JP4706707B2 - Polymer compound and polymer light emitting device using the same - Google Patents

Description

The present invention relates to a polymer compound and a polymer light emitting device using the polymer compound (hereinafter referred to as polymer L).
Sometimes called ED. )

High-molecular-weight light-emitting materials and charge transport materials, unlike low-molecular weight materials, are variously studied because they are soluble in a solvent and can form a light-emitting layer in a light-emitting element by a coating method. Examples include phenylene groups, nitrogen A polymer compound having a repeating unit having a structure in which an atom and a phenylene group are connected in this order and the nitrogen atom is substituted with a phenyl group and a repeating unit composed of an aromatic group such as a terphenylenediyl group is known. (For example, Patent Document 1).

Japanese Patent Laid-Open No. 11-246660

An object of the present invention is to provide a polymer compound having excellent properties as a light-emitting material and / or an electron transport material, such as fluorescence intensity and charge transport property.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have, as a repeating unit, an aromatic ring, a nitrogen atom, and an aromatic ring connected in this order, and the nitrogen atom is an aromatic group having a diarylamino group at the end. A polymer compound containing a repeating unit having a substituted structure and a repeating unit composed of an aromatic group such as a phenylene group is a luminescent material and
The inventors have found that the properties as an electron transport material are excellent and have reached the present invention.

〔式中、Ａｒ₁およびＡｒ₂はそれぞれ独立に、アリーレン基または２価の複素
環基を表す。また、Ａｒ₃はアリーレン基、アリーレンビニレン基または２価の
複素環基を表す。ｘは１〜１０の整数を表す。Ａｒ₃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。Ａｒ₄およびＡｒ₅はそれぞれ独立に、アリ
ール基または１価の複素環基を表す。〕

−Ａｒ₆− （２）

〔式中、Ａｒ₆は、フェニレン基、スチルベン−ジイル基、ジスチルベン−ジイ
ル基、フルオレン−ジイル基、２価の縮合多環芳香族基、２価の単環性複素環基
、２価の縮合多環複素環基、または２価の芳香族アミン基を表す。〕 That is, the present invention relates to a polymer compound containing repeating units represented by the following formulas (1) and (2) and having a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ .

[Wherein, Ar ₁ and Ar ₂ each independently represent an arylene group or a divalent heterocyclic group. Ar ₃ represents an arylene group, an arylene vinylene group or a divalent heterocyclic group. x represents an integer of 1 to 10. When a plurality of Ar ₃ are present, they may be the same or different. Ar ₄ and Ar ₅ each independently represents an aryl group or a monovalent heterocyclic group. ]

-Ar _6- (2)

[In the formula, Ar ₆ represents a phenylene group, a stilbene-diyl group, a distilbene-diyl group, a fluorene-diyl group, a divalent condensed polycyclic aromatic group, a divalent monocyclic heterocyclic group, and a divalent condensed group. Represents a polycyclic heterocyclic group or a divalent aromatic amine group. ]

The polymer compound of the present invention is excellent in properties as a light-emitting material and / or an electron transport material, and can be suitably used as a light-emitting material for a polymer LED or a charge transport material.

The polymer compound of the present invention has a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ and includes one or more repeating units represented by the above formulas (1) and (2). . Especially, what has fluorescence in a solid state is used suitably as a luminescent material (polymer fluorescent substance).

First, the repeating unit represented by the formula (1) in the polymer compound of the present invention will be described.
Ar ₁ and Ar ₂ contained in the repeating unit represented by the formula (1) are each independently an arylene group or a divalent heterocyclic group, and Ar ₃ is an arylene group, an arylene vinylene group or a divalent complex. It is a cyclic group.

In the present invention, an aryl group is an atomic group remaining after removing one hydrogen atom from an aromatic hydrocarbon. An arylene group is a remaining atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon. Here, aromatic hydrocarbons have a condensed ring,
Also included are those in which two or more independent benzene rings or condensed rings are bonded directly or via a group such as vinylene.

In the present invention, the monovalent heterocyclic group refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound. The divalent heterocyclic group refers to the remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound. Here, the heterocyclic compound is an organic compound having a cyclic structure, in which the elements constituting the ring are not only carbon atoms, but also oxygen, sulfur, nitrogen, phosphorus,
A substance containing a hetero atom such as boron, arsenic or silicon in the ring.

