JP4752192B2 - Composition and polymer light emitting device - Google Patents

Description

  The present invention relates to a composition comprising a polymer compound and a compound that emits light from a triplet excited state, a polymer complex compound, and a polymer light-emitting device (hereinafter sometimes referred to as polymer LED).

  As a light-emitting material, an element using a compound that emits light from a triplet excited state (hereinafter sometimes referred to as a triplet light-emitting compound) for a light-emitting layer is known.

And when using a triplet light emitting compound for a light emitting layer, it is normally used as a composition which added the matrix in addition to this compound.
As a composition using a polymer compound as a matrix, for example, a polymer compound having a fluorenediyl group as a repeating unit and 2,8,12,17-tetraethyl-3,7,13,18 which is a triplet light emitting compound. -A composition containing tetramethylporphyrin is disclosed (Non-patent Document 1).

APPLIED PHYSICS LETTERS, 80, 13, 2308 (2002)

However, a device using the above composition for the light emitting layer still has insufficient luminous efficiency.
An object of the present invention is to provide a light-emitting element that is excellent in light-emitting efficiency when it is used in a light-emitting layer of a light-emitting element, which is a composition containing a compound that exhibits light emission from a triplet excited state and a polymer compound. It is in providing the composition which can be performed.

〔式中、Ｐ環およびＱ環はそれぞれ独立に芳香環を示すが、Ｐ環は存在してもしなくてもよい。2つの結合手は、Ｐ環が存在する場合は、それぞれＰ環及び/またはＱ環上に存在し、Ｐ環が存在しない場合は、それぞれＹを含む５員環上及び/またはＱ環上に存在する。
また、芳香環上及び/またはＹを含む５員環上にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基およびシアノ基からなる群から選ばれる置換基を有していてもよい。Ｙは−Ｏ−、−Ｓ−、−Ｓｉ（Ｒ_１）（Ｒ_２）−、−Ｐ（Ｒ_３）−または−ＰＲ_４（＝Ｏ）−を表し、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、シリルオキシ基、置換シリルオキシ基または1価の複素環基を表す。〕 That is, the present invention comprises a polymer compound having a repeating unit represented by the following general formula (1) and having a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ and a compound that emits light from a triplet excited state. A composition comprising the composition is provided.

[Wherein, P ring and Q ring each independently represent an aromatic ring, but P ring may or may not exist. The two bonds are present on the P ring and / or Q ring, respectively, when a P ring is present, and on the 5-membered ring and / or the Q ring, respectively, when no P ring is present. Exists.
In addition, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group on an aromatic ring and / or a 5-membered ring containing Y , arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group And may have a substituent selected from the group consisting of a cyano group. Y represents —O—, —S—, —Si (R ₁ ) (R ₂ ) —, —P (R ₃ ) — or —PR ₄ (═O) —, and R ₁ , R ₂ , R ₃ and R ₄ each independently represents an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted It represents an amino group, a silyl group, a substituted silyl group, a silyloxy group, a substituted silyloxy group or a monovalent heterocyclic group . ]

［式中、Ａｒ₁₅およびＡｒ₁₆は、それぞれ独立に３価の芳香族炭化水素基または３価の複素環基を表し、Ｒ₄₀は、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、置換基を有していても良いアリール基または１価の複素環基を表し、Ｘは単結合、

（式中Ｒ₄₁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、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、アシル基、アシルオキシ基、イミノ基、アミド基、イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。を表す。Ｒ₄₁が複数存在する場合、それらは同一でも異なっていてもよい）〕

〔式中、Ａｒ₆、Ａｒ₇、Ａｒ₈およびＡｒ₉はそれぞれ独立にアリーレン基または２価の複素環基を示す。Ａｒ_１０、Ａｒ_１１およびＡｒ_１２はそれぞれ独立にアリール基、または１価の複素環基を示す。Ａｒ₆、Ａｒ₇、Ａｒ₈、Ａｒ₉、およびＡｒ_１０は置換基を有していてもよい。ｘおよびｙはそれぞれ独立に０または１を示し、０≦ｘ＋ｙ≦１である。〕 The present invention also includes a repeating unit represented by the above formula (1), a repeating unit selected from the following formulas (12) and (13), and a metal complex structure that emits light from a triplet excited state, and is visible in a solid state. The present invention relates to a polymer complex compound having the following luminescence.

[Wherein, Ar ₁₅ and Ar ₁₆ each independently represent a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and R ₄₀ represents an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkyl group, An amino group, an aryl group which may have a substituent or a monovalent heterocyclic group, wherein X is a single bond,

(Wherein R ₄₁ is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl. indicating group, an amino group, a substituted amino group, silyl group, substituted silyl group, a sill group, acyloxy group, imino group, amido group, imido group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group And when there are a plurality of R _{41 s} , they may be the same or different.)]

[Wherein, Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ each independently represent an arylene group or a divalent heterocyclic group. Ar ₁₀ , Ar ₁₁ and Ar ₁₂ each independently represent an aryl group or a monovalent heterocyclic group. Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ , and Ar ₁₀ may have a substituent. x and y each independently represents 0 or 1, and 0 ≦ x + y ≦ 1. ]

A light emitting device using the composition of the present invention for the light emitting layer is excellent in luminous efficiency. Therefore, the composition of the present invention can be suitably used as a light emitting material for polymer LEDs, and can be used as a material for polymer light emitting elements and organic EL devices using the polymer light emitting elements.

  The polymer compound used in the present invention has one or more repeating units represented by the above formula (1).

In the above formula (1), the aromatic rings in P ring and Q ring are aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, phenanthrene ring; pyridine ring, bipyridine And heteroaromatic rings such as a ring, a phenanthroline ring, a quinoline ring, an isoquinoline ring, a thiophene ring, a furan ring, and a pyrrole ring. The aromatic ring is preferably an aromatic hydrocarbon ring.

Y represents —O—, —S—, —Si (R ₁ ) (R ₂ ) —, —P (R ₃ ) — or —PR ₄ (═O) — [R ₁ , R ₂ , R ₃ and R ₄ each independently represents an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted Represents an amino group, a silyl group, a substituted silyl group, a silyloxy group, a substituted silyloxy group or a monovalent heterocyclic group ].
Y is preferably -S- or -O-.

〔式中、Ａ環、Ｂ環、およびＣ環はそれぞれ独立に芳香環を示す。式（1-1）、（1-2）および（1-3）は、それぞれアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基およびシアノ基からなる群から選ばれる置換基を有していてもよい。Ｙは前記と同じ意味を表す。〕；

下記式（１−４）または（１−５）で示される構造

〔式中、Ｄ環、Ｅ環、Ｆ環およびＧ環はそれぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基およびシアノ基からなる群から選ばれる置換基を有していてもよい芳香環を示す。Ｙは前記と同じ意味を表す。〕；
が挙げられる。 As the structure represented by the above formula (1), the structure represented by the following formula (1-1), (1-2) or (1-3)

[In formula, A ring, B ring, and C ring show an aromatic ring each independently. Formulas (1-1), (1-2) and (1-3) are respectively an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, and an arylalkylthio group. group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl It may have a substituent selected from the group consisting of a group, a substituted carboxyl group and a cyano group. Y represents the same meaning as described above. ];

Structure represented by the following formula (1-4) or (1-5)

[In the formula, D ring, E ring, F ring and G ring are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, An aromatic ring which may have a substituent selected from the group consisting of a substituted carboxyl group and a cyano group is shown. Y represents the same meaning as described above. ];
Is mentioned.

In the above formulas (1-1), (1-2), (1-3), (1-4), (1-5), A ring, B ring, C ring, D ring, E ring, F Examples of the aromatic ring in the ring and the G ring include aromatic hydrocarbon rings such as a benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, phenanthrene ring; pyridine ring, bipyridine ring, phenanthroline ring, quinoline ring, Heteroaromatic rings such as isoquinoline ring, thiophene ring, furan ring, pyrrole ring and the like can be mentioned.

Specific examples of the formula (1-1) include the following, and the following alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkoxy groups, arylalkylthio groups , arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group And those having a substituent selected from the group consisting of a substituted carboxyl group and a cyano group. In the following, the bond represents that it can take any position on the aromatic ring in which it is present.

Specific examples of the formula (1-2) include the following, the following: an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, Examples thereof include those having a substituent selected from the group consisting of a substituted carboxyl group and a cyano group. In the following, the bond represents that it can take any position on the aromatic ring in which it is present.

Specific examples of the formula (1-3) are as follows: alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, aryl alkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, a carboxyl group, a substituted Examples thereof include those having a substituent selected from the group consisting of a carboxyl group and a cyano group. In the following, the bond represents that it can take any position on the aromatic ring in which it is present.

Specific examples of the formula (1-4) include the following, alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkoxy groups, arylalkylthio groups, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, Examples thereof include those having a substituent selected from the group consisting of a substituted carboxyl group and a cyano group. In the following, the bond represents that it can take any position on the aromatic ring in which it is present.

Specific examples of the formula (1-5) include the following, and the following alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkoxy groups, arylalkylthio groups , arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group And those having a substituent selected from the group consisting of a substituted carboxyl group and a cyano group. In the following, the bond represents that it can take any position on the aromatic ring in which it is present.

〔式中、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃およびＲ₁₄は、それぞれ独立に、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、または置換カルボキシル基を示す。aおよびｂはそれぞれ独立に０〜３の整数を示す。ｃ、ｄ、ｅおよびｆはそれぞれ独立に０〜５の整数を示す。ｇ、ｈ、iおよびｊはそれぞれ独立に０〜７の整数を示す。Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃およびＲ₁₄がそれぞれ複数ある場合、それらは同一でも異なっていてもよい。Ｙは前記と同じ意味を表す。〕 Among the above formulas (1), (1-4) and (1-5) are preferable, (1-4) is more preferable, and the following formulas (1-6), (1-7), (1-8) ), (1-9) or (1-10) is more preferable, and (1-6) is particularly preferable.

[Wherein, R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently an alkyl group, an alkoxy group, an alkylthio group, or an aryl group. , Aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, acyloxy group, imine residue, amide A group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, or a substituted carboxyl group. a and b each independently represent an integer of 0 to 3. c, d, e and f each independently represent an integer of 0 to 5. g, h, i and j each independently represent an integer of 0 to 7. When there are a plurality of R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ , they may be the same or different. Y represents the same meaning as described above. ]

Further, from the viewpoint of solubility in a solvent, a + b, c + d, e + f, g + h, and i + j are preferably 1 or more.

−Ａｒ₄−Ｘ₂− （４）
−Ｘ₃− （５） The polymer compound used in the composition of the present invention may further have a repeating unit represented by the following formula (2), formula (3), formula (4) or formula (5).
-Ar _1- (2)

—Ar ₄ —X ₂ — (4)
-X _3- (5)

[Wherein, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. X ₁ , X ₂ and X ₃ each independently represent —CR ₁₅ ═CR ₁₆ —, —C≡C—, —N (R ₁₇ ) —, or — (SiR ₁₈ R ₁₉ ) _m —. R ₁₅ and R ₁₆ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. R ₁₇ , R ₁₈ and R ₁₉ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, an arylalkyl group or a substituted amino group. ff represents 1 or 2. m represents an integer of 1 to 12. When there are a plurality of R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ , they may be the same or different. ]

The arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and usually has about 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms. 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 figure), a naphthalenediyl group (formulas 4 to 13 in the following figure), an anthracene-diyl group (formulas 14 to 19 in the following figure), and a biphenyl-diyl group (in the following figure). Formulas 20 to 25), terphenyl-diyl groups (Formulas 26 to 28 in the following diagram), condensed ring compound groups (Formulas 29 to 35 in the diagram below), fluorene-diyl groups (Formulas 36 to 38 in the diagram below), stilbene-diyl ( Examples are formulas A to D) and distilben-diyl (formulas E and F) shown below. Of these, a phenylene group, a biphenylene group, and a stilbene-diyl group are preferable.

Moreover, a bivalent heterocyclic group means the remaining atomic groups remove | excluding two hydrogen atoms from the heterocyclic compound, and carbon number is about 3-60 normally.
Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic in the ring. Say things.

Examples of the divalent heterocyclic group include the following.
Divalent heterocyclic group containing nitrogen as a hetero atom; pyridine-diyl group (formula 39 to 44 in the following figure), diazaphenylene group (formula 45 to 48 in the figure below), quinoline diyl group (formula 49 to 63 in the figure below), quinoxaline Diyl groups (formulas 64 to 68 in the lower figure), acridine diyl groups (formulas 69 to 72 in the lower figure), bipyridyldiyl groups (formulas 73 to 75 in the lower figure), phenanthroline diyl groups (formulas 76 to 78 in the lower figure), and the like.
Groups containing silicon, nitrogen, selenium and the like as a hetero atom and having a fluorene structure (formulas 79 to 93 in the following figure).
5-membered heterocyclic groups containing silicon, nitrogen, 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, selenium and the like as a hetero atom: (Formulas 99 to 110 in the following figure).
A 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium or the like as a heteroatom and bonded to the α-position of the heteroatom to form a dimer or oligomer: (Formulas 111 to 112 in the following figure) Can be mentioned.
Examples include 5-membered ring heterocyclic groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom and bonded to a phenyl group at the α-position of the hetero atom (formulas 113 to 119 in the following figure).
Examples include groups in which a phenyl group, a furyl group, or a thienyl group is substituted on a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur, and the like as a hetero atom (formulas 120 to 125 in the following figure).

In the examples shown in the above formulas 1 to 125, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group. , arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group Represents a substituted carboxyl group or a cyano group. Moreover, the carbon atom which the group of Formula 1-125 has may be substituted with the nitrogen atom, the oxygen atom, or the sulfur atom.

Ar ₁ and Ar ₄ may be arylene groups or divalent heterocyclic groups contained in all materials conventionally used as EL light-emitting materials, as long as they do not inhibit triplet light emission. It is not limited. These materials are disclosed in, for example, WO99 / 12989 WO00 / 55927 WO01 / 49769A1 WO01 / 49768A2, WO98 / 06773 US5,777,070 WO99 / 54385 WO00 / 46321 US6,169,163B1.

