polymer complex compound containing a repeating unit of the polymer compound as shown below can be produced.

（ここにＺ₇は、例えば、ハロゲン原子、アルキルスルホニルオキシまたはアリールスルホニルオキシ基を示す。）
例えば、下図のような、反応活性基Ｚ₇と反応する反応活性基を有する金属錯体化合物

を、パラジウム触媒存在下、反応（Ｈｅｃｋ反応）させることにより、下図のような、高分子金属錯体化合物を得ることができる。

合成の容易さからは、上記〔２〕、〔３〕の方法が好ましい。 In addition, the polymer complex compound of the present invention can be specifically synthesized by the following method.
[3] For example, a polymer compound having a reactive group Z ₇ as shown below,

(Here, Z ₇ represents, for example, a halogen atom, an alkylsulfonyloxy group, or an arylsulfonyloxy group.)
For example, as shown in the figure below, a metal complex compound having a reactive group that reacts with the reactive group Z ₇

Is reacted in the presence of a palladium catalyst (Heck reaction) to obtain a polymer metal complex compound as shown below.

From the viewpoint of ease of synthesis, the methods [2] and [3] are preferred.

Examples of the halogen atom represented by X ₁ , X ₂ , X ₃ , X ₄ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ in the above formula include iodine, bromine, chlorine and the like. Examples of the arylsulfonyloxy group include a pentafluorophenylsulfonyloxy group and a paratoluenesulfonyloxy group, and examples of the alkylsulfonyloxy group include a methanesulfonyloxy group and a trifluoromethanesulfonyloxy group.

Examples of boric acid groups and boric acid ester groups represented by Y ₁ , Y ₂ , Y ₃ , and Y ₄ include boric acid groups, dimethyl boric acid esters, ethylene boric acid esters, and trimethylene boric acid esters.

Examples of the reaction using a Ni catalyst include a method of polymerizing in the presence of a zerovalent nickel complex {Ni (COD) 2}.
Examples of the zero-valent nickel complex include bis (1,5-cyclooctadiene) nickel (0), (ethylene) bis (triphenylphosphine) nickel (0), tetrakis (triphenylphosphine) nickel, Bis (1,5-cyclooctadiene) nickel (0) is preferred from the viewpoint of versatility and low cost.
Moreover, it is preferable from a viewpoint of a yield improvement to add a neutral ligand.
Here, the neutral ligand is a ligand having no anion or cation, and 2,2′-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline, N, N′-tetramethylethylenediamine. Nitrogen-containing ligands such as triphenylphosphine, tolylphosphine, tributylphosphine, triphenoxyphosphine, and the like, and nitrogen-containing ligands are preferred in terms of versatility and low cost. 2,2′-bipyridyl is particularly preferable in terms of high reactivity and high yield. In particular, from the viewpoint of improving the yield of the polymer, a system in which 2,2′-bipyridyl is added as a neutral ligand to a system containing bis (1,5-cyclooctadiene) nickel (0) is preferable.
The polymerization solvent is not particularly limited as long as it does not inhibit the polymerization, and examples thereof include amide solvents, aromatic hydrocarbon solvents, ether solvents and the like.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and the like.
The aromatic hydrocarbon solvent is a solvent composed of an aromatic hydrocarbon compound, for example, benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, butylbenzene, naphthalene, tetralin, etc., toluene, xylene, Tetralin, tetramethylbenzene and the like are preferable.
The ether solvent is a solvent composed of a compound in which a hydrocarbon group is bonded with an oxygen atom, such as diisopropyl ether, tetrahydrofuran, 1,4-dioxane, diphenyl ether, ethylene glycol dimethyl ether, and tert-butyl methyl ether. Preferred are tetrahydrofuran, 1,4-dioxane and the like, which are good solvents for the polymer compound.
Moreover, you may mix and use these solvents from a viewpoint of improving polymerizability and solubility.

The polymerization reaction is usually performed in an inert gas atmosphere such as argon or nitrogen.
The polymerization time is usually about 0.5 to 100 hours, but is preferably within 30 hours from the viewpoint of production cost.
The polymerization temperature is usually about 0 to 200 ° C, but 0 to 100 ° C is preferable from the viewpoint of high yield and low heating cost.