In Formula (1), x shows the integer of 1-10, Preferably it is 1-5, More preferably, it is 1-3.

Ar ₁ , Ar ₂ , and Ar ₃ may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an aryl group, an aryloxy group, and an arylsilyl group. Group, arylalkyl group, arylalkoxy group, arylalkylsilyl group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group, cyano group and the like.
When Ar ₁ , Ar ₂ , and Ar ₃ have a substituent, adjacent substituents may be bonded to form a ring. When Ar ₄ and Ar ₅ have a substituent, adjacent substituents may be bonded to form a ring, or the rings may be bonded by a single bond.

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

The alkoxy group may be linear, branched or cyclic, and usually has 1 to 1 carbon atoms.
About 20, specifically, methoxy group, ethoxy group, propyloxy group, i
-Propyloxy group, butoxy group, i-butoxy group, t-butoxy group, benzyloxy group, isoamyloxy group, hexyloxy group, cyclohexyloxy group,
Examples include heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, pentyloxy group, isoamyloxy group, hexyloxy group, octyl Oxy group, 2-ethylhexyloxy group, decyloxy group, 3,7-
A dimethyloctyloxy group is preferred.

The alkylthio group may be linear, branched or cyclic, and usually has 1 carbon atom.
Specifically, methylthio group, ethylthio group, propylthio group, i-propylthio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, isoamylthio group, hexylthio group, cyclohexylthio group Group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, etc., and pentylthio group, isoamylthio group, hexylthio group, octylthio group, 2 -An ethylhexylthio group, a decylthio group, and a 3,7-dimethyloctylthio group are preferable.

The alkylsilyl group may be linear, branched or cyclic, and usually has about 1 to 60 carbon atoms. Specifically, methylsilyl group, ethylsilyl group, propylsilyl group, i-propylsilyl group, butylsilyl group I-butylsilyl group, t
-Butylsilyl group, pentylsilyl group, isoamylsilyl group, hexylsilyl group, cyclohexylsilyl group, heptylsilyl group, octylsilyl group, 2-ethylhexylsilyl group, nonylsilyl group, decylsilyl group, 3,7-dimethyloctylsilyl group, lauryl Silyl group, trimethylsilyl group, ethyldimethylsilyl group, propyldimethylsilyl group, i-propyldimethylsilyl group, butyldimethylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, Octyldimethylsilyl group,
2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, and the like, such as pentylsilyl group, hexylsilyl group, octylsilyl group, 2-ethylhexylsilyl group, decylsilyl group, 3,7-dimethyloctylsilyl group, pentyldimethylsilyl group, isoamyldimethylsilyl group, hexyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, decyldimethylsilyl group 3,7-dimethyloctyl-dimethylsilyl group is preferred.

The aryl group is a remaining atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and usually has about 6 to 60 carbon atoms. Specifically, a phenyl group, C _{1 to} C ₁₂
Alkylphenyl groups (C ₁ -C ₁₂ is also shown. Hereinafter it is 1 to 12 carbon atoms.), 1-naphthyl group, 2-naphthyl group and the like, a phenyl group, C ₁ ~ C ₁₂ alkylphenyl group are preferred.

Aryloxy group, the carbon number of usually about 6 to 60, specifically, phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2- naphthyloxy group and the like, a phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ -C ₁₂ alkylphenoxy group are preferable.

Aryl silyl group has a carbon number of usually about 7 to 60, specifically, a phenyl dimethylsilyl group, C ₁ -C ₁₂ alkoxyphenyl-butyldimethylsilyl group, C ₁
-C ₁₂ alkylphenyl butyldimethylsilyl group, 1-naphthyl dimethyl silyl group,
2-naphthyl - dimethyl silyl group and the like, C ₁ -C ₁₂ alkoxyphenyl-butyldimethylsilyl group, is C ₁ -C ₁₂ alkylphenyl-butyldimethylsilyl group.

Arylalkyl group has a carbon number of usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C _1
2 alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group, 1-
Examples include naphthyl-C ₁ -C ₁₂ alkyl group, 2-naphthyl-C ₁ -C ₁₂ alkyl group, and C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group, C
₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group are preferable.