〔式中、Ｒ₂₀は、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。nは０〜４の整数を示す。Ｒ₂₀が複数存在する場合、それらは同一でも異なっていてもよい。〕

〔式中、Ｒ₂₁およびＲ₂₂は、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。oおよびpはそれぞれ独立に０〜３の整数を示す。Ｒ₂₁およびＲ₂₂がそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。〕

〔式中、Ｒ₂₃およびＲ₂₆は、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。qおよびrはそれぞれ独立に０〜４の整数を示す。Ｒ₂₄およびＲ₂₅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、カルボキシル基、置換カルボキシル基またはシアノ基を示す。Ｒ₂₃およびＲ₂₆がそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。〕

〔式中、Ｒ₂₇は、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。ｓは０〜２の整数を示す。Ａｒ₁₃およびＡｒ₁₄はそれぞれ独立にアリーレン基、２価の複素環基または金属錯体構造を有する２価の基を示す。ｓｓおよびｔｔはそれぞれ独立に０または１を示す。Ｘ₄は、Ｏ、Ｓ、ＳＯ、ＳＯ₂、Ｓｅ，またはＴｅを示す。Ｒ₂₇が複数存在する場合、それらは同一でも異なっていてもよい。〕

〔式中、Ｒ₂₈およびＲ₂₉は、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。tおよびuはそれぞれ独立に０〜４の整数を示す。Ｘ₅は、Ｏ、Ｓ、ＳＯ₂、Ｓｅ，Ｔｅ、Ｎ−Ｒ₃₀、またはＳｉＲ₃₁Ｒ₃₂を示す。Ｘ₆およびＸ₇は、それぞれ独立にＮまたはＣ−Ｒ₃₃を示す。Ｒ₃₀、Ｒ₃₁、Ｒ₃₂およびＲ₃₃はそれぞれ独立に水素原子、アルキル基、アリール基、アリールアルキル基または１価の複素環基を示す。Ｒ₂₈、Ｒ₂₉およびＲ₃₃がそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。〕

〔式中、Ｒ₃₄およびＲ₃₉は、それぞれ独立にアルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。vおよびwはそれぞれ独立に０〜４の整数を示す。Ｒ₃₅、Ｒ₃₆、Ｒ₃₇およびＲ₃₈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、カルボキシル基、置換カルボキシル基またはシアノ基を示す。Ａｒ₅はアリーレン基、２価の複素環基または金属錯体構造を有する２価の基を示す。Ｒ₃₄およびＲ₃₉がそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。〕 Examples of the repeating unit represented by the above formula (2) include the repeating units represented by the following formula (6), (7), (8), (9), (10) or (11).

[Wherein, R ₂₀ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, substituted amino group, a silyl group, a substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group. n represents an integer of 0 to 4. When a plurality of R ₂₀ are present, they may be the same or different. ]

[Wherein R ₂₁ and R ₂₂ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl alkynyl group, an amino group, a substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano Indicates a group. o and p each independently represent an integer of 0 to 3. When a plurality of R ₂₁ and R ₂₂ are present, they may be the same or different. ]

[ Wherein R ₂₃ and R ₂₆ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl alkynyl group, an amino group, a substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano Indicates a group. q and r each independently represents an integer of 0 to 4. R ₂₄ and R ₂₅ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. When a plurality of R ₂₃ and R ₂₆ are present, they may be the same or different. ]

[Wherein, R ₂₇ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, substituted amino group, a silyl group, a substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group. s shows the integer of 0-2. Ar ₁₃ and Ar ₁₄ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. ss and tt each independently represent 0 or 1. X ₄ represents O, S, SO, SO ₂ , Se, or Te. When a plurality of R ₂₇ are present, they may be the same or different. ]

Wherein R ₂₈ and R ₂₉ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl alkynyl group, an amino group, a substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano Indicates a group. t and u each independently represents an integer of 0 to 4. X ₅ represents O, S, SO ₂ , Se, Te, N—R ₃₀ , or SiR ₃₁ R ₃₂ . X ₆ and X ₇ each independently represent N or C—R ₃₃ . R ₃₀ , R ₃₁ , R ₃₂ and R ₃₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. When there are a plurality of R ₂₈ , R ₂₉ and R ₃₃ , they may be the same or different. ]

Wherein R ₃₄ and R ₃₉ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl alkynyl group, an amino group, a substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano Indicates a group. v and w each independently represent an integer of 0 to 4. R ₃₅ , R ₃₆ , R ₃₇ and R ₃₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. Ar ₅ represents an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. When a plurality of R ₃₄ and R ₃₉ are present, they may be the same or different. ]

Examples of the structure represented by the above formula (2) include a structure represented by the following formula (12).

［式中、Ａｒ₁₅およびＡｒ₁₆は、それぞれ独立に３価の芳香族炭化水素基または３価の複素環基を表し、Ｒ₄₀は、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、置換基を有していても良いアリール基または１価の複素環基を表し、Ｘは単結合、

（式中Ｒ₄₁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、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、アシル基、アシルオキシ基、イミノ基、アミド基、イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。を表す。Ｒ₄₁が複数存在する場合、それらは同一でも異なっていてもよい）〕

[Wherein, Ar ₁₅ and Ar ₁₆ each independently represent a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and R ₄₀ represents an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkyl group, An amino group, an aryl group which may have a substituent or a monovalent heterocyclic group, wherein X is a single bond,

(Wherein R ₄₁ is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl. indicating group, an amino group, a substituted amino group, silyl group, substituted silyl group, a sill group, acyloxy group, imino group, amido group, imido group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group And when there are a plurality of R _{41 s} , they may be the same or different.)]

Here, Ar ₁₅ and Ar ₁₆ in the formula independently represent a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group.
Here, the trivalent aromatic hydrocarbon group means an atomic group remaining after removing three hydrogen atoms from a benzene ring or condensed ring. In the following exemplary formula, of the three bonds, the bonds in the relationship of adjacent ortho positions are represented by the general formulas (12), (12-1), (12-3), and (12-4). It represents that each of X and N is bonded.

Incidentally, trivalent aromatic hydrocarbon groups mentioned may have one or more substituents on the aromatic ring, the substituent, A alkyl group, an alkyloxy group, an alkylthio group , Alkylamino group, aryl group, aryloxy group, arylthio group, arylamino group, arylalkyl group, arylalkyloxy group, arylalkylthio group, arylalkylamino group, acyl group, acyloxy group, amide group, imino group, substitution Examples include a silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a monovalent heterocyclic group, an arylalkenyl group, an arylalkynyl group, or a cyano group.
The number of carbon atoms constituting the ring of the trivalent aromatic hydrocarbon group is usually 6 to 60, preferably 6 to 20.

  The trivalent heterocyclic group refers to the remaining atomic group obtained by removing three hydrogen atoms from the heterocyclic compound.

  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. Say.

  Examples of the trivalent heterocyclic group include the following. In the following exemplary formula, of the three bonds, the bonds in the relationship of adjacent ortho positions are represented by the general formulas (12), (12-1), (12-3), and (12-4). It represents that each of X and N is bonded.

The trivalent heterocyclic group may have one or more substituents on the ring. Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, and an aryloxy group. group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, A sill group, acyloxy group, imino group, amide And a group, an imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group.
The number of carbon atoms constituting the ring of the trivalent heterocyclic group is usually 4 to 60, preferably 4 to 20.
In the above formula, each R ′ is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl. alkynyl group, an amino group, a substituted amino group, silyl group, substituted silyl group, a sill group, acyloxy group, imino group, amido group, imido group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group Show.
R ″ each independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a substituted silyl group, an acyl group, or a monovalent heterocyclic group.

（式中Ｒ₄₁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、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、アシル基、アシルオキシ基、イミノ基、アミド基、イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。Ｒ₄₁が複数存在する場合、それらは同一でも異なっていてもよい）を表す。 In the formula (12), X is a single bond,

(Wherein R ₄₁ is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl. indicating group, an amino group, a substituted amino group, silyl group, substituted silyl group, a sill group, acyloxy group, imino group, amido group, imido group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group And when there are a plurality of R ₄₁ , they may be the same or different.

が好ましく、単結合がより好ましい。
Among them, single bond,

Are preferable, and a single bond is more preferable.

Of the repeating units represented by the above formula (12), the formulas (12-1), (12-2), (12-3), (12-4), (12-5), (12- 6), more preferably, (12-1), (12-4), (12-5), (12-6), and more preferably Formula (12-6).

〔式中、Ｘ、Ａｒ₁₅およびＡｒ₁₆は、上記と同じ意味を表す。R₄₂、R₄₃、R₄₄、R₄₅およびR₄₆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、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、アシル基、アシルオキシ基、イミノ基、アミド基、イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。〕

[Wherein, X, Ar ₁₅ and Ar ₁₆ represent the same meaning as described above. R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ and R ₄₆ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, aryl alkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, a sill group, acyloxy group, imino group, amido group, imido group, monovalent heterocyclic group, carboxyl group Represents a substituted carboxyl group or a cyano group. ]

〔式中、R₄₂、R₄₃、R₄₄、R₄₅、R₄₆およびＸは上記と同じ意味を表す。R₄₇、R₄₈、R₄₉、R₅₀、R₅₁およびR₅₂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、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、アシル基、アシルオキシ基、イミノ基、アミド基、イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。〕

[Wherein, R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ , R ₄₆ and X represent the same meaning as described above. R ₄₇ , R ₄₈ , R ₄₉ , R ₅₀ , R ₅₁ and R ₅₂ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group , arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, a sill group, acyloxy group, imino group, amido group, imido group, monovalent heterocyclic group, A carboxyl group, a substituted carboxyl group or a cyano group is shown. ]

〔式中、R₄₀、Ａｒ₁₅およびＡｒ₁₆は、上記と同じ意味を表す。〕

[Wherein, R ₄₀ , Ar ₁₅ and Ar ₁₆ represent the same meaning as described above. ]

〔式中、R₄₂、R₄₃、R₄₄、R₄₅、R₄₆、Ａｒ₁₅およびＡｒ₁₆は、上記と同じ意味を表す。〕

[Wherein, R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ , R ₄₆ , Ar ₁₅ and Ar ₁₆ represent the same meaning as described above. ]

〔式中、R₄₀、R₄₇、R₄₈、R₄₉、R₅₀、R₅₁、およびR₅₂は上記と同じ意味を表す。〕

[Wherein, R ₄₀ , R ₄₇ , R ₄₈ , R ₄₉ , R ₅₀ , R ₅₁ , and R ₅₂ represent the same meaning as described above. ]

〔式中、R₄₂、R₄₃、R₄₄、R₄₅、R₄₆、R₄₇、R₄₈、R₄₉、R₅₀、R₅₁、およびR₅₂は上記と同じ意味を表す。〕

[Wherein, R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ , R ₄₆ , R ₄₇ , R ₄₈ , R ₄₉ , R ₅₀ , R ₅₁ , and R ₅₂ represent the same meaning as described above. ]

〔式中、Ａｒ₆、Ａｒ₇、Ａｒ₈およびＡｒ₉はそれぞれ独立にアリーレン基または２価の複素環基を示す。Ａｒ_１０、Ａｒ_１１およびＡｒ_１２はそれぞれ独立にアリール基、または１価の複素環基を示す。Ａｒ₆、Ａｒ₇、Ａｒ₈、Ａｒ₉、およびＡｒ_１０は置換基を有していてもよい。ｘおよびｙはそれぞれ独立に０または１を示し、０≦ｘ＋ｙ≦１である。〕 Examples of the repeating unit represented by the above formula (3) include a repeating unit represented by the following formula (13).

[Wherein, Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ each independently represent an arylene group or a divalent heterocyclic group. Ar ₁₀ , Ar ₁₁ and Ar ₁₂ each independently represent an aryl group or a monovalent heterocyclic group. Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ , and Ar ₁₀ may have a substituent. x and y each independently represents 0 or 1, and 0 ≦ x + y ≦ 1. ]

In Ar ₆ , Ar ₇ , Ar ₈ and Ar _{9 represented by the} formula (13), the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and usually has 6 to 60 carbon atoms. It is a grade, Preferably it is 6-20. 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 figure), a naphthalenediyl group (formulas 4 to 13 in the figure), an anthracene-diyl group (formulas 14 to 19 in the figure), and a biphenyl-diyl group. (Formula 20-25 in the above figure), terphenyl-diyl group (Formula 26-28 in the above figure), condensed ring compound group (Formula 29-35 in the above figure), fluorene-diyl group (Formula 36- in the above figure) 38), stilbene-diyl (formulas A to D in the figure), distilbene-diyl (formulas E and F in the figure), and the like. Of these, a phenylene group, a biphenylene group, and a stilbene-diyl group are preferable.

Moreover, a bivalent heterocyclic group means the remaining atomic groups remove | excluding two hydrogen atoms from the heterocyclic compound, and carbon number is about 3-60 normally.
Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic in the ring. Say things.

Examples of the divalent heterocyclic group include the following.
A divalent heterocyclic group containing nitrogen as a hetero atom; pyridine-diyl group (formulas 39 to 44 in the figure), diazaphenylene group (formulas 45 to 48 in the figure), quinoline diyl group (formulas 49 to 63 in the figure) ), A quinoxaline diyl group (formulas 64-68 in the figure), an acridine diyl group (formulas 69-72 in the figure), a bipyridyldiyl group (formulas 73-75 in the figure), a phenanthroline diyl group (formula 76 in the figure) ~ 78), etc.
Groups containing silicon, nitrogen, selenium and the like as a hetero atom and having a fluorene structure (formulas 79 to 93 in the above figure).
5-membered heterocyclic groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom: (Formulas 94 to 98 in the above figure).
5-membered ring condensed hetero groups containing silicon, nitrogen, selenium and the like as a hetero atom: (Formulas 99 to 108 in the above figure).
A 5-membered heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom and bonded to the α-position of the heteroatom to form a dimer or oligomer: (Formulas 109 to 113 in the above figure) Is mentioned.
Examples include 5-membered ring heterocyclic groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom and bonded to a phenyl group at the α-position of the hetero atom (formulas 113 to 119 in the above figure).
Examples include groups in which a phenyl group, a furyl group, or a thienyl group is substituted on a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur, and the like as a hetero atom (formulas 120 to 125 in the above figure).