Examples of the reaction in the presence of a Pd catalyst include a Suzuki coupling reaction.
Examples of the palladium catalyst used in the Suzuki coupling reaction include palladium acetate, palladium [tetrakis (triphenylphosphine)] complex, and bis (tricyclohexylphosphine) palladium complex.
For example, using palladium [tetrakis (triphenylphosphine)], an inorganic base such as potassium carbonate, sodium carbonate, barium hydroxide, etc., an organic base such as triethylamine, and an inorganic salt such as cesium fluoride are equivalent to the monomer, preferably 1 to 10 equivalents are added and reacted. An inorganic salt may be used as an aqueous solution and reacted in a two-phase system. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. Although depending on the solvent, a temperature of about 50 to 160 ° C. is preferably used. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 1 hour to 200 hours.

Examples of the palladium catalyst used in the Heck reaction include palladium acetate, palladium [tetrakis (triphenylphosphine)] complex, and bis (tricyclohexylphosphine) palladium complex. Examples of the phosphorus ligand include triphenylphosphine, tri (o-tolyl) phosphine, 1,3-bis (diphenylphosphino) propane, and the like.
For example, palladium [tetrakis (triphenylphosphine)] is used, and a base such as triethylamine is added in an amount of not less than an equivalent amount, preferably 1 to 10 equivalents, relative to the monomer. Examples of the solvent include N, N-dimethylformamide, toluene, acetonitrile, tetrahydrofuran and the like. Although depending on the solvent, a temperature of about 50 to 160 ° C. is preferably used. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 1 hour to 200 hours.

  After the reaction, the polymer complex compound of the present invention is subjected to conventional separation operations such as acid washing, alkali washing, neutralization, water washing, organic solvent washing, reprecipitation, centrifugation, extraction, column chromatography, etc., if necessary. You may use for refinement | purification operation, drying, and other operations.

When the polymer complex compound of the present invention is used as a light emitting material of a polymer LED, the purity affects the light emission characteristics. Therefore, in the production method of the present invention, the separation operation and the purification operation are sufficiently performed, and an unreacted monomer is obtained. It is preferable to sufficiently remove by-products, catalyst residues and the like.
In the case of drying, it is sufficient that the remaining solvent is sufficiently removed. In order to prevent deterioration of the polymer compound, it is preferable to dry it while shielding light in an inert atmosphere. Moreover, it is preferable to dry at a temperature at which the polymer complex compound is not thermally denatured.

  The polymer complex compound of the present invention can be used as an active ingredient of a light emitting material. Furthermore, it can also be used as a charge transporting material, an organic semiconductor material, an optical material, or a conductive material by doping.

Next, the polymer LED of the present invention will be described.
The polymer LED of the present invention has a light emitting layer between electrodes composed of an anode and a cathode, and the light emitting layer contains the polymer complex compound of the present invention.

  In addition, as the polymer LED of the present invention, a polymer LED having an electron transport layer provided between the cathode and the light emitting layer, a polymer LED having a hole transport layer provided between the anode and the light emitting layer, Examples include a polymer LED in which an electron transport layer is provided between the cathode and the light emitting layer, and a hole transport layer is provided between the anode and the light emitting layer.

  In the polymer LED of the present invention, a polymer LED in which a layer containing a conductive polymer is provided between at least one electrode and the light emitting layer adjacent to the electrode; between at least one electrode and the light emitting layer A polymer LED provided with an insulating layer having a thickness of 2 nm or less adjacent to the electrode is also included.

For example, the following structures a) to d) are specifically exemplified.
a) Anode / light emitting layer / cathode b) Anode / hole transport layer / light emitting layer / cathode c) Anode / light emitting layer / electron transport layer / cathode d) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (Here, / indicates that each layer is laminated adjacently. The same shall apply hereinafter.)

Here, the light emitting layer is a layer having a function of emitting light, the hole transporting layer is a layer having a function of transporting holes, and the electron transporting layer is a layer having a function of transporting electrons. It is. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer.
Two or more light emitting layers, hole transport layers, and electron transport layers may be used independently.

  Further, among the charge transport layers provided adjacent to the electrodes, those having a function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element are particularly charge injection layers (hole injection layers). , An electron injection layer).

Further, in order to improve adhesion with the electrode and charge injection from the electrode, the charge injection layer or an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode, and the adhesion at the interface may be improved. In order to prevent mixing, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.
The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

In the present invention, a polymer LED provided with a charge injection layer (electron injection layer, hole injection layer) includes a polymer LED provided with a charge injection layer adjacent to the cathode, and a charge injection layer adjacent to the anode. The provided polymer LED is mentioned.
For example, the following structures e) to p) are specifically mentioned.
e) Anode / charge injection layer / light emitting layer / cathode
f) Anode / light emitting layer / charge injection layer / cathode
g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode
h) Anode / charge injection layer / hole transport layer / light emitting layer / cathode
i) Anode / hole transport layer / light emitting layer / charge injection layer / cathode
j) Anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode
k) Anode / charge injection layer / light emitting layer / charge transport layer / cathode
l) Anode / light-emitting layer / electron transport layer / charge injection layer / cathode
m) Anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode
n) Anode / charge injection layer / hole transport layer / light emitting layer / charge transport layer / cathode o) Anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode p) Anode / charge injection layer / Hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode

  Specific examples of the charge injection layer include a layer containing a conductive polymer, an anode and a hole transport layer provided between the anode material and the hole transport material included in the hole transport layer. A layer containing a material having an ionization potential of a value, a layer provided between a cathode and an electron transport layer, and a layer containing a material having an electron affinity of an intermediate value between the cathode material and the electron transport material contained in the electron transport layer, etc. Is exemplified.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less. in order to reduce the current, more preferably less 10 ^-5 S / cm or more and 10 ² S / cm, more preferably less 10 ^-5 S / cm or more and 10 ¹ S / cm.
Usually, in order to set the electric conductivity of the conductive polymer to 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, the conductive polymer is doped with an appropriate amount of ions.

The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and examples of cations include lithium ions, sodium ions, potassium ions, tetrabutylammonium ions, and the like.
The thickness of the charge injection layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.

  The material used for the charge injection layer may be appropriately selected in relation to the electrode and the material of the adjacent layer. Polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene And derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanines (such as copper phthalocyanine), and carbon .

  An insulating layer having a thickness of 2 nm or less has a function of facilitating charge injection. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. As the polymer LED provided with the insulating layer having a thickness of 2 nm or less, the polymer LED provided with the insulating layer having a thickness of 2 nm or less adjacent to the cathode, or the insulating layer having a thickness of 2 nm or less provided adjacent to the anode. Polymer LED is mentioned.

Specific examples include the following structures q) to ab).
q) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / cathode r) Anode / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode s) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / film thickness 2 nm Insulating layer / cathode t) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / cathode
u) Anode / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode
v) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode
w) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / cathode
x) Anode / light-emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode
y) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode
z) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / cathode
aa) Anode / hole transport layer / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode
ab) Anode / insulating layer with a thickness of 2 nm or less / hole transporting layer / light emitting layer / electron transporting layer / insulating layer with a thickness of 2 nm or less / cathode

  The film thickness of the light emitting layer in the polymer LED of the present invention varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate values. For example, it is 1 nm to 1 μm, preferably Is 2 nm to 500 nm, more preferably 5 nm to 200 nm.

In the polymer LED of the present invention, a light emitting material other than the polymer complex compound may be mixed and used in the light emitting layer. In the polymer LED of the present invention, a light emitting layer containing a light emitting material other than the polymer complex compound may be laminated with a light emitting layer containing the polymer complex compound.
As the light emitting material, known materials can be used. Examples of the low molecular weight compound include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine dyes, xanthene dyes, coumarin dyes, cyanine dyes, 8-hydroxyquinoline or metal complexes of derivatives thereof, aromatic amines, and the like. , Tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used. Moreover, the triplet light emitting complex as described above can also be used.
Specifically, known ones such as those described in JP-A-57-51781 and 59-194393 can be used.

  Although there is no restriction | limiting in the film-forming method of a light emitting layer, The method by the film-forming from a solution is illustrated. As a film forming method from a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, Application methods such as a flexographic printing method, an offset printing method, and an ink jet printing method can be used.

  When the polymer LED of the present invention has a hole transport layer, the hole transport material used includes polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in a side chain or a main chain. , Pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thieni Lembinylene) or a derivative thereof is exemplified.

  Specifically, as the hole transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, Examples described in JP-A-3-37992 and JP-A-3-152184 are exemplified.

  Among these, as a hole transport material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, polyaniline or a derivative thereof, Preferred is a polymer hole transport material such as polythiophene or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, or poly (2,5-thienylene vinylene) or a derivative thereof, more preferably polyvinyl carbazole or a derivative thereof, Polysilane or a derivative thereof, or a polysiloxane derivative having an aromatic amine in the side chain or main chain. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.

  Polyvinylcarbazole or a derivative thereof is obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.

  Examples of polysilane or derivatives thereof include compounds described in Chem. Rev. 89, 1359 (1989) and GB 2300196 published specification. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.

  Since polysiloxane or a derivative thereof has almost no hole transporting property in the siloxane skeleton structure, those having the structure of the low molecular hole transporting material in the side chain or main chain are preferably used. Particularly, those having a hole transporting aromatic amine in the side chain or main chain are exemplified.