The arylamino group usually has about 6 to 60 carbon atoms, a phenylamino group,
Diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C
₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, etc., and C ₁ -C
_{A 12} alkylphenylamino group and a di (C ₁ -C ₁₂ alkylphenyl) amino group are preferred.

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

The arylalkylsilyl group usually has about 7 to 60 carbon atoms, specifically,
The number of carbon atoms is usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ dimethyl silyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ dimethyl silyl group, C ₁ -C ₁₂ alkyl Examples include phenyl-C ₁ -C ₁₂ dimethylsilyl group, 1-naphthyl-C ₁ -C ₁₂ dimethylsilyl group, 2-naphthyl-C ₁ -C ₁₂ dimethylsilyl group, etc., and C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ dimethyl silyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ butyldimethylsilyl group is preferred.

Arylalkenyl group has a carbon number of usually about 8 to 60, specifically, a phenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C _1
2 alkenyl groups, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl group,
Examples include 1-naphthyl-C ₂ -C ₁₂ alkenyl group, 2-naphthyl-C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkyl, etc. phenyl -C ₂ -C ₁₂ alkenyl groups are preferred.

The arylalkynyl group usually has about 8 to 60 carbon atoms, and specifically includes a phenyl-C ₂ -C ₁₂ alkynyl group, a C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C _1.
2 alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group,
1-naphthyl -C ₂ -C ₁₂ alkynyl group, 2-naphthyl -C ₂ -C ₁₂ alkynyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkyl phenyl -C ₂ -C ₁₂ alkynyl group are preferable.

The monovalent heterocyclic group refers to the 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 30 carbon atoms. The carbon number of the heterocyclic group does not include the carbon number of the substituent. Specifically, a thienyl group,
C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ ~
C ₁₂ is like the illustration alkylpyridyl group, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

Among the substituents, in the substituents 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, adjacent substituents may be bonded to form a ring. further,
A part of carbon atoms of alkyl may be replaced with a hetero atom or a group containing a hetero atom, and examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.

ここで、Ｒ’としては、例えば、水素原子、炭素数１〜２０のアルキル基、炭
素数６〜６０のアリール基、炭素数４〜６０の１価の複素環基が挙げられる。 Examples of the hetero atom or the group containing a hetero atom include the following groups.

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

In the present invention, the arylene group includes a phenylene group (for example, the formula 1 in the following figure).
-3), naphthalenediyl group (formulas 4 to 13 in the figure below), anthracenylene group (formulas 14 to 19 in the figure below), biphenylene group (formulas 20 to 25 in the figure below), triphenylene group (formulas 26 to 28 in the figure below), condensation Examples thereof include ring compound groups (formulas 29 to 38 in the following figure). Among these, a phenylene group, a biphenylene group, a fluorene-diyl group (formulas 36 to 38 in the following figure), and an indenofluorene-diyl (bottom figures 38A to 38B) are preferable.

In the present invention, examples of the divalent heterocyclic group include the following.
A group containing nitrogen as a heteroatom; a pyridine-diyl group (formulae 39 to 44 in the following figure)
), A diazaphenylene group (formulas 45 to 48 in the following figure), a quinoline diyl group (formulas 49 to 63 in the figure below), a quinoxaline diyl group (formulas 64 to 68 in the figure below), an acridinediyl group (formulas 69 to 72 in the figure below), Bipyridyldiyl groups (formulas 73-75 in the figure below), phenanthroline diyl groups (formulas 76-78 in the figure below), and the like.
Groups having a fluorene structure containing oxygen, silicon, nitrogen, sulfur, selenium and the like as a hetero atom (formulas 79 to 93 in the following figure).
5-membered heterocyclic groups containing oxygen, 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, sulfur, selenium and the like as a hetero atom: (Formulas 99 to 110 in the following figure).
5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium or the like as a hetero atom, and a group bonded to the phenyl group at the α-position of the hetero atom: (Formulas 111 to 119 in the following figure)
).

In Ar ₃ , the arylene vinylene group means a group in which an arylene group is bonded with a vinylene group, and the arylene group at this time represents the same group as described above.
The arylene group of the arylene vinylene group can be replaced with a divalent heterocyclic group.