〔式中、Ｒ₅₃、Ｒ₅₄およびＲ₅₅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、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、アシル基、アシルオキシ基、イミノ基、アミド基、イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を示す。ｘ1およびｙ１はそれぞれ独立に０〜４の整数を示す。ｚ1は１〜２の整数を示す。aaは０〜５の整数を示す。Ｒ₅₃、Ｒ₅₄およびＲ₅₅がそれぞれ複数存在する場合それらは同一でも異なっていてもよい。〕 Moreover, in the structure shown by said Formula (13), the structure shown by following formula (13-1) is preferable.

[Wherein R ₅₃ , R ₅₄ and R ₅₅ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group or an arylalkylthio group. , arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, a sill group, acyloxy group, imino group, amido group, imido group, monovalent heterocyclic group, a carboxyl group, a substituted A carboxyl group or a cyano group is shown. x1 and y1 each independently represents an integer of 0 to 4. z1 represents an integer of 1 to 2. aa represents an integer of 0 to 5. When a plurality of R ₅₃ , R ₅₄ and R ₅₅ are present, they may be the same or different. ]

R ₅₅ in the above formula (13-1) is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, or a substituted amino group. The substituted amino group is preferably a diarylamino group, more preferably a diphenylamino group.

Among the above, a preferable combination is preferably the above formula (1-6) and the above formula (5), (7), (8) or (11), more preferably the formula (1-6) and the formula (8). ) And (11).
In the structure represented by the above formula (1-6), Y is more preferably an S atom or an O atom.

Among the above, a preferable combination is preferably the above formula (1-6) and the above formula (12-2), (12-5), (12-6) or (13-1), more preferably the formula ( 1-6) and formulas (12-6) and (13-1).
In the structure represented by the above formula (1-6), Y is more preferably an S atom or an O atom.

An alkyl group represented by the above formulas (1) to (13), (12-1) to (12-6), (13-1), (1-1) to (1-10) and the above exemplary formulas , alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, A sill group, acyloxy Group, imine residue, amide group, acid imide group, monovalent heterocyclic group and substituted carboxyl group all have the same meaning.

The alkyl group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, and a 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-dimethyl octyl group, and etc. lauryl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, decyl group, 3,7-dimethyl octyl group are preferable.

The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, and a 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-dimethyl octyloxy group, lauryl group, main butoxy methyl group, such as 2-methoxyethyl group and the like, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyl group, A decyloxy group and a 3,7-dimethyloctyloxy group are preferred.

The alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include a methylthio group, an ethylthio group, a propylthio group, i -Propylthio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyl octylthio group, etc. laurylthio group and the like, pentylthio group, hexylthio group, octylthio group, 2-ethylhexyl group, decylthio group, 3,7-dimethyloctylthio group are preferable.

The aryl group usually has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specifically, the aryl group is a phenyl group or a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ has ₁ to ₁₂ carbon atoms. the same is true. below indicate that is.), C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl, 2-naphthyl, 1-anthracenyl group, etc. 9-anthracenyl group Examples thereof include a C ₁ -C ₁₂ alkoxyphenyl group and a C ₁ -C ₁₂ alkylphenyl group. Here, the aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. 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.
Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2 -Ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ alkylphenyl group as specifically methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, i- propylphenyl group, butylphenyl group, i- butyl Examples include phenyl group, t-butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group and the like.

The aryloxy group usually has about 6 to 60 carbon atoms, preferably 7 to 48, and specific examples thereof include phenoxy group, C _{1 to} C ₁₂ alkoxyphenoxy group, C _{1 to} C ₁₂ alkylphenoxy group, 1 - naphthyloxy group, etc. 2-naphthyloxy group and the like, C ₁ -C ₁₂ alkoxy phenoxy group, a C ₁ -C ₁₂ alkylphenoxy group are preferable.
Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2 -Ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ alkylphenoxy such as methyl phenoxy groups as group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-methylphenoxy group, methylethylphenoxy group, i- propyl phenoxy group, Examples include butylphenoxy, i-butylphenoxy, t-butylphenoxy, pentylphenoxy, isoamylphenoxy, hexylphenoxy, heptylphenoxy, octylphenoxy, nonylphenoxy, decylphenoxy, dodecylphenoxy Is done.

Arylthio group, usually about 6 to 60 carbon atoms, preferably 7 to 48, and specific examples thereof include a phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2-etc.-naphthylthio group are exemplified, C ₁ -C ₁₂ alkoxyphenyl-thio group, a C ₁ -C ₁₂ alkyl phenylthio group are preferable.

The arylalkyl group usually has about 7 to 60 carbon atoms, preferably 7 to 48, and specific examples thereof include a phenyl-C ₁ -C ₁₂ alkyl group and a 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 groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group are preferable.

The arylalkoxy group usually has about 7 to 60 carbon atoms, preferably 7 to 48. Specific examples thereof include phenylmethoxy group, phenylethoxy group, phenylbutoxy group, phenylpentyloxy group, phenylhexyloxy group, phenyl heptene Ciro alkoxy group, a phenyl -C ₁ -C ₁₂ alkoxy groups such as phenyl Ok Ciro alkoxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C Examples include ₁₂ alkoxy groups, 1-naphthyl-C ₁ -C ₁₂ alkoxy groups, 2-naphthyl-C ₁ -C ₁₂ alkoxy groups, etc., C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxy groups, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy group are preferable.

Arylalkylthio group has usually about 7 to 60 carbon atoms, preferably 7 to 48, and examples thereof include phenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group, 1-naphthyl -C ₁ -C ₁₂ alkylthio group, 2-naphthyl -C ₁ -C ₁₂ alkylthio groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group are preferable.

Arylalkenyl group has usually about 7 to 60 carbon atoms, preferably 7 to 48, and examples thereof include 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 alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, C ₂ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkenyl groups are preferred.

The arylalkynyl group has usually about 7 to 60 carbon atoms, preferably 7 to 48, and examples thereof include phenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl, 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.

The substituted amino group refers to an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and the alkyl group, aryl group, arylalkyl group or The monovalent heterocyclic group may have a substituent. The substituted amino group usually has about 1 to 60 carbon atoms, preferably 2 to 48, not including the carbon number of the substituent, and specific examples thereof include a methylamino group, a dimethylamino group, an ethylamino group, Diethylamino group, propylamino group, dipropylamino group, i-propylamino group, diisopropylamino 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, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, diphenylmethane Arylamino 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, 2-naphthylamino group , Pi Rijiruamino group, pyridazinylamino group, pyrimidylamino group, Pirajiruamino group, triazyl amino group phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ ~ C ₁₂ alkyl) amino groups, 1-naphthyl -C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ alkylamino groups.

Examples of the substituted silyl group include a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. The substituted silyl group usually has about 1 to 60 carbon atoms, preferably 3 to 48 carbon atoms. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
Specific examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, t-butylsilyldimethylsilyl. Group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group , lauryl dimethyl silyl group, a phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group , 1-naphthyl -C ₁ -C ₁₂ Arukirushiri Group, 2-naphthyl -C ₁ -C ₁₂ alkylsilyl group, a phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzylsilyl group, diphenylmethylsilyl group, t -A butyl diphenylsilyl group, a dimethylphenylsilyl group, etc. are illustrated.

Acyl group, usually about 2 to 20 carbon atoms, preferably 2 to 18, and examples thereof include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, are exemplified etc. benzoyl group .

The acyloxy group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a benzoyloxy group. etc. groups.

As the imine residue, an imine compound (refers to an organic compound having —N═C— in the molecule. For example, aldimine, ketimine, and hydrogen atoms on these N are substituted with alkyl groups or the like. And a residue obtained by removing one hydrogen atom from the compound, usually having about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples include groups represented by the following structural formulas.

The amide group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group , diformamide group, diacetamide. group, Jipuropioamido group, dipropioamide group, etc. dibenzamide groups.

The acid imide group includes a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide, and usually has about 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms. Specific examples include the following groups.

The monovalent heterocyclic group refers to a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms, preferably 4 to 20 carbon atoms. The carbon number of the heterocyclic group does not include the carbon number of the substituent. Here, the heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, etc. in the ring. Say. Specifically, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, piperidyl group, quinolyl group, isoquinolyl group and the like, a thienyl group , C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

Examples of the substituted carboxyl group include a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and the carbon number is usually about 2 to 60, preferably 2 to 48. Specific examples include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, i-propoxycarbonyl group, butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyl group. Siloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl , Full E Roh alkoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group, and the like. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The carbon number of the substituted carboxyl group does not include the carbon number of the substituent.

Among the above, in the group containing alkyl, they may be linear, branched or cyclic, or a combination thereof. When they are not linear, for example, isoamyl group, 2-ethylhexyl group, 3, 7 - dimethyl octyl group, a cyclohexyl group, etc. 4-C ₁ ~C ₁₂ alkyl cyclohexyl groups. Further, the ends of two alkyl chains may be connected to form a ring. Furthermore, some methyl groups and methylene groups of alkyl may be replaced with groups containing heteroatoms, and examples of these heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms and the like.
Furthermore, among the examples of substituents, when an aryl group or a heterocyclic group is included in a part thereof, they may further have one or more substituents.

In order to increase the solubility in organic solvents, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ preferably have a substituent, and one or more of them contain a cyclic or long-chain alkyl group or alkoxy group. Are preferred, cyclopentyl group, cyclohexyl group, pentyl group, isoamyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, 3,7-dimethyloctyl group, pentyloxy group, isoamyloxy group, hexyloxy group Octyloxy group, 2-ethylhexyloxy group, decyloxy group and 3,7-dimethyloctyloxy group.

  Two substituents may be connected to form a ring. Furthermore, some carbon atoms of the alkyl may be replaced with a group containing a hetero atom, and examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.

  The terminal group of the polymer compound used in the present invention may be 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 life when the device is made may be reduced. . Those having a conjugated bond continuous with the conjugated structure of the main chain are preferable, and examples thereof include a structure in which an aryl group or a heterocyclic group is bonded via a carbon-carbon bond. Specific examples include substituents described in Chemical formula 10 of JP-A-9-45478.

  The polymer compound used in the present invention may be a random, block or graft copolymer, or a polymer having an intermediate structure thereof, for example, a random copolymer having a block property. Also good. From the viewpoint of obtaining a polymer compound having a high 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.

The polymer compound used in the present invention preferably has a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ . More preferably, it is 10 ⁴ to 10 ⁷ .

Next, the manufacturing method of the high molecular compound used for the composition of this invention is demonstrated.
The polymer compound used in the composition of the present invention is specifically a monomer, a compound having a plurality of reactive substituents, if necessary, dissolved in an organic solvent, for example, using an alkali or a suitable catalyst, The organic solvent can be produced at a melting point or higher and a boiling point or lower. For example, “Organic Reactions”, Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965, “Organic Synthesis”, Collective Vol. (Collective Volume VI), 407-411, John Wiley & Sons, Inc., 1988, Chemical Review (Chem. Rev.), 95, 2457 (1995), Journal of Organometallic. Chemistry (J. Organomet. Chem.), 576, 147 (1999), Macromolecular Chemistry Macromolecular Known methods described in the symposium (Macromol. Chem., Macromol. Symp.), Vol. 12, 229 (1987) can be used.

In the method for producing a polymer compound used in the composition of the present invention, the condensation polymerization can be carried out by using a known condensation reaction. In the condensation polymerization, when a double bond is generated, for example, a method described in JP-A-5-202355 can be mentioned. That is, polymerization by Wittig reaction of a compound having a formyl group and a compound having a phosphonium methyl group, or a compound having a formyl group and a phosphonium methyl group, by Heck reaction between a compound having a vinyl group and a compound having a halogen atom. Polymerization, polycondensation of compounds having two or more monohalogenated methyl groups by dehydrohalogenation method, polycondensation of compounds having two or more sulfonium methyl groups by decomposing sulfonium salt, having a formyl group Examples include a method such as polymerization by a Knoevenagel reaction between a compound and a compound having a cyano group, and a method such as polymerization by a McMurry reaction of a compound having two or more formyl groups.
When the polymer compound of the present invention forms a triple bond in the main chain by condensation polymerization, for example, the Heck reaction can be used.

Further, when a double bond or triple bond is not generated, for example, a method of polymerizing from a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a Ni (0) complex, FeCl ₃ or the like Examples thereof include a method of polymerizing with an oxidizing agent, a method of electrochemically oxidatively polymerizing, a method of decomposing an intermediate polymer having an appropriate leaving group, and the like.

  Among these, the structure is controlled by the polymerization by the Wittig reaction, the polymerization by the Heck reaction, the polymerization by the Knoevenagel reaction, the polymerization by the Suzuki coupling reaction, the polymerization by the Grignard reaction, and the polymerization by the nickel zero-valent complex. It is preferable because it is easy.

When the reactive substituent of the raw material monomer of the polymer compound used in the present invention is a halogen atom, an alkyl sulfonate group, an aryl sulfonate group or an aryl alkyl sulfonate group, a production method in which condensation polymerization is performed in the presence of a nickel zero-valent complex Is preferred.
As raw material compounds, dihalogenated compounds, bis (alkyl sulfonate) compounds, bis (aryl sulfonate) compounds, bis (aryl alkyl sulfonate) compounds or halogen-alkyl sulfonate compounds, halogen-aryl sulfonate compounds, halogen-aryl alkyl sulfonate compounds, Examples include alkyl sulfonate-aryl sulfonate compounds, alkyl sulfonate-aryl alkyl sulfonate compounds, and aryl sulfonate-aryl alkyl sulfonate compounds.