  Although there is no restriction | limiting in the film-forming method of a positive hole transport layer, In the low molecular hole transport material, the method by the film-forming from a mixed solution with a polymer binder is illustrated. In the case of a polymer hole transport material, a method of film formation from a solution is exemplified.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transport material. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  Examples of film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those showing no strong absorption against visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  The film thickness of the hole transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If it is too thick, the driving voltage of the element becomes high, which is not preferable. Therefore, the film thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  When the polymer LED of the present invention has an electron transport layer, known electron transport materials can be used, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof. Derivatives, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or Examples thereof include polyfluorene or a derivative thereof.

  Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992, The thing etc. which are described in the same 3-152184 gazette are illustrated.

  Of these, oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinones or derivatives thereof, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof are preferred, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

  There are no particular restrictions on the method for forming the electron transport layer, but for low molecular weight electron transport materials, vacuum deposition from powder, or by film formation from a solution or molten state, and for polymer electron transport materials, solution or Each method is exemplified by film formation from a molten state. In film formation from a solution or a molten state, a polymer binder may be used in combination.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve an electron transport material and / or a polymer binder. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  Examples of film formation methods from a solution or a molten state include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen. Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those not strongly absorbing visible light are suitably used. As the polymer binder, poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, poly (2,5-thienylenevinylene) or a derivative thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, or polysiloxane.

  The film thickness of the electron transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  The substrate on which the polymer LED of the present invention is formed may be any substrate that does not change when the electrode is formed and the organic layer is formed, and examples thereof include glass, plastic, polymer film, and silicon substrate. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

In the present invention, it is preferable that at least one of the electrode composed of the anode and the cathode is transparent or translucent, and the anode side is transparent or translucent.
As a material for the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film made of conductive glass made of indium, tin, oxide (ITO), indium, zinc, oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Further, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.
The film thickness of the anode can be appropriately selected in consideration of light transmittance and electrical conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm. is there.
Further, in order to facilitate charge injection on the anode, a layer made of a phthalocyanine derivative, a conductive polymer, carbon or the like, or an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like. A layer may be provided.

As a material for the cathode used in the polymer LED of the present invention, a material having a small work function is preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and their Two or more alloys, or one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite intercalation compound, etc. Is used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, and the like. The cathode may have a laminated structure of two or more layers.
The film thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

  As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used. Further, a layer made of a conductive polymer or a layer made of a metal oxide, a metal fluoride, an organic insulating material or the like having an average film thickness of 2 nm or less may be provided between the cathode and the organic material layer. A protective layer for protecting the polymer LED may be attached. In order to stably use the polymer LED for a long period of time, it is preferable to attach a protective layer and / or a protective cover in order to protect the element from the outside.

  As the protective layer, a polymer compound, metal oxide, metal fluoride, metal boride and the like can be used. Further, as the protective cover, a glass plate, a plastic plate having a low water permeability treatment on the surface, or the like can be used, and a method of sealing the cover by bonding it to the element substrate with a heat effect resin or a photo-curing resin is preferable. Used for. If a space is maintained using a spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, the cathode can be prevented from being oxidized, and moisture adsorbed in the manufacturing process by installing a desiccant such as barium oxide in the space. It becomes easy to suppress giving an image to an element. Among these, it is preferable to take any one or more measures.

Further, a polymer LED having a charge transport layer and a light emitting layer between electrodes composed of an anode and a cathode, and the charge transport layer containing the polymer complex compound of the present invention is also possible.

  The polymer light emitting device of the present invention can be used as a backlight of a planar light source, a segment display device, a dot matrix display device, and a liquid crystal display device.

In order to obtain planar light emission using the polymer LED of the present invention, the planar anode and cathode may be arranged so as to overlap each other. In addition, in order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element, an organic layer of a non-light-emitting portion is formed extremely thick and substantially non-light-emitting. There are a method of emitting light and a method of forming either or both of the anode and the cathode in a pattern. By forming a pattern by any of these methods and arranging some electrodes so that they can be turned on / off independently, a segment type display element capable of displaying numbers, letters, simple symbols, and the like can be obtained. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multicolor display are possible by a method of separately coating a plurality of types of light emitting materials having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix element can be driven passively or may be driven actively in combination with TFTs. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.
Furthermore, the planar light-emitting element is a self-luminous thin type, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source or display device.