In each example of Ar ₁ , Ar ₂ , Ar ₃ above, R is a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an aryl group, an aryloxy group, an arylsilyl group, an arylalkyl group, An arylalkoxy group, an arylalkylsilyl group, an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group, a cyano group and the like can be mentioned.
In the above examples of Ar ₁ , Ar ₂ , and Ar ₃ , one structural formula has a plurality of Rs, but they may be the same or different groups, each independently. Selected. In addition, the carbon atom of the substituent of Ar ₁ , Ar ₂ , Ar ₃ may be replaced with an oxygen atom or a sulfur atom, and further, a hydrogen atom may be replaced with a fluorine atom.

Among Ar ₁ and Ar ₂ , phenylene, naphthalenediyl, anthracenediyl, phenanthrene, pyridinediyl and quinoxalinediyl are more preferable, phenylene, pyridinediyl and naphthalenediyl are more preferable, and phenylene is particularly preferable.

（式中、Ａ環は、フェニレン、ビフェニレン、ターフェニレン、フルオレンジイ
ル、ナフタレンジイル、アントラセンジイル、フェナンスレンジイル、ピリジン
ジイル、キノキサリンジイル、チエニレンを表し、Ｒ₁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、アリール基、アリールオキシ基、
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
キルシリル基、アリールアルケニル基、アリールアルキニル基、1価の複素環基
またはシアノ基を表す。ｙは０〜１２の整数、好ましくは０〜４の整数を表す。
Ｒ₁ 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。） Ar _{3 in the} formula (1) is preferably a group represented by the following formula (3).

(In the formula, A ring represents phenylene, biphenylene, terphenylene, fluorenediyl, naphthalenediyl, anthracenediyl, phenanthrene diyl, pyridinediyl, quinoxalinediyl, thienylene, R ₁ represents an alkyl group, an alkoxy group, Alkylthio group, alkylsilyl group, aryl group, aryloxy group,
An arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylsilyl group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group or cyano group is represented. y represents an integer of 0 to 12, preferably an integer of 0 to 4.
When a plurality of R ₁ are present, they may be the same or different. )

In R ₁ , an alkyl group, an alkoxy group, an aryl group, an aryloxy group,
An arylsilyl group, an arylalkyl group, and an arylalkoxy group are preferable, and an alkyl group, an alkoxy group, an aryl group, and an aryloxy group are more preferable.
Specific examples of these groups include the same groups listed as the substituents for Ar ₁ , Ar ₂ and Ar ₃ .

（式中、Ｒ₂およびＲ₃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、アルキルシリル基、アリール基、アリールオキシ基、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、アリールアルキルシリル基
、アリールアルケニル基、アリールアルキニル基、1価の複素環基またはシアノ
基を表す。Ｒ₄およびＲ₅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、1価の複素環基またはシアノ基を表す。ｚおよびｗ
はそれぞれ独立に０〜４の整数を表す。Ｒ₂およびＲ₃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。） In addition, Ar _{3 in the} above formula (1) is preferably a group represented by the following formula (4).

(Wherein R ₂ and R ₃ are each independently an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an aryl group, an aryloxy group, an arylsilyl group, an arylalkyl group, an arylalkoxy group, an arylalkylsilyl group) A group, an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group or a cyano group, wherein R ₄ and R ₅ each independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a monovalent heterocycle; Represents a cyclic group or a cyano group, z and w
Each independently represents an integer of 0 to 4. When a plurality of R ₂ and R ₃ are present, they may be the same or different. )

In the case where Ar _{3 in} formula (1) is formula (4), x is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.

Here, the aryl group represented by Ar ₄ and Ar ₅ is an atomic group obtained by removing one hydrogen atom from a monocyclic aromatic compound or a condensed polycyclic aromatic compound. 6-6 carbon atoms
It is about 0, preferably 6-30. Specifically, a phenyl group or an aromatic compound group condensed with 2 to 5 benzene rings is preferable. Specific examples include phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, naphthacenyl, pentacenyl, chrycenyl, coronyl and the like, and phenyl, naphthyl, and anthracenyl are preferable. More preferred is phenyl.