Further, when the reactive substituent of the raw material monomer of the polymer compound used in the present invention is a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a boric acid group, or a boric acid ester group, The ratio of the total number of moles of halogen atoms, alkyl sulfonate groups, aryl sulfonate groups and arylalkyl sulfonate groups to the total number of moles of boric acid groups and boric acid ester groups is substantially 1 (usually 0.7 to 1. 2), and a production method in which condensation polymerization is performed using a nickel catalyst or a palladium catalyst is preferable.
Specific combinations of raw material compounds include a combination of a dihalogenated compound, a bis (alkyl sulfonate) compound, a bis (aryl sulfonate) compound or a bis (aryl alkyl sulfonate) compound and a diboric acid compound or a diboric acid ester compound. .
Further, halogen-boric acid compounds, halogen-boric acid ester compounds, alkyl sulfonate-boric acid compounds, alkyl sulfonate-boric acid ester compounds, aryl sulfonate-boric acid compounds, aryl sulfonate-boric acid ester compounds, aryl alkyl sulfonate-borates Examples include acid compounds, arylalkyl sulfonate-boric acid compounds, and arylalkyl sulfonate-boric acid ester compounds.

  The organic solvent varies depending on the compound and reaction to be used, but it is generally preferable that the solvent to be used is sufficiently deoxygenated and the reaction proceeds in an inert atmosphere in order to suppress side reactions. Similarly, it is preferable to perform a dehydration treatment. However, this is not the case in the case of a two-phase reaction with water, such as the Suzuki coupling reaction.

  In order to make it react, an alkali and a suitable catalyst are added suitably. These may be selected according to the reaction used. The alkali or catalyst is preferably one that is sufficiently dissolved in the solvent used in the reaction. As a method of mixing the alkali or catalyst, slowly add the alkali or catalyst solution while stirring the reaction solution under an inert atmosphere such as argon or nitrogen, or conversely, slowly add the reaction solution to the alkali or catalyst solution. And the method of adding.

  When the polymer compound used in the present invention is used in a polymer LED or the like, the purity of the polymer affects the performance of the device such as light emission characteristics. Therefore, the monomer before polymerization is purified by a method such as distillation, sublimation purification, and recrystallization. It is preferable to polymerize later. Further, after the polymerization, it is preferable to carry out a purification treatment such as reprecipitation purification and fractionation by chromatography.

  Next, a compound (triplet luminescent compound) that emits light from a triplet excited state used in the composition of the present invention will be described. Examples of the compound 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.

  Among the triplet light-emitting compounds, examples of the complex compound (triplet light-emitting complex compound) include metal complex compounds 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 compound is usually a metal having an atomic number of 50 or more, which has a spin-orbit interaction in the complex and can cause intersystem crossing between the singlet state and the triplet state. .

  Examples of the central metal of the triplet light-emitting complex compound include rhenium, iridium, osmium, scandium, yttrium, platinum, gold, and lanthanoids such as 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.

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

As a triplet light-emitting complex compound, a structure shown by the following formula (15) can be given as an example in more detail.

(H) _o1- M- (K) _m1 (15)

In the formula, K represents a ligand, a halogen atom or a hydrogen atom containing an atom bonded to one or more M selected from a nitrogen atom, an oxygen atom, a carbon atom, a sulfur atom and a phosphorus atom. O1 represents an integer of 0 to 5, and m1 represents an integer of 1 to 5.

  Here, as a ligand containing an atom bonded to one or more M selected from a nitrogen atom, an oxygen atom, a carbon atom, a sulfur atom and a phosphorus atom, an alkyl group, an alkoxy group, an acyloxy group, an alkylthio group, an alkyl Amino group, aryl group, aryloxy group, arylthio group, arylamino group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group, sulfonate group, cyano group, heterocyclic ligand, carbonyl compound, ether , Amines, imines, phosphines, phosphites, and sulfides. The bond of the ligand to M may be a coordination bond or a covalent bond. Moreover, the multidentate ligand which combined these may be sufficient.

The alkyl group may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms is usually about 1 to 20, 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, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, Examples include perfluorooctyl group, and 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 may have a substituent, and usually has about 1 to 20 carbon atoms. Specifically, a methoxy group, an ethoxy group, a 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, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group, methoxymethyloxy group, 2-methoxyethyloxy group Pentyloxy group, hexyloxy group, Yloxy group, 2-ethylhexyl group, decyloxy group, 3,7-dimethyl octyloxy group are preferable.

  The acyloxy group usually has about 2 to 20 carbon atoms, and specific examples thereof include an acetyloxy group, a trifluoroacetyloxy group, a propionyloxy group, and a benzoyloxy group. Examples of the sulfoneoxy group include a benzenesulfoneoxy group, a p-toluenesulfoneoxy group, a methanesulfoneoxy group, an ethanesulfoneoxy group, and a trifluoromethanesulfoneoxy group.

  The alkylthio group may be linear, branched or cyclic, and may have a substituent, and usually has about 1 to 20 carbon atoms. Specific examples thereof include a methylthio group, an ethylthio group, and a propylthio group. I-propylthio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7 -A dimethyloctylthio group, a laurylthio group, a trifluoromethylthio group etc. are mentioned, A pentylthio group, a hexylthio group, an octylthio group, 2-ethylhexylthio group, a decylthio group, and a 3,7- dimethyloctylthio group are preferable.

  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. Specific examples thereof include a methylamino group, dimethylamino group Group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, i-propylamino group, diisopropylamino 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, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group Group, dicyclohexyl Amino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group and the like can be mentioned, and pentylamino group, hexylamino group, octylamino group, 2-ethylhexylamino group, decylamino group and 3,7-dimethyloctylamino group are preferable. .

The aryl group may have a substituent and usually has about 3 to 60 carbon atoms. Specific examples thereof include a phenyl group, a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ are C ₁ -C ₁₂ alkyl phenyl group, 1-naphthyl group, 2-naphthyl group, pentafluorophenyl group, pyridyl group, pyridazinyl group, pyrimidyl. group, pyrazyl group, etc. triazyl group and the _like, C 1 _{-C 12} alkoxyphenyl _group, is C 1 _{-C 12} alkylphenyl group are preferable.

The aryloxy group may have a substituent on the aromatic ring and usually has about 3 to 60 carbon atoms. Specific examples thereof include a phenoxy group, a C _{1 to} C ₁₂ alkoxyphenoxy group, and C _1. -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group, pyridyloxy group, pyridazinyloxy group, pyrimidyloxy group, pyrazyloxy group, triazyl group is exemplified , _C 1 _{-C 12} alkoxy phenoxy _group, a C 1 _{-C 12} alkylphenoxy group are preferable.

The arylthio group may have a substituent on the aromatic ring and usually has about 3 to 60 carbon atoms. Specific examples thereof include a phenylthio group, a C _{1 to} C ₁₂ alkoxyphenylthio group, and C _1. -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group, pentafluorophenylthio group, pyridylthio group, pyridazinylthio group, pyrimidylthio group, pyrazylthio group, etc. Toriajiruchio group and the _like, C 1 _{-C 12} alkoxyphenyl _thio, C 1 _{-C 12} alkyl phenylthio group are preferable.

Arylamino group may have a substituent on the aromatic ring is usually about 3 to 60 carbon atoms, and specific examples thereof include phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxy phenylamino group, a di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group And a pyridazinylamino group, a pyrimidylamino group, a pyrazylamino group, a triazylamino group and the like are exemplified, and a C ₁ -C ₁₂ alkylphenylamino group and a di (C ₁ -C ₁₂ alkylphenyl) amino group are preferable.

The arylalkyl group may have a substituent and usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl-C ₁ -C ₁₂ alkyl group and a 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 exemplified _is, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkyl _group, C 1 _{-C 12} alkylphenyl _-C 1 _{-C 12} alkyl group.

The arylalkoxy group may have a substituent and usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl-C ₁ -C ₁₂ alkoxy group and a C ₁ -C ₁₂ alkoxyphenyl- C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkoxy group, 1-naphthyl-C ₁ -C ₁₂ alkoxy group, 2-naphthyl-C ₁ -C ₁₂ alkoxy group and the like are exemplified _is, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkoxy _group, a C 1 _{-C 12} alkylphenyl _-C 1 _{-C 12} alkoxy group are preferred.

The arylalkylthio group may have a substituent and usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl-C ₁ -C ₁₂ alkoxy group, a C ₁ -C ₁₂ alkoxyphenyl- C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkoxy group, 1-naphthyl-C ₁ -C ₁₂ alkoxy group, 2-naphthyl-C ₁ -C ₁₂ alkoxy group and the like are exemplified _is, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkoxy _group, a C 1 _{-C 12} alkylphenyl _-C 1 _{-C 12} alkoxy group are preferred.

Arylalkylamino group has usually about 7 to 60 carbon atoms, and specific examples thereof include a phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl-C ₁₎ -C ₁₂ alkyl) amino groups, 1-naphthyl -C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ alkylamino groups and the like, etc. are exemplified, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino group are preferable.

Examples of the sulfonate group include a benzene sulfonate group, a p-toluene sulfonate group, a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group.

  Heterocyclic ligands include ligands composed of pyridine rings, pyrrole rings, thiophene rings, oxazole, furan rings and other heterocyclic rings and benzene rings, 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) benzoxazole, 2-phenylbenzothiazole, 2- (paraphenylphenyl) benzothiazole, 2- (benzothiophen-2-yl) pyridine, 1,10-phenanthroline, 2,3,7,8, Examples include 12,13,17,18-octaethyl-21H, 23H-porphyrin, which may be a coordination bond or a covalent bond.

  Examples of the carbonyl compound are those having a coordinate bond with M at an oxygen atom, and examples thereof include ketones such as carbon monoxide, acetone and benzophenone, and diketones such as acetylacetone and acenaphthoquinone.

  Ethers are those that coordinate with M through an oxygen atom, and examples thereof include dimethyl ether, diethyl ether, tetrahydrofuran, and 1,2-dimethoxyethane.

  Examples of amines include those that coordinately bond with M at a nitrogen atom, such as monoamines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, triphenylamine, dimethylphenylamine, and methyldiphenylamine, 1,1,2,2 Examples include diamines such as tetramethylethylenediamine, 1,1,2,2-tetraphenylethylenediamine, and 1,1,2,2-tetramethyl-o-phenylenediamine.

  As the imine, it is coordinated to M by a nitrogen atom. For example, monoimines such as benzylideneaniline, benzylidenebenzylamine, benzylidenemethylamine, dibenzylideneethylenediamine, dibenzylidene-o-phenylenediamine, 2,3-bis ( Animino) butane and other diimines are exemplified.

  Examples of the phosphine are those having a coordinate bond with M at a phosphorus atom, and examples thereof include triphenylphosphine, diphenylphosphinoethane, and diphenylphosphinopropane. Examples of the phosphite are those having a coordinate bond with M at a phosphorus atom, and examples thereof include trimethyl phosphite, triethyl phosphate, and triphenyl phosphite.

  Examples of the sulfide include those having a coordinate bond with M at a sulfur atom, and examples thereof include dimethyl sulfide, diethyl sulfide, diphenyl sulfide, and thioanisole.

  M represents a metal atom having an atomic number of 50 or more and capable of causing an intersystem crossing between a singlet state and a triplet state in the present compound by spin-orbit interaction.

Alkyl group, alkoxy group, acyloxy group, alkylthio group, alkylamino group, aryl group, aryloxy group, arylthio group, arylamino group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group, sulfonate group, Multi-dentate ligands combining cyano groups, heterocyclic ligands, carbonyl compounds, ethers, amines, imines, phosphines, phosphites, and sulfides include acetylacetonate, dibenzomethylate, thenoyltrifluoro Examples include acetonates such as acetonate.

  As atoms represented by M, rhenium atom, osmium atom, iridium atom, platinum atom, gold atom, lanthanum atom, cerium atom, praseodymium atom, neodymium atom, promethium atom, samarium atom, europium atom, gadolinium atom, terbium atom, Examples include dysprosium atoms, preferably rhenium atom, osmium atom, iridium atom, platinum atom, gold atom, samarium atom, europium atom, gadolinium atom, terbium atom, dysprosium atom, and more preferably iridium in terms of luminous efficiency. Atoms, platinum atoms, gold atoms, europium atoms.

H represents a ligand containing one or more atoms selected from a nitrogen atom, an oxygen atom, a carbon atom, a sulfur atom and a phosphorus atom as an atom bonded to M.
The ligand containing one or more atoms selected from a nitrogen atom, an oxygen atom, a carbon atom, a sulfur atom and a phosphorus atom as the atom bonded to M is the same as that exemplified for K.

Examples of H include the following. In the formula, * represents an atom bonded to M.

  Here, each R is independently a hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio group, alkylamino group, alkylsilyl group, aryl group, aryloxy group, arylthio group, arylamino group, arylsilyl group. , Arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group, arylalkylsilyl group, acyl group, acyloxy group, imine residue, amide group, arylalkenyl group, arylalkynyl group, cyano group, or monovalent The heterocyclic group of is shown. R may combine with each other to form a ring. In order to enhance the solubility in a solvent, it is preferable that at least one of R includes a long-chain alkyl group.

  Here, alkyl group, alkoxy group, acyloxy group, alkylthio group, alkylamino group, aryl group, aryloxy group, arylthio group, arylamino group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group A specific example is the same as Y above.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

  The alkylsilyl group may be linear, branched or cyclic, and usually has about 1 to 60 carbon atoms. Specifically, the trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-i-propylsilyl group Group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, t-butylsilyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethyl Examples include silyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, octyldimethylsilyl group, 2- Ethylhexyl-dimethyl Rushiriru group, decyldimethylsilyl group, a 3,7-dimethyl silyl group.

  The arylsilyl group may have a substituent on the aromatic ring, and usually has about 3 to 60 carbon atoms. The triphenylsilyl group, tri-p-xylylsilyl group, tribenzylsilyl group, diphenylmethyl Examples include silyl group, t-butyldiphenylsilyl group, dimethylphenylsilyl group and the like.

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

  Acyl groups usually have about 2 to 20 carbon atoms, and specific examples include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, benzoyl, trifluoroacetyl, and pentafluorobenzoyl groups. Is done.

  The acyloxy group usually has about 2 to 20 carbon atoms. Specifically, the acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetyloxy group, pentane Examples include a fluorobenzoyloxy group.