EXAMPLES Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
Here, regarding the number and the weight average molecular weight, the number in terms of polystyrene and the weight average molecular weight were determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

この化合物と１，４−ジクロロー２−｛４−（３，７−ジメチルオクチルオキシ）フェニル｝ベンゼンと２，２‘−ビピリジルとをテトラヒドロフラン（脱水）に溶解する。窒素ガスでバブリングして、系内を窒素ガス置換する。この溶液に、ビス（１，５−シクロオクタジエン）ニッケル（０）｛Ni(COD)2｝を加え、室温で約１０分間程度攪拌する。次に、昇温し、６０℃で８時間程度反応する。なお、反応は、窒素雰囲気中で行う。
この反応液を、冷却する。この反応溶液から、通常の一連の単離操作によって重合体を得ることができるが、例えば、この反応溶液に、２５％アンモニア水／メタノール／イオン交換水混合溶液を加え、約１時間攪拌する。この溶液を室温で一夜静置する。生成した沈殿をろ過することにより、回収する。次に、この沈殿を乾燥する。この沈殿をトルエンに溶解する。不溶物をろ過することにより、除去する。次に、このトルエン溶液を、アルミナを充填したカラムを通過させることにより精製する。次に、このトルエン溶液をメタノール中に注ぎ込み、再沈精製する。沈殿を回収し、エタノールで洗浄する。次に、この沈殿を減圧乾燥して、重合体を得る。
この重合体を高分子化合物１と呼ぶ。 Example 1
<Synthesis of Polymer Compound 1>
1- (4- (Bromomethyl) phenyl) -1 ′-(4-chlorophenyl) -1 ″-(4-chlorophenyl) methane is reacted with triethyl phosphite to give the phosphonic acid ester. This phosphonate ester is reacted with 4- (2-pyridyl) benzaldehyde to obtain the following compound.

This compound, 1,4-dichloro-2- {4- (3,7-dimethyloctyloxy) phenyl} benzene and 2,2′-bipyridyl are dissolved in tetrahydrofuran (dehydration). Bubbling with nitrogen gas replaces the system with nitrogen gas. To this solution, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) 2} is added and stirred at room temperature for about 10 minutes. Next, the temperature is raised and the reaction is performed at 60 ° C. for about 8 hours. The reaction is performed in a nitrogen atmosphere.
The reaction is cooled. From this reaction solution, a polymer can be obtained by a normal series of isolation operations. For example, a 25% aqueous ammonia / methanol / ion-exchanged water mixed solution is added to this reaction solution and stirred for about 1 hour. The solution is left overnight at room temperature. The resulting precipitate is collected by filtration. The precipitate is then dried. This precipitate is dissolved in toluene. Insolubles are removed by filtration. The toluene solution is then purified by passing through a column packed with alumina. Next, this toluene solution is poured into methanol and purified by reprecipitation. The precipitate is collected and washed with ethanol. Next, this precipitate is dried under reduced pressure to obtain a polymer.
This polymer is referred to as polymer compound 1.

The structure of the repeating unit contained in the polymer compound 1 estimated from the preparation is shown below.

とをジエチレングリコール等の脱水溶媒に溶解する。この溶液を窒素ガスでバブリングすることにより、反応系内を窒素ガスで置換する。次に、この溶液を昇温し、１７５℃程度の高温で数十時間反応する。反応液を冷却した後、この反応溶液から、通常の、一連の単離操作により、重合体を得ることができるが、例えば、トルエンを加え攪拌、反応生成物を抽出する。分液により、トルエン層を回収する。次に、このトルエン溶液をメタノール中に注ぎ込み、再沈精製する。生成した沈殿を回収し、エタノールで洗浄した後、これを減圧乾燥して、重合体を得る。
この重合体を高分子錯体化合物１と呼ぶ。 Example 2
<Synthesis of Polymer Complex Compound 1>
Polymer compound 1 of Example 1 and the following Ir metal complex compound

Are dissolved in a dehydrating solvent such as diethylene glycol. By bubbling this solution with nitrogen gas, the inside of the reaction system is replaced with nitrogen gas. Next, this solution is heated and reacted at a high temperature of about 175 ° C. for several tens of hours. After cooling the reaction solution, a polymer can be obtained from this reaction solution by a series of normal isolation operations. For example, toluene is added and the reaction product is extracted by stirring. The toluene layer is collected by liquid separation. Next, this toluene solution is poured into methanol and purified by reprecipitation. The produced precipitate is collected and washed with ethanol, and then dried under reduced pressure to obtain a polymer.
This polymer is called polymer complex compound 1.

The structure of the repeating unit contained in the polymer complex compound 1 estimated from preparation is shown below.

Example 3
<Preparation of thin film and PL spectrum of thin film>
The polymer complex compound 1 is spin-coated on a quartz glass plate at 1000 rpm for about 40 seconds, and the resulting thin film is dried under reduced pressure for a whole day and night to remove the residual solvent in the film. The PL spectrum of the thin film is measured with JASCO FP-6500 spectrofluorometer.