The monovalent heterocyclic group represented by Ar ₄ and Ar ₅ is an atomic group obtained by removing one hydrogen atom from a monocyclic aromatic compound or a condensed polycyclic aromatic compound. The number of carbon atoms is usually 4 ~
It is about 60, preferably 4-30.
The monocyclic heterocyclic compound and condensed polycyclic heterocyclic group represented by Ar ₄ and Ar ₅ are not only carbon atoms as elements constituting the ring, but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, arsenic, and silicon. An atom containing an atom in the ring. Specifically, pyridyl, pyrimidyl, pyrazyl, thienyl, furyl, pyrrolyl, imidazolyl, oxadiazoyl, quinolyl, quinoxalyl, acridinyl, phenanthrolinyl, benzoxazolyl, benzothiazolyl, benzooxadiazolyl, benzothiadiazolyl, dibenzo Furyl, dibenzothienyl, carbazoyl and the like, and pyridyl, pyrimidyl, thienyl, oxadiazoyl, quinoline, benzooxadiazole, benzothiadiazole, and carbazole are preferable.
Ar ₄ and Ar ₅ may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an aryl group, an aryloxy group, an arylsilyl group, and an arylalkyl. Group, arylalkoxy group, arylalkylsilyl group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group and the like. Adjacent substituents may be bonded to form a ring. Ar ₄ and Ar ₅ may be linked by a carbon-carbon single bond to form a carbazole ring.

Next, the repeating unit represented by the formula (2) contained in the polymer compound of the present invention will be described.
Ar ₆ represented by the formula (2) is a phenylene group, a stilbene-diyl group, a distilbene-diyl group, a fluorene-diyl group, a divalent condensed polycyclic aromatic compound group, 2
A divalent condensed polycyclic heterocyclic group or a divalent aromatic amine group.
Ar ₆ may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an aryl group, an aryloxy group, an arylsilyl group, an arylalkyl group, and an arylalkoxy group. Group, arylalkylsilyl group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group and the like.
When Ar ₆ has a plurality of substituents, the substituents may be bonded to form a ring. Further, when the substituent is a group containing an alkyl chain, the alkyl chain may be interrupted by a group containing a hetero atom.

〔式中、Ｒ₆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、アリールオキシ基、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、アリールアルキルシリル基、アリールアルケニル基、アリールアルキ
ニル基、1価の複素環基またはシアノ基を示す。Ｒ₆として好ましくは、アルキ
ル基、アルコキシ基、アルキルチオ基、アリールオキシ基、アリールアルキル基
、アリールアルコキシ基であり、より好ましくは、アルキル基、アルコキシ基、
アルキルチオ基、アリールオキシ基、アリールアルコキシ基であり、特に好まし
くはアルコキシ基である。ｎは０〜４の整数を表す。Ｒ₆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、Ｒ₇およびＲ₈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、アルキルシリル基、アリール基、アリールオキシ基、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、アリールアルキルシリル基
、アリールアルケニル基、アリールアルキニル基、1価の複素環基またはシアノ
基を表す。ｌは０〜５の整数を表す。ｍは０〜３の整数を表す。Ｒ₇およびＲ₈
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。〕 Here, the phenylene group is preferably a group represented by the following formula (5) or formula (6).

[Wherein, R ₆ represents an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an aryloxy group, an arylsilyl group, an arylalkyl group, an arylalkoxy group, an arylalkylsilyl group, an arylalkenyl group, an arylalkynyl group, A monovalent heterocyclic group or a cyano group is shown. R ₆ is preferably an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylalkyl group, or an arylalkoxy group, more preferably an alkyl group, an alkoxy group,
An alkylthio group, an aryloxy group, and an arylalkoxy group, particularly preferably an alkoxy group. n represents an integer of 0 to 4. When there are multiple R _{6 s} ,
They may be the same or different. ]

[Wherein R ₇ and R ₈ are each independently an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an aryl group, an aryloxy group, an arylsilyl group, an arylalkyl group, an arylalkoxy group, an arylalkylsilyl group. A group, an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group or a cyano group; l represents an integer of 0 to 5; m represents an integer of 0 to 3. R ₇ and R ₈
When there are a plurality of each, they may be the same or different. ]

R ₇ and R ₈ are preferably an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylalkyl group, and an arylalkoxy group, and more preferably an alkyl group, an alkoxy group, an alkylthio group, and an aryloxy group. Group, an arylalkoxy group, particularly preferably an alkoxy group.
In Formula (5), n shows the integer of 0-4. From the viewpoint of solubility, at least n is preferably 1. From the viewpoint of synthesis, n is preferably 1 to 2. Moreover, in Formula (6), l shows the integer of 0-5, m shows the integer of 0-3. From the viewpoint of synthesis, l and m are preferably 0 to 2.