  The definition and specific examples of the imine residue are as described above.

  The amide group usually has about 2 to 20 carbon atoms, and specifically includes a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diamide group. Examples include an acetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group, a dipentafluorobenzamide group, a succinimide group, and a phthalimide group.

The arylalkenyl group has a carbon number of usually about 7 to 60, specifically, phenyl _-C 1 _{-C 12} alkenyl _group, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkenyl group, _{C 1} -C ₁₂ alkylphenyl _-C 1 _{-C 12} alkenyl group, 1-naphthyl _-C 1 _{-C 12} alkenyl groups, 2-naphthyl _-C 1 _{-C 12} alkenyl groups and the _like, C 1 _{-C 12} alkoxyphenyl - C ₁ -C ₁₂ alkenyl _group, C 1 _{-C 12} alkylphenyl _-C 1 _{-C 12} alkenyl groups are preferred.

The arylalkynyl group has a carbon number of usually about 7 to 60, specifically, phenyl _-C 1 _{-C 12} alkynyl _group, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkynyl group, _{C 1} -C ₁₂ alkylphenyl _-C 1 _{-C 12} alkynyl group, 1-naphthyl _-C 1 _{-C 12} alkynyl groups, 2-naphthyl _-C 1 _{-C 12} alkynyl groups and the _like, C 1 _{-C 12} alkoxyphenyl - C ₁ -C ₁₂ alkynyl _group, C 1 _{-C 12} alkylphenyl _-C 1 _{-C 12} alkynyl group are preferable.

The monovalent heterocyclic group refers to a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms. Specifically, a thienyl group, C _{1 to} C Examples include ₁₂ alkyl thienyl groups, pyrrolyl groups, furyl groups, pyridyl groups, C ₁ -C ₁₂ alkyl pyridyl groups, and the like, and thienyl groups, C ₁ -C ₁₂ alkyl thienyl groups, pyridyl groups, C ₁ -C ₁₂ alkyl pyridyl groups. Is preferred.

  In terms of stability of the compound, H is preferably bonded to M through at least one nitrogen atom or carbon atom, and more preferably, H is bonded to M in a multidentate manner.

（式中、Ｒ₅₈〜Ｒ₆₅はそれぞれ独立に水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、アルキルアミノ基、アルキルシリル基、アリール基、アリールオキシ基、アリールチオ基、アリールアミノ基、アリールシリル基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルキルアミノ基、アリールアルキルシリル基、アシル基、アシルオキシ基、イミン残基、アミド基、アリールアルケニル基、アリールアルキニル基、シアノ基、１価の複素環基を示し、＊はＭと結合する部位を表す。） More preferably, H is represented by the following formula (H-1) or (H-2).

Wherein R _{58 to} R ₆₅ are each independently a hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio group, alkylamino group, alkylsilyl group, aryl group, aryloxy group, arylthio group, arylamino group, Arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group, arylalkylsilyl group, acyl group, acyloxy group, imine residue, amide group, arylalkenyl group, arylalkynyl group, cyano group, Represents a monovalent heterocyclic group, and * represents a site bonded to M.)

（式中、Ｔは酸素原子または硫黄原子を示す。Ｒ₆₆〜Ｒ₇₁はそれぞれ独立に水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、アルキルアミノ基、アルキルシリル基、アリール基、アリールオキシ基、アリールチオ基、アリールアミノ基、アリールシリル基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルキルアミノ基、アリールアルキルシリル基、アシル基、アシルオキシ基、イミン残基、アミド基、アリールアルケニル基、アリールアルキニル基、シアノ基を示し、＊はＭと結合する部位を表す。）

(In the formula, T represents an oxygen atom or a sulfur atom. R _{66 to} R ₇₁ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an alkylsilyl group, an aryl group, an aryl group) Oxy group, arylthio group, arylamino group, arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group, arylalkylsilyl group, acyl group, acyloxy group, imine residue, amide group, aryl An alkenyl group, an arylalkynyl group or a cyano group is shown, and * represents a site bonded to M.)

Further, the triplet light emitting complex compound used in the present invention may be a polymer compound containing a triplet complex structure in the molecule. Such compounds are disclosed in JP2003-073480, JP2003-073479, JP2002-280183, JP2003-77673, and the like.

  The composition of the present invention may contain two or more metal complexes that emit light from a triplet excited state. Each metal complex may have the same metal as each other or different metals. Moreover, each metal complex structure may have mutually different luminescent color. For example, a case where both a metal complex that emits green light and a metal complex that emits red light are included in one polymer complex compound is exemplified. At this time, it is preferable to design so that an appropriate amount of the metal complex is included because the emission color can be controlled.

The amount of the triplet light-emitting compound in the composition of the present invention is not particularly limited because it varies depending on the type of polymer compound to be combined and the property to be optimized, but when the amount of the polymer compound is 100 parts by weight, 0.01 to 80 parts by weight, preferably 0.1 to 60 parts by weight.

  When the composition of the present invention is used as a light emitting material of a polymer LED, the purity affects the light emission characteristics. Therefore, the monomer before polymerization is polymerized after being purified by methods such as distillation, sublimation purification, and recrystallization. In addition, after the synthesis, it is preferable to carry out a purification treatment such as reprecipitation purification and fractionation by chromatography. Note that the polymer compound of the present invention can be used not only as a light emitting material but also as an organic semiconductor material, an optical material, or a conductive material by doping.

The polymer complex compound according to another embodiment of the present invention is characterized by having in its molecular chain a metal complex structure that emits light from a triplet excited state in addition to a specific repeating unit. Specifically, the polymer complex has a repeating unit represented by the above formula (1), a repeating unit selected from the above formulas (12) and (13), and a metal complex structure that emits light from a triplet excited state. And having visible light emission in a solid state.
The definitions and specific examples of the formulas (1), (12), and (13) are the same as those of the polymer compound used in the above composition.

Y in Formula (1) is preferably an O atom or an S atom.

As the polymer complex compound of the present invention, the formula (1) is represented by the above (1-1), (1-2), (1-3), (1-4), (1-5), (1- 6), (1-7), (1-8), (1-9), or a repeating unit selected from (1-10) is preferred, (1-4), (1-5), (1-6), (1-7), (1-8), (1-9), (1-10) are more preferred, (1-6), (1-7), (1-8) , (1-9) and (1-10) are more preferable, and (1-6) is particularly preferable.

  Among the repeating units of the formula (12) or (13), the above (12-1), (12-2), (12-3), (12-4), (12-5), (12-6) ), (13-1) are preferred, (12-2), (12-5), (12-6), (13-1) are more preferred, and (12-6), (13-1) are more preferred. ).

A preferable combination among the above is selected from a metal complex structure that emits light from a triplet excited state, a repeating unit represented by (1-6), and either (12-6) or (13-1). Includes repeat units.
Particularly preferred is a metal complex structure that emits light from a triplet excited state, a repeating unit represented by (1-6), and a repeating unit of (12-6).

  The metal complex structure showing light emission from the triplet excited state may be contained in the polymer main chain, may be present in the side chain, or may be present at the terminal.

Examples of the metal complex structure that emits light from the triplet excited state include a structure represented by the following formula (16).

(L) _o2 -M- (Ar) _m2 (16)

In the formula, M represents the same meaning as described above.

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, and the polymer complex compound of the present invention is at an arbitrary position that does not bind to M of Ar Having one or more bonds that bind to the polymer chain.
The number of bonds is usually 2 when the metal complex structure is contained in the polymer main chain, and is usually 1 when it is present in the side chain or the terminal.

  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 (16), 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 (16), 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 that forms a 5-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 (16-1).

In the formula, R _{72 to} R ₇₉ 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 _{72 to} R ₇₉ is a bond with a polymer chain.

  In the formula, L is a hydrogen atom, alkyl group, aryl group, heterocyclic ligand, acyloxy 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. m2 represents an integer of 1 to 5. o2 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 an acyloxy 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.

Examples of the metal complex structure that emits light from the triplet excited state include residues obtained by removing the number of hydrogen atoms according to the number of bonds from the ligand to the polymer chain of the triplet light-emitting complex compound,
Specifically, residues obtained by removing R of a number corresponding to the number of bonds to the polymer chain from each of the specific examples of the triplet light-emitting complex represented by the structural formula are given.

  As described above, the metal complex structure showing light emission from the triplet excited state may be contained in the polymer main chain, may be present in the side chain, or may be present at the terminal.

As a case where the main chain contains a metal complex structure that emits light from a triplet excited state, for example, the remaining bond from which two hydrogen atoms are eliminated from the ligand of the triplet light emitting complex A structural unit having two structural units (specifically, a structural unit that is a residue obtained by removing two Rs from each of the specific examples of the triplet light-emitting complex represented by the above structural formula) is preferably included as a repeating unit. A high molecular compound is mentioned.
Examples of such structural units include the following.

  When at least one of the ligands contained in the metal complex structure of the polymer compound of the present invention contains the same structure as the repeating unit contained in the polymer main chain, the metal content in the polymer compound is controlled. It is preferable in that it can be performed. For example, it is preferable in that complexation is performed after the polymer compound is produced, and the metal content in the polymer compound can be controlled by changing the amount of metal used. Specifically, the following structures are exemplified.

As an example in which a metal complex structure that emits light from a triplet excited state is present in the side chain, a group having one bond from which one hydrogen is removed from the ligand of the triplet light emitting complex. , (Specifically, a residue obtained by removing one R from each of the specific examples of the triplet light-emitting complex represented by the above structural formula) is a direct bond such as a single bond or a double bond; an oxygen atom And a bond via an atom such as a sulfur atom or a selenium atom; or a bond via a divalent linking group such as a methylene group, an alkylene group or an arylene group.
Among these, it is preferable to have a structure conjugated with a metal complex structure that emits light from a triplet excited state of a side chain, such as a single bond, a double bond, or an arylene group.

As the structural unit (repeating unit) having such a side chain, for example, a substituent of Ar ₁ or Ar ₄ of the repeating unit selected from the above formulas (2) and (4), or X ₂ in the formula (4) In which R ₁₅ and R ₁₆ are monovalent groups having a metal complex structure that emits light from a triplet excited state.
Specifically, the following structural units are exemplified.

式中、Ｒは前記と同じ定義である。

In the formula, R is as defined above.

  In the case where a metal complex structure that emits light from a triplet excited state is present at the end of the polymer main chain, the remaining bond from which one hydrogen is eliminated from the ligand of the triplet light-emitting complex (Specifically, a residue obtained by removing one R from each of the specific examples of the triplet light-emitting complex represented by the above structural formula). Specifically, the following groups include Illustrated.

  The polymer complex compound of the present invention includes, for example, a repeating unit represented by the formula (1), a repeating unit represented by the formula (12) or (13), and a metal complex structure that emits light from a triplet excited state. In addition, a repeating unit selected from the above (2) and (4) may be included.

When the polymer complex compound of the present invention contains a repeating unit selected from the above (2) and (4), the repeating unit selected from the general formula (1) and the above (2) and (4), and triplet excitation The number of repeating units having a metal complex structure that emits light from a triplet excited state is 0.01 mol% or more and 10 mol based on the total of the structural units (repeating units) having a metal complex structure that emits light from the state. % Or less is preferable.
Further, the repeating unit represented by the general formula (1) is preferably 10 mol% or more and 98% or less, and the repeating unit represented by the general formula (12) or (13) is preferably 2% or more and 90% or less.
Among the polymer complex compounds of the present invention, those that are conjugated polymer compounds are preferred.

  The polymer complex compound of the present invention may have two or more metal complex structures that emit light from a triplet excited state. That is, the polymer complex compound of the present invention may have a metal complex structure that emits light from a triplet excited state in any two or more of its main chain, side chain, and terminal. Each metal complex structure may have the same metal as each other or different metals. Moreover, each metal complex structure may have mutually different luminescent color. For example, a case where both a metal complex structure that emits green light and a metal complex structure that emits red light are included in one polymer complex compound is exemplified. At this time, it is preferable to design so as to include an appropriate amount of the metal complex structure because the emission color can be controlled.

  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 examples thereof include a structure in which an aryl group or a heterocyclic group is bonded via a carbon-carbon bond. Specific examples include substituents described in Chemical formula 10 of JP-A-9-45478.

  The polymer complex compound of the present invention may be a random, block or graft copolymer, or a polymer having an intermediate structure thereof, for example, a random copolymer having a block property. Also good. From the viewpoint of obtaining a polymer compound having a high 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.

The polymer complex compound of the present invention preferably has a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ .

Next, the polymer light emitting device (polymer LED) of the present invention will be described. A layer containing the composition of the present invention or the polymer complex compound of the present invention is provided between electrodes composed of an anode and a cathode.
The layer containing the composition of the present invention or the polymer complex compound of the present invention is preferably a light emitting layer.

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 addition, a polymer LED having a layer containing a conductive polymer adjacent to the electrode between the at least one electrode and the light emitting layer; adjacent to the electrode between the at least one electrode and the light emitting layer Polymer LED provided with a buffer layer having an average film thickness of 2 nm or less.

Specifically, the following structures a) to d) are 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).

  In addition, in order to improve adhesion with the electrode or improve 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. In order to improve or prevent mixing, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.

  Further, a hole blocking layer may be inserted at the interface with the light emitting layer in order to transport electrons and confine holes.

  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 material of the electrode and 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 transporting 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 / film 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 / thickness 2nm or less of the insulating layer / cathode ab) anode / thickness 2nm or less of the insulating layer / hole transport layer / light emitting layer / electron transporting layer / thickness 2nm or less of the insulating layer / cathode

  The hole blocking layer has a function of transporting electrons and confining holes transported from the anode, and is provided at an interface on the cathode side of the light emitting layer, and has an ionization potential larger than the ionization potential of the light emitting layer. For example, a metal complex of bathocuproine, 8-hydroxyquinoline or a derivative thereof.

  The film thickness of the hole blocking layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.