単量体（２）

単量体（３）

４，４‘、４’‘−トリヒドロキシトリフェニルメタンにトリフルオロメタンスルホン酸無水物を反応させて、トリフルオロメタンスルホネート｛単量体（１）｝を得た。この単量体（１）０．６６ｇと単量体（２）０．５６ｇと単量体（３）０．３８ｇとを、トルエン２５ｇに溶解した。この溶液に、４ｗｔ％Ｋ₂ＣＯ₃水溶液２５ｇを加え、この溶液に、アルゴンガスをバブリンして、反応系内をアルゴンガスで置換した。この溶液にテトラキス（トリフェニルホスフィン）パラジウム（０）０．１ｇを、あらかじめアルゴンガスで脱気したトルエン１５ｇに溶解した溶液を加え、９５℃で８時間反応させた。なお、反応は窒素雰囲気中で行った。
反応後、この溶液を室温まで冷却した後、トルエンを加え、攪拌した後、静置、分液、トルエン溶液を回収した。このトルエン溶液をろ過し、不溶物を除去した後、このトルエン溶液を、アルミナを充填したカラムを通すことにより、精製した。このトルエン溶液を減圧濃縮し、トルエンを留去して、重合体を得た。この重合体をメタノールで洗浄した後、減圧乾燥して、重合体０．０３ｇを得た。この重合体を高分子化合物２と呼ぶ。
高分子化合物２のポリスチレン換算数平均分子量は２ｘ１０³であり、重量平均分子量は、４ｘ１０³であった。
仕込みから推定される高分子化合物２に含まれる繰り返し単位の構造を下記に示す。

Example 4
Monomer (1)

Monomer (2)

Monomer (3)

Trifluoromethanesulfonate {monomer (1)} was obtained by reacting 4,4 ′, 4 ″ -trihydroxytriphenylmethane with trifluoromethanesulfonic anhydride. 0.66 g of this monomer (1), 0.56 g of monomer (2) and 0.38 g of monomer (3) were dissolved in 25 g of toluene. To this solution, 25 g of 4 wt% K ₂ CO ₃ aqueous solution was added, argon gas was bubbled into this solution, and the inside of the reaction system was replaced with argon gas. To this solution was added a solution prepared by dissolving 0.1 g of tetrakis (triphenylphosphine) palladium (0) in 15 g of toluene previously degassed with argon gas, and reacted at 95 ° C. for 8 hours. The reaction was performed in a nitrogen atmosphere.
After the reaction, this solution was cooled to room temperature, toluene was added and stirred, and then allowed to stand, liquid separation, and a toluene solution were collected. The toluene solution was filtered to remove insoluble matters, and the toluene solution was purified by passing through a column packed with alumina. The toluene solution was concentrated under reduced pressure, and toluene was distilled off to obtain a polymer. This polymer was washed with methanol and then dried under reduced pressure to obtain 0.03 g of a polymer. This polymer is referred to as polymer compound 2.
The polystyrene reduced number average molecular weight of the polymer compound 2 is 2x10 ^3, weight average molecular weight was 4x10 ^3.
The structure of the repeating unit contained in the polymer compound 2 estimated from the preparation is shown below.

高分子化合物２と単量体（４）とを、ジエチレングリコールモノエチルエーテルなどの脱水溶媒に溶解した後、この溶液をアルゴンガスでバブリングすることにより、反応系内をアルゴンガスで置換する。次に、昇温して、１７５℃程度の高温で、数十時間反応する。なお、反応は、窒素雰囲気中で行う。
反応後、反応溶液を冷却した後、この反応溶液から、通常の、一連の単離操作によって、重合体を得ることができるが、例えば、この溶液をメタノール中に注ぎ込み、再沈精製する。生成した沈殿を回収し、エタノールで洗浄した後、これを減圧乾燥して、重合体を得る。
この重合体を高分子錯体化合物２と呼ぶ。
仕込みから推定される高分子錯体化合物２に含まれる繰り返し単位の構造を下記に示す

Example 5
Monomer (4)

After the polymer compound 2 and the monomer (4) are dissolved in a dehydrating solvent such as diethylene glycol monoethyl ether, the inside of the reaction system is replaced with argon gas by bubbling this solution with argon gas. Next, the temperature is raised and the reaction is performed at a high temperature of about 175 ° C. for several tens of hours. The reaction is performed in a nitrogen atmosphere.
After the reaction, the reaction solution is cooled, and then a polymer can be obtained from the reaction solution by a normal series of isolation operations. For example, this solution is poured into methanol and purified by reprecipitation. The produced precipitate is collected and washed with ethanol, and then dried under reduced pressure to obtain a polymer.
This polymer is referred to as polymer complex compound 2.
The structure of the repeating unit contained in the polymer complex compound 2 estimated from the preparation is shown below.