〔ここで、Ｒ₁₁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、アルキルシリル基、アリール基、アリールオキシ基、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、アリールアルキルシ
リル基、アリールアルケニル基、アリールアルキニル基、1価の複素環基または
シアノ基を表す。ｃおよびｄは、それぞれ独立に０〜４の整数を表す。Ｒ₁₁お
よびＲ₁₄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
。Ｒ₁₂およびＲ₁₃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、1価の複素環基またはシアノ基を示す。〕
The stilbene-diyl group may have a substituent, and the same group as the substituent of the phenylene group described above is selected as the substituent. The stilbene-diyl group is preferably a group represented by the following formula (8).

[Wherein R ₁₁ and R ₁₄ are each independently an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an aryl group, an aryloxy group, an arylsilyl group, an arylalkyl group, an arylalkoxy group, an arylalkylsilyl group. A group, an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group or a cyano group; c and d each independently represents an integer of 0 to 4. When a plurality of R ₁₁ and R ₁₄ are present, they may be the same or different. R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a monovalent heterocyclic group or a cyano group. ]

R ₁₁ and R ₁₄ are preferably an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylalkyl group, and an arylalkoxy group, and more preferably an alkyl group, an alkoxy group, an alkylthio group, and an aryloxy group. Group, an arylalkoxy group, more preferably an alkoxy group,
An arylalkoxy group and an aryloxy group.
In the formula (8), R ₁₂ and R ₁₃ are each independently a hydrogen atom, an alkyl group,
An aryl group, an arylalkyl group, a monovalent heterocyclic group or a cyano group is shown. Specific examples of these substituents are the same as those shown as R ₁ .

In formula (8), R ₁₂ and R ₁₃ are preferably a hydrogen atom, an alkyl group, an aryl group, or a cyano group, and more preferably a hydrogen atom or a cyano group.
c and d each independently represent an integer of 0 to 4. From the viewpoint of solubility, c and d are 1
The above is preferable, and 3 or less is desirable from a synthetic viewpoint. More preferably, c, d
Is 1-2.

〔ここで、Ｒ₁₅およびＲ₁₈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、アルキルシリル基、アリール基、アリールオキシ基、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、アリールアルキルシリル
基、アリールアルケニル基、アリールアルキニル基、1価の複素環基またはシア
ノ基を表す。ｅは、０〜５の整数を表す。ｆは、０〜３の整数を表す。Ｒ₁₅お
よびＲ₁₈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
。Ｒ₁₆およびＲ₁₇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、1価の複素環基またはシアノ基を示す。〕 The stilbene-diyl group is preferably a group represented by the following formula (9).

Wherein R ₁₅ and R ₁₈ are each independently an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an aryl group, an aryloxy group, an arylsilyl group, an arylalkyl group, an arylalkoxy group, an arylalkylsilyl group, An arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group or a cyano group is represented. e represents an integer of 0 to 5; f represents an integer of 0 to 3. When a plurality of R ₁₅ and R ₁₈ are present, they may be the same or different. R ₁₆ and R ₁₇ each independently represent a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a monovalent heterocyclic group or a cyano group. ]

R ₁₅ and R ₁₈ are preferably an alkyl group, an alkoxy group, an alkylthio group,
An aryl group, an aryloxy group, an arylamino group, an arylalkyl group, an arylalkoxy group, and a cyano group, and more preferably an alkoxy group, an aryl group, an aryloxy group, an arylamino group, an arylalkoxy group, and a cyano group. .
e shows the integer of 0-5. From the viewpoint of solubility, e is preferably 1 or more, and preferably 3 or less from a synthetic viewpoint. More preferably, e is 1-2. f is from 0 to
Represents an integer of 3, preferably f is an integer of 0-2.