Specifically, for example, the following structures ac) to an) are mentioned.
ac) anode / charge injection layer / light emitting layer / hole blocking layer / cathode ad) anode / light emitting layer / hole blocking layer / charge injection layer / cathode ae) anode / charge injection layer / light emitting layer / hole blocking layer / Charge injection layer / cathode af) anode / charge injection layer / hole transport layer / light emitting layer / hole blocking layer / cathode ag) anode / hole transport layer / light emitting layer / hole blocking layer / charge injection layer / cathode ah ) Anode / charge injection layer / hole transport layer / light emitting layer / hole blocking layer / charge injection layer / cathode ai) anode / charge injection layer / light emitting layer / hole blocking layer / charge transport layer / cathode aj) anode / Light emitting layer / hole blocking layer / electron transport layer / charge injection layer / cathode ak) anode / charge injection layer / light emitting layer / hole blocking layer / electron transport layer / charge injection layer / cathode al) anode / charge injection layer / Hole transport layer / light emitting layer / hole blocking layer / charge transport layer / cathode am) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer Charge injection layer / cathode an) anode / charge injection layer / hole transport layer / luminescent layer / hole blocking layer / electron transport layer / charge injection layer / cathode

  When forming a polymer LED by using the complex composition and the polymer complex compound of the present invention to form a film from a solution, it is only necessary to remove the solvent by drying after applying the solution, and charge transporting material. The same technique can be applied even when a light emitting material is mixed, and it is very advantageous in manufacturing. 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.

  As the film thickness of the light emitting layer, the optimum value varies depending on the material to be used, and it may be selected so that the drive voltage and the light emission efficiency are appropriate values. For example, the thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm. More preferably, it is 5 nm-200 nm.

  In the polymer LED of the present invention, a light emitting material other than the complex composition and polymer complex compound of the present invention 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 present invention may be laminated with a light emitting layer containing the complex composition or polymer complex compound of the present invention.

  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.

  Specifically, for example, known ones such as those described in JP-A-57-51781 and 59-194393 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 for forming the polymer LED of the present invention may be any substrate as long as it forms an electrode and does not change when each layer of the polymer LED is formed. Examples thereof include glass, plastic, polymer film, and silicon substrate. Is done. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

Usually, it is preferable that at least one of the electrodes composed of an anode and a cathode is transparent or translucent, and the anode side is transparent or translucent.
As the material of 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 electric conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, 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 of 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 of these alloys, or an alloy of 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 thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, but 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, metal fluoride, 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 layer. A protective layer for protecting the polymer LED may be attached. In order to use the polymer LED stably for a long period of time, it is preferable to attach a protective layer and / or 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. 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. 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.

  The polymer light emitting device of the present invention can be used for a backlight of a planar light source, a segment display device, a dot matrix display device or 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 material layer of a non-light-emitting portion is formed extremely thick and substantially non- There are a method of emitting light and a method of forming either one of the anode or the cathode or both electrodes 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 multi-color 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 light emission conversion filter. The dot matrix element can be driven passively, or can be actively driven in combination with a TFT or the like. 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 will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
The number average molecular weight in terms of polystyrene was determined by gel permeation chromatography (GPC: HLC-8220GPC, manufactured by Tosoh Corporation or SCL-10A, manufactured by Shimadzu Corporation) using tetrahydrofuran as a solvent.
Column: TOSOH TSKgel SuperHM-H (2) + TSKgel SuperH2000 (4.6mm Id x 15cm), Detector: RI (SHIMADZU RID-10A) is used. The mobile phase was chloroform or tetrahydrofuran (THF).

化合物Ａ
不活性雰囲気下１ｌの三つ口フラスコにベンゾフラン(23.2ｇ、137.9mmol)と酢酸(232ｇ)を入れ、室温で撹拌、溶かした後、７５℃まで昇温した。昇温後、臭素(92.6ｇ、579.3mmol)を酢酸(54ｇ)で希釈したものを滴下した。滴下終了後、温度を保持したまま３時間撹拌し、放冷した。ＴＬＣで原料の消失を確認した後、チオ硫酸ナトリウム水を加え反応を終了させ、室温で１時間撹拌した。撹拌後、ろ過を行いケーキをろ別し、さらにチオ硫酸ナトリウム水、水で洗浄した後、乾燥した。得られた粗生成物をヘキサンにて再結晶し、目的物を得た。（収量：21.8ｇ、収率：49％）
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ７．４４（ｄ、２Ｈ）、７．５７（ｄ、２Ｈ）、８．０３（ｓ、２Ｈ） Synthesis Example 1 (Synthesis of Compound A)

Compound A
Benzofuran (23.2 g, 137.9 mmol) and acetic acid (232 g) were placed in a 1 l three-necked flask under an inert atmosphere, stirred and dissolved at room temperature, and then heated to 75 ° C. After raising the temperature, bromine (92.6 g, 579.3 mmol) diluted with acetic acid (54 g) was added dropwise. After completion of the dropwise addition, the mixture was stirred for 3 hours while maintaining the temperature and allowed to cool. After confirming disappearance of the raw material by TLC, sodium thiosulfate water was added to terminate the reaction, and the mixture was stirred at room temperature for 1 hour. After stirring, the mixture was filtered to separate the cake, further washed with aqueous sodium thiosulfate and water, and dried. The obtained crude product was recrystallized from hexane to obtain the desired product. (Yield: 21.8 g, Yield: 49%)
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 7.44 (d, 2H), 7.57 (d, 2H), 8.03 (s, 2H)

化合物Ｂ
不活性雰囲気下で５００ｍｌの四つ口フラスコに化合物Ａ(16.6ｇ、50.9mmol)とテトラヒドロフラン(293ｇ)を入れ、−７８℃まで冷却した。ｎ−ブチルリチウム(80ml<1.6モルヘキサン溶液>、127.3mmol)を滴下した後、温度を保持したまま１時間撹拌した。この反応液を、不活性雰囲気下で１０００ｍｌの四つ口フラスコにトリメトキシボロン酸(31.7ｇ、305.5mmol)とテトラヒドロフラン(250ml)を入れ、−７８℃まで冷却したものに滴下した。滴下終了後、ゆっくり室温まで戻し、２時間室温で撹拌後、ＴＬＣで原料の消失を確認した。反応終了マスを、２０００ｍｌビーカーに濃硫酸(30g)と水(600ml)をいれたものに、注入し、反応を終了させた。トルエン(300ml)を加え、有機層を抽出し、さらに水を加えて洗浄した。溶媒を留去後、そのうち８ｇと酢酸エチル(160ml)を３００ｍｌの四つ口フラスコにいれ、つづいて３０％過酸化水素水(7.09g)を加え、４０℃で２時間撹拌した。この反応液を、１０００ｍｌのビーカーに硫酸アンモニウム鉄（II）(71g)と水(500ml)の水溶液に注入した。撹拌後、有機層を抽出し、有機層を水で洗浄した。溶媒を除去することにより、化合物Ｂ粗製物６．７２ｇを得た。
ＭＳスペクトル：Ｍ⁺ 200.0
Synthesis Example 2 (Synthesis of Compound B)

Compound B
Compound A (16.6 g, 50.9 mmol) and tetrahydrofuran (293 g) were placed in a 500 ml four-necked flask under an inert atmosphere and cooled to -78 ° C. After dropwise addition of n-butyllithium (80 ml <1.6 mol hexane solution>, 127.3 mmol), the mixture was stirred for 1 hour while maintaining the temperature. The reaction solution was added dropwise to a 1000 ml four-necked flask in an inert atmosphere with trimethoxyboronic acid (31.7 g, 305.5 mmol) and tetrahydrofuran (250 ml) cooled to -78 ° C. After completion of the dropwise addition, the temperature was slowly returned to room temperature, and after stirring for 2 hours at room temperature, disappearance of the raw material was confirmed by TLC. The reaction completed mass was poured into a 2000 ml beaker containing concentrated sulfuric acid (30 g) and water (600 ml) to complete the reaction. Toluene (300 ml) was added, the organic layer was extracted, and further washed with water. After distilling off the solvent, 8 g of the mixture and ethyl acetate (160 ml) were placed in a 300 ml four-necked flask, followed by addition of 30% aqueous hydrogen peroxide (7.09 g) and stirring at 40 ° C. for 2 hours. This reaction solution was poured into an aqueous solution of iron (II) ammonium sulfate (71 g) and water (500 ml) in a 1000 ml beaker. After stirring, the organic layer was extracted, and the organic layer was washed with water. By removing the solvent, 6.72 g of Compound B crude product was obtained.
MS spectrum: M ⁺ 200.0

化合物Ｃ
不活性雰囲気下で２００ｍｌの四つ口フラスコに合成例２と同様の方法で合成した化合物Ｂ(2.28ｇ、11.4mmol)とＮ，Ｎ−ジメチルホルムアミド(23ｇ)を入れ、室温で撹拌、溶かした後、炭酸カリウム(9.45ｇ、68.3mmol) を入れ６０℃まで昇温した。昇温後、臭化ｎ−オクチル(6.60ｇ、34.2mmol)をＮ，Ｎ−ジメチルホルムアミド(11ｇ)で希釈したものを滴下した。滴下終了後、６０℃まで昇温し、温度を保持したまま２時間撹拌し、ＴＬＣで原料の消失を確認した。水(20ml)を加え反応を終了させ、つづいてトルエン(20ml)を加え、有機層を抽出し、有機層を水で２回洗浄した。無水硫酸ナトリウムで乾燥後、溶媒留去した。得られた粗生成物をシリカゲルカラムで精製することにより、目的物を得た。（収量：1.84ｇ、収率：38％）
ＭＳスペクトル：Ｍ⁺ 425.3
Synthesis Example 3 (Synthesis of Compound C)

Compound C
Compound B (2.28 g, 11.4 mmol) and N, N-dimethylformamide (23 g) synthesized in the same manner as in Synthesis Example 2 were placed in a 200 ml four-necked flask under an inert atmosphere, and stirred and dissolved at room temperature. Thereafter, potassium carbonate (9.45 g, 68.3 mmol) was added and the temperature was raised to 60 ° C. After heating, n-octyl bromide (6.60 g, 34.2 mmol) diluted with N, N-dimethylformamide (11 g) was added dropwise. After completion of the dropwise addition, the temperature was raised to 60 ° C., the mixture was stirred for 2 hours while maintaining the temperature, and disappearance of the raw material was confirmed by TLC. Water (20 ml) was added to terminate the reaction, followed by addition of toluene (20 ml) to extract the organic layer, and the organic layer was washed twice with water. After drying over anhydrous sodium sulfate, the solvent was distilled off. The obtained crude product was purified by a silica gel column to obtain the desired product. (Yield: 1.84 g, Yield: 38%)
MS spectrum: M ⁺ 425.3

化合物Ｄ
不活性雰囲気下５００ｍｌ四つ口フラスコに合成例３と同様の方法で合成した化合物Ｃ(7.50ｇ、17.7mmol)とＮ，Ｎ−ジメチルホルムアミドを入れ、室温で撹拌、溶かした後、氷浴で冷却した。冷却後、Ｎ−ブロモスクシンイミド(6.38ｇ、35.9mmol)をＮ，Ｎ−ジメチルホルムアミド(225ml)で希釈したものを滴下した。滴下終了後、氷浴で１時間、室温で１８．５時間、４０℃まで昇温し、温度を保持したまま６．５時間撹拌し、液体クロマトグラフィーで原料の消失を確認した。溶媒を除去し、トルエン(75ml)を加え溶解した後、有機層を水で３回洗浄した。無水硫酸ナトリウムで乾燥後、溶媒留去した。得られた粗生成物の約半量をシリカゲルカラムおよび液体クロマトグラフィー分取で精製することにより、目的物を得た。（収量：0.326ｇ）
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９０（ｔ、６Ｈ）、１．２６〜１．９５（ｍ、２４Ｈ）、４．１１（ｔ、４Ｈ）、７．３４（ｓ、２Ｈ）、７．７４（ｓ、２Ｈ）
ＭＳスペクトル：Ｍ⁺ 582.1 Synthesis Example 4 (Synthesis of Compound D)

Compound D
Compound C (7.50 g, 17.7 mmol) and N, N-dimethylformamide synthesized in the same manner as in Synthesis Example 3 were placed in a 500 ml four-necked flask under an inert atmosphere, stirred and dissolved at room temperature, and then in an ice bath. Cooled down. After cooling, a solution prepared by diluting N-bromosuccinimide (6.38 g, 35.9 mmol) with N, N-dimethylformamide (225 ml) was added dropwise. After completion of the dropwise addition, the mixture was heated to 40 ° C. for 1 hour in an ice bath, 18.5 hours at room temperature, stirred for 6.5 hours while maintaining the temperature, and disappearance of the raw materials was confirmed by liquid chromatography. The solvent was removed, toluene (75 ml) was added and dissolved, and the organic layer was washed 3 times with water. After drying over anhydrous sodium sulfate, the solvent was distilled off. About half of the resulting crude product was purified by silica gel column and liquid chromatography fractionation to obtain the desired product. (Yield: 0.326g)
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 6H), 1.26 to 1.95 (m, 24H), 4.11 (t, 4H), 7.34 (s, 2H), 7.74 (s, 2H)
MS spectrum: M ⁺ 582.1

Synthesis Example 5 <Synthesis of Polymer Compound 1-1>
6.26 g of compound D and 4.7 g of 2,2′-bipyridyl were charged into the reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. To this, 350 g of tetrahydrofuran (THF) (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, 8.3 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) 2} was added to this mixed solution, stirred at room temperature for 10 minutes, and then reacted at 60 ° C. for 3 hours. . The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled and then poured into a mixed solution of 25% aqueous ammonia 40 ml / methanol 200 ml / ion-exchanged water 200 ml and stirred for about 1 hour. Next, the produced precipitate was recovered by filtration. This precipitate was dried under reduced pressure and then dissolved in 600 g of toluene. The solution was filtered to remove insoluble matters, and then the solution was purified by passing through a column filled with alumina. Next, this solution was washed with 1N hydrochloric acid. After separation, the toluene phase was washed with about 3% aqueous ammonia. After separation, the toluene phase was washed with ion exchange water. After separation, the toluene solution was recovered. Next, methanol was poured into this toluene solution with stirring, and reprecipitation purification was performed. After the produced precipitate was recovered, this precipitate was washed with methanol. This precipitate was dried under reduced pressure to obtain 2.6 g of a polymer.
The number average molecular weight in terms of polystyrene of this polymer was Mn = 1.1 × 10 ⁵ , and the weight average molecular weight in terms of polystyrene was Mw = 2.7 × 10 ⁵ .