Example 6
Trifluoromethanesulfonate {monomer (1)} was obtained by reacting 4,4 ′, 4 ″ -trihydroxytriphenylmethane with trifluoromethanesulfonic anhydride. 0.66 g of this monomer (1) and 0.56 g of monomer (2) were dissolved in 35 g of toluene. To this solution, 35 g of a 4 wt% K ₂ CO ₃ aqueous solution was added, and argon gas was bubbled into this solution, whereby the reaction system was replaced with argon gas. Next, a solution prepared by dissolving 0.058 g of tetrakis (triphenylphosphine) palladium (0) in a toluene solution previously deaerated with argon gas was added to this solution, and reacted at 90 to 95 ° C. for 8 hours. The reaction was performed in a nitrogen atmosphere.
After the reaction, this solution was cooled to room temperature, and then toluene was added. After stirring and stirring, the solution was allowed to stand and liquid-separated to recover the toluene solution. The toluene solution was filtered to remove insoluble matters, and the toluene solution was purified by passing through a column packed with alumina. The toluene solution was concentrated under reduced pressure, and toluene was distilled off to obtain 0.09 g of a polymer. This polymer is referred to as polymer compound 3.
The polymer compound 3 had a polystyrene-equivalent number average molecular weight of 3.2 × 10 ³ and a weight average molecular weight of 3.7 × 10 ³ .
The structure of the repeating unit contained in the polymer compound 3 estimated from the preparation is shown below.

高分子化合物３をＮ，Ｎ−ジメチルホルムアミド等の脱水溶媒に溶解した後、この溶液をアルゴンガスでバブリングすることにより、反応系内をアルゴンガスで置換する。次に、この溶液に、トリス（ｏ−トリル）ホスフィンなどのリン配位子と酢酸パラジウムＰｄ（ＯＡｃ）₂を加え、攪拌する。次に、この溶液に、単量体（５）とトリエチルアミン等の塩基を加えた後、１００℃程度の温度で数十時間反応する。なお、反応は窒素雰囲気中で行う。
反応後、反応溶液を冷却した後、この反応溶液から、通常の、一連の単離操作によって、重合体を得ることができるが、例えば、この溶液をメタノール中に注ぎ込み、再沈精製する。生成した沈殿を回収し、エタノールで洗浄した後、減圧乾燥して、重合体を得る。この重合体を高分子錯体化合物３と呼ぶ。
仕込みから推定される高分子錯体化合物３に含まれる繰り返し単位の構造を下記に示す。

Example 7
Monomer (5)

After the polymer compound 3 is dissolved in a dehydrating solvent such as N, N-dimethylformamide, this reaction system is bubbled with argon gas to replace the inside of the reaction system with argon gas. Next, a phosphorus ligand such as tris (o-tolyl) phosphine and palladium acetate Pd (OAc) ₂ are added to this solution and stirred. Next, the monomer (5) and a base such as triethylamine are added to this solution, and then reacted at a temperature of about 100 ° C. for several tens of hours. The reaction is performed in a nitrogen atmosphere.
After the reaction, the reaction solution is cooled, and then a polymer can be obtained from the reaction solution by a normal series of isolation operations. For example, this solution is poured into methanol and purified by reprecipitation. The produced precipitate is collected, washed with ethanol, and then dried under reduced pressure to obtain a polymer. This polymer is referred to as polymer complex compound 3.
The structure of the repeating unit contained in the polymer complex compound 3 estimated from preparation is shown below.

単量体（７）

単量体（８）

単量体（６）０．７３ｇと単量体（７）１．４２ｇとを、テトラヒドロフラン（脱水）５０ｇに溶解した。この溶液に、あらかじめカリウム−ｔｅｒｔ．−ブトキシド ０．６７ｇをテトラヒドロフラン（脱水）１０ｇに溶解した溶液を、室温で滴下した。引き続き、室温で、５時間反応させた。なお、反応は、窒素雰囲気中で行った。
反応後、反応液を減圧濃縮して、沈殿を得た。次に、この沈殿を、メタノールで洗浄した。次に、この沈殿をトルエンに溶解した後、この溶液をろ過して、不溶物を除いた。次に、このトルエン溶液を、アルミナを充填したカラムを通すことにより、精製した。次に、このトルエン溶液を、減圧濃縮、続いて、生成した沈殿を減圧乾燥して、単量体（８）０．６ｇを得た。
Example 8
Monomer (6)

Monomer (7)

Monomer (8)

Monomer (6) 0.73 g and monomer (7) 1.42 g were dissolved in tetrahydrofuran (dehydrated) 50 g. In this solution, potassium tert. -A solution prepared by dissolving 0.67 g of butoxide in 10 g of tetrahydrofuran (dehydrated) was added dropwise at room temperature. Then, it was made to react at room temperature for 5 hours. The reaction was performed in a nitrogen atmosphere.
After the reaction, the reaction solution was concentrated under reduced pressure to obtain a precipitate. The precipitate was then washed with methanol. Next, this precipitate was dissolved in toluene, and then this solution was filtered to remove insoluble matters. Next, this toluene solution was purified by passing through a column filled with alumina. Next, this toluene solution was concentrated under reduced pressure, and then the produced precipitate was dried under reduced pressure to obtain 0.6 g of monomer (8).

Example 9
After the monomer (1) is dissolved in a dehydrating solvent such as N, N-dimethylformamide, this solution is bubbled with argon gas to replace the inside of the reaction system with argon gas. Next, a phosphorus ligand such as tris (o-tolyl) phosphine and palladium acetate Pd (OAc) ₂ are added to this solution and stirred. Next, after adding the monomer (5), the monomer (8) and a base such as triethylamine to the solution, the reaction is performed at a temperature of about 100 ° C. for several tens of hours. The reaction is performed in a nitrogen atmosphere.
After the reaction, the reaction solution is cooled, and then a polymer can be obtained from the reaction solution by a normal series of isolation operations. For example, this solution is poured into methanol and purified by reprecipitation. The produced precipitate is collected, washed with ethanol, and then dried under reduced pressure to obtain a polymer. This polymer is referred to as polymer complex compound 4.
The structure of the repeating unit contained in the polymer complex compound 4 estimated from the preparation is shown below.

Claims (8)

A polymer complex compound comprising a repeating unit represented by the following formula (1) and having a polystyrene-equivalent number average molecular weight of 1 × 10 ³ to 1 × 10 ⁸ .

[Wherein, Ar ₁ and Ar ₂ each independently represent an arylene group, a divalent heterocyclic group or a divalent aromatic amine group, and A ₁ represents an aryl group, a monovalent heterocyclic group or 1 Represents a divalent aromatic amine group, and A ₁ represents the following formula (2):
-ZT (2)
(Wherein T represents a monovalent metal complex group, Z represents a direct bond, —CR ₂₀ ═CR ₂₁ —, —C≡C—, —R ₂₂ —, —O—R ₂₂ —, —R _22. —O—, —O—R ₂₂ —O—, —C (O) —O—, —O—C (O) —, —C (O) —, —O—, —N (R ₂₃ ) —C (O) -, - C ( O) -N (R 23) -, - N = CH- or .R ₂₀ and R ₂₁ represents a -CH = N-are independently a hydrogen atom, an alkyl group, an aryl group A monovalent heterocyclic group or a cyano group, R ₂₂ represents an alkylene group or an alkenylene group, and R ₂₃ represents a hydrogen atom, an alkyl group, an aryl group or a monovalent heterocyclic group.
It has the group shown by.
B ₁ is a hydrogen atom, halogen atom, alkyl group, hydroxyl group, alkoxy group, carboxyl group, phenoxy group, alkyloxycarbonyl group, alkylcarbonyloxy group, amino group, alkylamino group, aryl group, monovalent heterocyclic group Or a monovalent aromatic amine group, and when B ₁ is an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine group, these have a group represented by the above formula (2) Z ₁ represents —CR ₁ ═CR ₂ — or —C≡C—. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. n represents 0 or 1. ] The polymer complex compound according to claim 1, further comprising a repeating unit represented by the following formula (10).

− Ar ₂₃ − (Z ′) _p − (10)
[Wherein Ar ₂₃ represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine group. Z ′ represents —CR ₄ ═CR ₅ — or —C≡C—. R ₄ and R ₅ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. p represents 0 or 1. ]   A light emitting material comprising the polymer complex compound according to claim 1.   A polymer light emitting device comprising a light emitting layer between electrodes composed of an anode and a cathode, wherein the light emitting layer contains the light emitting material according to claim 3.   5. A planar light source using the polymer light emitting device according to claim 4.   5. A segment display device using the polymer light emitting device according to claim 4.   A dot matrix display using the polymer light emitting device according to claim 4. A liquid crystal display device comprising the polymer light emitting device according to claim 4 as a backlight.