Polymer Compound 1-1 A polymer consisting essentially of the following repeating units

Example 1
A 0.8 wt% chloroform solution of a mixture obtained by adding 5 wt% of iridium complex A (manufactured by American Dice Source) to the polymer compound 1-1 was prepared.

Iridium complex A

A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is used to form a film with a thickness of 50 nm by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Bayer, BaytronP). Dried on plate for 10 minutes at 200 ° C. Next, a film was formed at a rotational speed of 2500 rpm by spin coating using the prepared chloroform solution. The film thickness was about 100 nm. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then LiF was deposited as a cathode buffer layer at about 4 nm, calcium was deposited as a cathode at about 5 nm, and then aluminum was deposited at about 80 nm to produce an EL device. After the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started. By applying a voltage to the obtained device, EL light emission having a peak at 520 nm was obtained. The device showed light emission of 100 cd / m ² at about 16V. The maximum luminous efficiency was 4.5 cd / A.

化合物Ｅ
不活性雰囲気下１ｌの四つ口フラスコに２，８−ジブロモジベンゾチオフェン ７ｇとＴＨＦ ２８０ｍｌを入れ、室温で撹拌、溶かした後、−７８℃まで冷却した。ｎ−ブチルリチウム ２９ｍｌ（１．６モルヘキサン溶液）を滴下した。滴下終了後、温度を保持したまま２時間撹拌し、トリメトキシボロン酸 １３ｇを滴下した。滴下終了後、ゆっくり室温まで戻した。３時間室温で撹拌後、ＴＬＣで原料の消失を確認した。５％硫酸 １００ｍｌを加えて反応を終了させ、室温で１２時間撹拌した。水を加えて洗浄し、有機層を分液した。溶媒を酢酸エチルに置換した後、３０％過酸化水素水 ５ｍｌを加え、４０℃で５時間撹拌した。その後有機層を分液し、１０％硫酸アンモニウム鉄（II）水溶液で洗浄後乾燥、溶媒を留去することにより、茶色の固体 ４．４３ｇを得た。ＬＣ−ＭＳ測定からは二量体などの副生成物も生成しており、化合物Ｅの純度は７７％であった（ＬＣ面百）。
ＭＳ（ＡＰＣＩ（−））：（Ｍ−Ｈ）^- ２１５ Synthesis Example 6 (Synthesis of Compound E)

Compound E
Under an inert atmosphere, 7 g of 2,8-dibromodibenzothiophene and 280 ml of THF were placed in a 1 l four-necked flask, stirred and dissolved at room temperature, and then cooled to -78 ° C. 29 ml of n-butyllithium (1.6 molar hexane solution) was added dropwise. After completion of dropping, the mixture was stirred for 2 hours while maintaining the temperature, and 13 g of trimethoxyboronic acid was added dropwise. After completion of dropping, the temperature was slowly returned to room temperature. After stirring at room temperature for 3 hours, disappearance of the raw material was confirmed by TLC. The reaction was terminated by adding 100 ml of 5% sulfuric acid and stirred at room temperature for 12 hours. Water was added for washing, and the organic layer was separated. After replacing the solvent with ethyl acetate, 5 ml of 30% aqueous hydrogen peroxide was added and stirred at 40 ° C. for 5 hours. Thereafter, the organic layer was separated, washed with a 10% aqueous ammonium iron (II) sulfate solution, dried, and the solvent was distilled off to obtain 4.43 g of a brown solid. By-products such as dimers were also produced from LC-MS measurement, and the purity of Compound E was 77% (LC area percentage).
MS (APCI (-)) :( M-H) - 215

化合物Ｆ
不活性雰囲気下で２００ｍｌの三つ口フラスコに化合物Ｅ ４．４３ｇと臭化ｎ−オクチル ２５．１ｇ、および炭酸カリウム １２．５ｇ（２３．５ｍｍｏｌ）を入れ、溶媒としてメチルイソブチルケトン ５０ｍｌを加えて１２５℃で６時間加熱還流した。反応終了後、溶媒を留去、クロロホルムと水を加えて、有機層を分液し、さらに水で２回洗浄した。無水硫酸ナトリウムで乾燥後、シリカゲルカラム（展開溶媒：トルエン／シクロヘキサン＝１／１０）で精製することにより、８．４９ｇ（ＬＣ面百９７％、収率９４％）の化合物Ｆを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９１（ｔ、６Ｈ）、１．３１〜１．９０（ｍ、２４Ｈ）、４．０８（ｔ、４Ｈ）、７．０７（ｄｄ、２Ｈ）、７．５５（ｄ、２Ｈ）、７．６８（ｄ、２Ｈ） Synthesis Example 7 (Synthesis of Compound F)

Compound F
Under an inert atmosphere, 4.43 g of compound E, 25.1 g of n-octyl bromide, and 12.5 g (23.5 mmol) of potassium carbonate were placed in a 200 ml three-necked flask, and 50 ml of methyl isobutyl ketone was added as a solvent. The mixture was heated to reflux at 125 ° C. for 6 hours. After completion of the reaction, the solvent was distilled off, chloroform and water were added, the organic layer was separated, and further washed twice with water. After drying over anhydrous sodium sulfate, purification was performed with a silica gel column (developing solvent: toluene / cyclohexane = 1/10) to obtain 8.49 g (LC area percentage 97%, yield 94%) of Compound F.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.91 (t, 6H), 1.31-1.90 (m, 24H), 4.08 (t, 4H), 7.07 (dd, 2H), 7.55 (d, 2H), 7 .68 (d, 2H)

化合物Ｇ Synthesis Example 8 (Synthesis of Compound G)

Compound G

A 100 ml three-necked flask was charged with 6.67 g of compound F and 40 ml of acetic acid, and the temperature was raised to 140 ° C. in an oil bath. Subsequently, 13 ml of 30% aqueous hydrogen peroxide was added from the condenser, and after vigorously stirring for 1 hour, the reaction was terminated by pouring into 180 ml of cold water. After extraction with chloroform and drying, the solvent was distilled off to obtain 6.96 g (LC area percentage 90%, yield 97%) of Compound G.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 6H), 1.26 to 1.87 (m, 24H), 4.06 (t, 4H), 7.19 (dd, 2H), 7.69 (d, 2H), 7 .84 (d, 2H)
MS (APCI (+)): (M + H) ^<+> 473

化合物Ｈ
不活性雰囲気下２００ｍｌ四つ口フラスコに化合物Ｇ ３．９６ｇと酢酸／クロロホルム＝１：１混合液 １５ｍｌを加え、７０℃で撹拌し、溶解させた。続いて、臭素 ６．０２ｇを上記の溶媒 ３ｍｌに溶かして加え、３時間撹拌した。チオ硫酸ナトリウム水溶液を加えて未反応の臭素を除き、クロロホルムと水を加えて、有機層を分液し乾燥した。溶媒を留去し、シリカゲルカラム（展開溶媒：クロロホルム／ヘキサン＝１／４）で精製することにより、４．４６ｇ（ＬＣ面百９８％、収率８４％）の化合物Ｈを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９５（ｔ、６Ｈ）、１．３０〜１．９９（ｍ、２４Ｈ）、４．１９（ｔ、４Ｈ）、７．０４（ｓ、２Ｈ）、７．８９（ｓ、２Ｈ）
ＭＳ（ＦＤ⁺）Ｍ^＋ ６３０ Synthesis Example 9 (Synthesis of Compound H)

Compound H
Under an inert atmosphere, 3.96 g of Compound G and 15 ml of a mixed solution of acetic acid / chloroform = 1: 1 were added to a 200 ml four-necked flask and stirred at 70 ° C. to dissolve. Subsequently, 6.02 g of bromine was dissolved in 3 ml of the above solvent, and the mixture was stirred for 3 hours. A sodium thiosulfate aqueous solution was added to remove unreacted bromine, chloroform and water were added, and the organic layer was separated and dried. The solvent was distilled off and purified by a silica gel column (developing solvent: chloroform / hexane = 1/4) to obtain 4.46 g (LC area percentage 98%, yield 84%) of Compound H.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.95 (t, 6H), 1.30 to 1.99 (m, 24H), 4.19 (t, 4H), 7.04 (s, 2H), 7.89 (s, 2H)
MS (FD ⁺ ) M ⁺ 630

化合物Ｊ
不活性雰囲気下２００ｍｌ三つ口フラスコに化合物Ｈ ３．９ｇとジエチルエーテル ５０ｍｌを入れ、４０℃まで昇温、撹拌した。水素化アルミニウムリチウム １．１７ｇを少量ずつ加え、５時間反応させた。水を少量ずつ加えることによって過剰な水素化アルミニウムリチウムを分解し、３６％塩酸 ５．７ｍｌで洗浄した。クロロホルム、水を加えて、有機層を分液し乾燥した。シリカゲルカラム（展開溶媒：クロロホルム／ヘキサン＝１／５）で精製することにより、１．８ｇ（ＬＣ面百９９％、収率４９％）の化合物Ｊを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９０（ｔ、６Ｈ）、１．２６〜１．９７（ｍ、２４Ｈ）、４．１５（ｔ、４Ｈ）、７．４５（ｓ、２Ｈ）、７．９４（ｓ、２Ｈ）
ＭＳ（ＦＤ^＋）Ｍ^＋ ５９８ Synthesis Example 10 (Synthesis of Compound J)

Compound J
Under an inert atmosphere, 3.9 g of Compound H and 50 ml of diethyl ether were placed in a 200 ml three-necked flask, heated to 40 ° C. and stirred. Lithium aluminum hydride 1.17 g was added little by little and allowed to react for 5 hours. Excess lithium aluminum hydride was decomposed by adding water little by little and washed with 5.7 ml of 36% hydrochloric acid. Chloroform and water were added, and the organic layer was separated and dried. By purification with a silica gel column (developing solvent: chloroform / hexane = 1/5), 1.8 g (LC area percentage 99%, yield 49%) of Compound J was obtained.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 6H), 1.26 to 1.97 (m, 24H), 4.15 (t, 4H), 7.45 (s, 2H), 7.94 (s, 2H)
MS (FD ⁺ ) M ⁺ 598

According to the MS (APCI (+)) method, peaks were detected at 615 and 598.

Synthesis Example 11 (Synthesis of polymer compound 1-2)
After dissolving 400 mg of Compound J and 180 mg of 2,2′-bipyridyl in 20 mL of dehydrated tetrahydrofuran, this solution was added to bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) under a nitrogen atmosphere. ₂ } 320 mg was added, and the temperature was raised to 60 ° C. and reacted for 3 hours. After the reaction, this reaction solution was cooled to room temperature, dropped into a mixed solution of 25% aqueous ammonia 10 ml / methanol 120 ml / ion exchanged water 50 ml and stirred for 30 minutes, and then the deposited precipitate was filtered and dried under reduced pressure for 2 hours. And dissolved in 30 ml of toluene. After adding 30 mL of 1N hydrochloric acid and stirring for 3 hours, the aqueous layer was removed, and 30 mL of 4% aqueous ammonia was added to the organic layer and stirred for 3 hours, and then the aqueous layer was removed. The organic layer was dropped into 150 mL of methanol and stirred for 30 minutes, the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 30 mL of toluene. Then, it refine | purified through the alumina column (alumina amount 20g), the collect | recovered toluene solution was dripped at methanol 100mL, and it stirred for 30 minutes, and deposited precipitation. The deposited precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained polymer compound 1-2 was 120 mg.
The number average molecular weight in terms of polystyrene of the polymer compound 1-2 was Mn = 1.3 × 10 ⁵ , and the weight average molecular weight was Mw = 2.8 × 10 ⁵ .

Polymer Compound 1-2 A polymer consisting essentially of the following repeating units

Example 2
A device was produced in the same manner as in Example 1 except that the polymer compound 1-2 was used instead of the polymer compound 1-1. The spin coater rotation speed during film formation was 2000 rpm, and the film thickness was about 160 nm. By applying voltage to the resulting device, EL light emission having a peak at 520 nm was obtained. The device showed light emission of 100 cd / m ² at about 29V. The maximum luminous efficiency was 3.1 cd / A.

Example 3
A 0.8 wt% chloroform solution of a mixture obtained by adding 5 wt% of iridium complex B to the polymer compound 1-1 was prepared. Using this, a device was fabricated in the same manner as in Example 1. The spin coater rotation speed at the time of film formation was 2500 rpm, and the film thickness was about 100 nm. By applying voltage to the resulting device, EL light emission having a peak at 620 nm was obtained. The device showed light emission of 100 cd / m ² at about 18V. The maximum luminous efficiency was 1.6 cd / A.

Iridium complex B

Comparative Example 1
The polymer compound R1 (polystyrene equivalent number average molecular weight is Mn = 8.0 × 10 ⁴ , weight average molecular weight is Mw = 3.0 × 10 ⁵ ), and a mixture obtained by adding 5 wt% of iridium complex A to the polymer compound R1. A 6% chloroform solution was prepared, and a device was produced in the same manner as in Example 1. The spin coater rotation speed at the time of film formation was 2600 rpm, and the film thickness was about 90 nm. When voltage was applied to the resulting device, EL light emission having a peak at 508 nm was obtained, but the maximum light emission efficiency of the device was as low as 0.12 cd / A.
The polymer compound R1 was synthesized by the method described in US6512083.

Polymer compound R1: Homopolymer substantially consisting of the following repeating units

Synthesis Example 12 (Synthesis of polymer compound 1-3)
After dissolving 419 mg of Compound J, 146 mg of Compound K, 310 mg of 2,2′-bipyridyl in 28 mL of dehydrated tetrahydrofuran, this solution was added to bis (1,5-cyclooctadiene) nickel (0) {Ni under a nitrogen atmosphere. (COD) ₂ } 550 mg was added, and the temperature was raised to 60 ° C. and reacted for 3 hours. After the reaction, this reaction solution was cooled to room temperature, dropped into a mixed solution of 25% ammonia water 13 ml / methanol 150 ml / ion exchanged water 75 ml and stirred for 30 minutes, and then the deposited precipitate was filtered and dried under reduced pressure for 2 hours. And dissolved in 40 ml of toluene. After adding 40 mL of 1N hydrochloric acid and stirring for 3 hours, the aqueous layer was removed, 40 mL of 4% aqueous ammonia was added to the organic layer, and the mixture was stirred for 3 hours, and then the aqueous layer was removed. The organic layer was dropped into 200 mL of methanol and stirred for 30 minutes, the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 40 mL of toluene. Then, it refine | purified through the alumina column (alumina amount 10g), The collect | recovered toluene solution was dripped at methanol 200mL, and was stirred for 30 minutes. The obtained methanol suspension was concentrated under reduced pressure to about 20 ml, and 30 ml of methanol was added thereto and stirred to precipitate a precipitate. The deposited precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained polymer compound 1-3 was 190 mg.
The number average molecular weight in terms of polystyrene of the polymer compound 1-3 was Mn = 4.5 × 10 ⁴ , and the weight average molecular weight was Mw = 2.0 × 10 ⁵ .

Compound K

Polymer Compound 1-3 A polymer consisting essentially of the following repeating units

Example 4
A device was fabricated in the same manner as in Example 1 except that the following polymer compound 1-3 was used instead of the polymer compound 1-1. A film having a thickness of 50 nm is formed by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Bayer, Baytron P). A 0.8 wt% chloroform solution of a mixture obtained by adding 5 wt% of iridium complex A to polymer compound 1-3 was prepared, and a film was formed at a rotational speed of 1600 rpm by a spin coater. Aluminum was deposited by about 50 nm. By applying voltage to the resulting device, EL light emission having a peak at 516 nm was obtained. The device showed light emission of 100 cd / m ² at about 7.9V. The maximum luminous efficiency was 8.3 cd / A.

Comparative Example 2
A device was prepared in the same manner as in the above example except that the iridium complex A was not added to the polymer compound 1-3. By applying voltage to the resulting device, EL light emission having a peak at 436 nm was obtained. The device showed light emission of 100 cd / m ² at about 7.4V. The maximum luminous efficiency was 0.37 cd / A.

Synthesis Example 13 (Polymer Compound 1-4)
6.45 g of compound J, 2.07 g of compound L, and 5.5 g of 2,2′-bipyridyl were charged into the reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. To this, 400 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, 10.0 g of bis (1,5-cyclooctadiene) nickel (0) was added to the mixed solution, and the mixture was stirred at room temperature for 10 minutes and then reacted at 60 ° C. for 3 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled, and then a mixed solution of 25% aqueous ammonia 100 ml / methanol 200 ml / ion-exchanged water 200 ml was poured and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. This solution was filtered to remove insoluble matters, and then this toluene solution was washed with 1N hydrochloric acid, and then the liquid separation and the toluene solution were recovered. Next, this toluene solution was washed with about 3% aqueous ammonia, and then a liquid separation and a toluene solution were recovered. Next, this toluene solution was washed with ion-exchanged water, and then a liquid separation and a toluene solution were recovered. The toluene solution was purified by reprecipitation by adding methanol with stirring.
Next, the produced precipitate was recovered, and this precipitate was dried under reduced pressure to obtain 4.0 g of a polymer. This polymer is called a polymer compound. The obtained polymer compound had a polystyrene-reduced weight average molecular weight of 3.9 × 10 ⁵ and a number average molecular weight of 4.3 × 10 ⁴ .

Compound L

Polymer Compound 1-4 Copolymer made substantially of the following repeating units

Example 5
A device was prepared in the same manner as in Example 3 except that the polymer compound 1-4 was used instead of the polymer compound 1-1. The spin coater rotation speed at the time of film formation was 4000 rpm, and the film thickness was about 100 nm. By applying voltage to the resulting device, EL light emission having a peak at 620 nm was obtained. The device showed light emission of 100 cd / m ² at about 7.2V. The maximum luminous efficiency was 0.7 cd / A.

Comparative Example 3
A device was prepared in the same manner as in the above example except that the iridium complex B was not added to the polymer compound 1-4. By applying voltage to the resulting device, EL light emission having a peak at 452 nm was obtained. The device showed light emission of 100 cd / m ² at about 7.7 V, and the maximum light emission efficiency was 0.5 cd / A.

Synthesis Example 14 (Polymer Compound 1-5)
0.61 g of Compound D, 0.22 g of Compound K, and 0.55 g of 2,2′-bipyridyl were charged into the reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. To this was added 50 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. Next, 1.0 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and the mixture was stirred at room temperature for 10 minutes and then reacted at 60 ° C. for 3 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this solution was cooled, and then a mixed solution of 25% aqueous ammonia 10 ml / methanol 40 ml / ion exchanged water 40 ml was poured and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. The solution was filtered to remove insoluble matters, and then the toluene solution was purified through a column filled with alumina. Next, this toluene solution was poured into methanol for reprecipitation purification.
Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure to obtain 0.4 g of a polymer. This polymer is called a polymer compound. The obtained polymer compound had a polystyrene equivalent weight average molecular weight of 4.6 × 10 ⁴ and a number average molecular weight of 6.5 × 10 ³ .

実施例６
高分子化合物１−１のかわりに、高分子化合物１−５を使う以外は上記実施例１と同様に素子を作製した。製膜時のスピンコーター回転数は１４００ｒｐｍ、膜厚は約９５ｎｍであった。得られた素子に電圧を印加することにより５１６ｎｍにピークを有するＥＬ発光が得られた。該素子は、約８．５Ｖで１００ｃｄ／ｍ^２の発光を示した。また最大発光効率は６．２ｃｄ／Ａであった。
Polymer Compound 1-5 Copolymer made of the following repeating units

Example 6
A device was produced in the same manner as in Example 1 except that the polymer compound 1-5 was used instead of the polymer compound 1-1. The spin coater rotation speed during film formation was 1400 rpm, and the film thickness was about 95 nm. By applying voltage to the resulting device, EL light emission having a peak at 516 nm was obtained. The device showed light emission of 100 cd / m ² at about 8.5V. The maximum luminous efficiency was 6.2 cd / A.

Comparative Example 4
A device was produced in the same manner as in the above example except that the iridium complex A was not added to the polymer compound 1-5. By applying voltage to the resulting device, EL light emission having a peak at 444 nm was obtained. The device showed light emission of 100 cd / m ² at about 6.1 V, and the maximum light emission efficiency was 0.6 cd / A.

Claims (24)

A triplet light-emitting complex having a repeating unit represented by the following general formula ( 1-4 ) and having a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ and a central metal of iridium, platinum or gold A composition comprising a compound.

[In the formula, D ring and E ring are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl. Group, amino group, substituted amino group, silyl group, substituted silyl group, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group and cyano group An aromatic ring which may have a substituent selected from the group consisting of Y represents —O—, —S—, —Si (R ₁ ) (R ₂ ) —, —P (R ₃ ) — or —PR ₄ (═O) —, and R ₁ , R ₂ , R ₃ and R ₄ each independently represents an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted It represents an amino group, a silyl group, a substituted silyl group, a silyloxy group, a substituted silyloxy group or a monovalent heterocyclic group . ] The composition according to claim 1, wherein Y is an O atom or an S atom. The composition according to claim 1 or 2 , wherein the D ring and the E ring are aromatic hydrocarbon rings. The repeating unit represented by the formula (1-4) is a repeating unit selected from the following formulas (1-6), (1-7), (1-8), (1-9) and (1-10) The composition according to claim 3, wherein

[Wherein, R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently an alkyl group, an alkoxy group, an alkylthio group, or an aryl group. , Aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, acyloxy group, imine residue, amide A group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, or a substituted carboxyl group. a and b each independently represent an integer of 0 to 3. c, d, e and f each independently represent an integer of 0 to 5. g, h, i and j each independently represent an integer of 0 to 7. When there are a plurality of R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ , they may be the same or different. Y represents the same meaning as described above. ] The composition according to any one of claims 1 to 4 , wherein the polymer compound further has a repeating unit represented by the following formula (2), formula (3), formula (4), or formula (5). object.
-Ar _1- (2)

—Ar ₄ —X ₂ — (4)
-X _3- (5)

[Wherein, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. X ₁ , X ₂ and X ₃ each independently represent —CR ₁₅ ═CR ₁₆ —, —C≡C—, —N (R ₁₇ ) —, or — (SiR ₁₈ R ₁₉ ) _m —. R ₁₅ and R ₁₆ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. R ₁₇ , R ₁₈ and R ₁₉ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, an arylalkyl group or a substituted amino group. ff represents 1 or 2. m represents an integer of 1 to 12. When there are a plurality of R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ , they may be the same or different. ] The repeating unit represented by the formula (2) is a repeating unit represented by the following formula (6), (7), (8), (9), (10) or (11). Item 6. The composition according to Item 5 .

[Wherein, R ₂₀ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, substituted amino group, a silyl group, a substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group. n represents an integer of 0 to 4. When a plurality of R ₂₀ are present, they may be the same or different. ]

[Wherein R ₂₁ and R ₂₂ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl alkynyl group, an amino group, a substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano Indicates a group. o and p each independently represent an integer of 0 to 3. When a plurality of R ₂₁ and R ₂₂ are present, they may be the same or different. ]

In the formula, R ₂₃ and R ₂₆ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl. group, an amino group, a substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group Indicates. q and r each independently represents an integer of 0 to 4. R ₂₄ and R ₂₅ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. When a plurality of R ₂₃ and R ₂₆ are present, they may be the same or different. ]

[Wherein, R ₂₇ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, substituted amino group, a silyl group, a substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group. s shows the integer of 0-2. Ar ₁₃ and Ar ₁₄ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. ss and tt each independently represent 0 or 1. X ₄ represents O, S, SO, SO ₂ , Se, or Te. When a plurality of R ₂₇ are present, they may be the same or different. ]

Wherein R ₂₈ and R ₂₉ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl alkynyl group, an amino group, a substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano Indicates a group. t and u each independently represents an integer of 0 to 4. X ₅ represents O, S, SO ₂ , Se, Te, N—R ₃₀ , or SiR ₃₁ R ₃₂ . X ₆ and X ₇ each independently represent N or C—R ₃₃ . R ₃₀ , R ₃₁ , R ₃₂ and R ₃₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. When there are a plurality of R ₂₈ , R ₂₉ and R ₃₃ , they may be the same or different. ]

Wherein R ₃₄ and R ₃₉ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl alkynyl group, an amino group, a substituted amino group, silyl group, substituted silyl group, a sill group, an acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano Indicates a group. v and w each independently represent an integer of 0 to 4. R ₃₅ , R ₃₆ , R ₃₇ and R ₃₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. Ar ₅ represents an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. When a plurality of R ₃₄ and R ₃₉ are present, they may be the same or different. ] The composition according to claim 5, wherein the repeating unit represented by the formula (2) is a repeating unit represented by the following formula (12).

[Wherein, Ar ₁₅ and Ar ₁₆ each independently represent a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and R ₄₀ represents an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkyl group, An amino group, an aryl group which may have a substituent or a monovalent heterocyclic group, wherein X is a single bond,

(Wherein R ₄₁ is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl. indicating group, an amino group, a substituted amino group, silyl group, substituted silyl group, a sill group, acyloxy group, imino group, amido group, imido group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group And when there are a plurality of R _{41 s} , they may be the same or different.)] The composition according to claim 7, wherein the polymer compound has a repeating unit represented by the general formula (1-4) and a repeating unit represented by the formula (2). 6. The composition according to claim 5, wherein the repeating unit represented by the formula (3) is a repeating unit represented by the following formula (13).

[Wherein, Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ each independently represent an arylene group or a divalent heterocyclic group. Ar ₁₀ , Ar ₁₁ and Ar ₁₂ each independently represent an aryl group or a monovalent heterocyclic group. Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ , and Ar ₁₀ may have a substituent. x and y each independently represents 0 or 1, and 0 ≦ x + y ≦ 1. ] Moreover hole transporting material comprises at least one material selected from electron transporting materials and light emitting materials, composition according to any one of claims 1-9. The ink composition characterized by containing a composition according to any one of claims 1-9. The ink composition of claim 1 1 having a viscosity characterized in that it is a 1 to 100 mPa · s at 25 ° C.. Light-emitting thin film comprising the composition of any of claims 1-9. Conductive thin film comprising the composition of any of claims 1-9. The organic semiconductor thin film comprising the composition of any of claims 1-9. Between electrodes consisting of an anode and a cathode, a polymer light emitting device characterized by having a layer comprising a composition according to any one of claims 1-9. The polymer light emitting device of claim 16, the layer comprising a composition according to any one of claims 1 to 9, characterized in that it is a light-emitting layer. The polymer light-emitting device according to claim 17, wherein the light-emitting layer further contains a hole transport material, an electron transport material, or a light-emitting material. Between the anode and cathode electrodes,
It has a repeating unit represented by the general formula (1-4) and has a polystyrene-equivalent number average molecular weight of 10 ³ -10 ⁸ The polymer is iridium, platinum or gold and the ligand is 8-quinolinol or a derivative thereof, benzoquinolinol or a derivative thereof, 2-phenyl-pyridine or a derivative thereof, 2-phenyl-benzo A polymer light-emitting element having a layer including a composition containing thiazole or a derivative thereof, 2-phenyl-benzoxazole or a derivative thereof, or a triplet light-emitting complex compound that is porphyrin or a derivative thereof. A planar light source comprising the polymer light-emitting device according to claim 16 . A segment display device using the polymer light-emitting device according to claim 16 . A dot matrix display device comprising the polymer light emitting device according to claim 16 . A liquid crystal display device comprising the polymer light emitting device according to claim 16 as a backlight. An illumination using the polymer light-emitting device according to claim 16 .