R ₁₆ and R ₁₇ each independently represent a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a monovalent heterocyclic group or a cyano group. Specific examples of these substituents are the same as those shown as R ₁ .
R ₁₆ and R ₁₇ are preferably a hydrogen atom, an alkyl group, an aryl group, or a cyano group, and more preferably a hydrogen atom or a cyano group.

〔式中、Ａｒ₉は、アリーレン基または２価の複素環基を表す。Ｒ₂₇およびＲ
₃₂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、アルキル
シリル基、アリール基、アリールオキシ基、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、アリールアルキルシリル基、アリールアルケニル
基、アリールアルキニル基、1価の複素環基またはシアノ基を表す。ｑおよびｒ
は、それぞれ独立に０〜４の整数を表す。Ｒ₂₇およびＲ₃₂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Ｒ₂₈、Ｒ₂₉、Ｒ₃₀およ
びＲ₃₁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、1価の複素環基またはシアノ基を表す。〕 The distilbene-diyl group may have a substituent, and has two phenylene groups and an arylene group or divalent heterocyclic group in the center, and the two phenylene groups and the central arylene group. Each of them is a group having a vinylene group. These arylene groups may have a substituent, and specific examples thereof include Ar ₁ , A
Examples thereof include the same groups as mentioned as the substituents for r ₂ and Ar ₃ .
The distilbene-diyl group is preferably a group represented by the following formula (12).

[Wherein Ar ₉ represents an arylene group or a divalent heterocyclic group. R ₂₇ and R
₃₂ are each independently an alkyl group, alkoxy group, alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylsilyl group, arylalkenyl group, arylalkynyl group Represents a monovalent heterocyclic group or a cyano group. q and r
Each independently represents an integer of 0 to 4. When there are a plurality of R ₂₇ and R ₃₂ , they may be the same or different; R ₂₈ , R ₂₉ , R ₃₀ and R ₃₁ are each independently a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group; Represents a monovalent heterocyclic group or a cyano group. ]

Ar ₉ in the formula (12) is an arylene group or a divalent heterocyclic group. Specific examples of these groups are the same as those of the above Ar ₁ to Ar _3. In the formula (12), R ₂₇ and R ₃₂ each independently represent the same group as R ₁ .
R ₂₇ and R ₃₂ are preferably an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylalkyl group, and an arylalkoxy group, and more preferably an alkyl group, an alkoxy group, an alkylthio group, and an aryloxy group. Group, an arylalkoxy group, more preferably an alkoxy group, an arylalkoxy group, and an aryloxy group.

In Formula (12), q and r each independently represent an integer of 0 to 4. 3 or less is desirable from a synthetic viewpoint. More preferably, q and r are 0-2. q is 2
In the above case, a plurality of R ₂₇ may be the same or different. When r is 2 or more, a plurality of R ₃₂ may be the same or different.

In the formula (12), R _{28 to} R ₃₁ each independently represent a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a monovalent heterocyclic group or a cyano group. Specific examples of these substituents are the same as those shown as R ₁ .
R _{28 to} R ₃₁ are preferably a hydrogen atom, an alkyl group, an aryl group, or a cyano group, and more preferably a hydrogen atom or a cyano group.

〔式中、Ｒ₃₃、Ｒ₃₄、Ｒ₃₅およびＲ₃₆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、アルキルシリル基、アリール基、アリールオ
キシ基、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
ールアルキルシリル基、アリールアルケニル基、アリールアルキニル基、1価の
複素環基またはシアノ基を表す。ａａおよびｂｂは、それぞれ独立に０〜３の整
数を表す。〕 Among the fluorene-diyl groups, a group represented by the following formula (13) is preferable.

[Wherein R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ are each independently an alkyl group, alkoxy group, alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, arylalkyl group, aryl Represents an alkoxy group, an arylalkylsilyl group, an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group or a cyano group; aa and bb each independently represents an integer of 0 to 3; ]

R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ are preferably an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylalkyl group, and an arylalkoxy group, and more preferably an alkyl group and an alkoxy group. , An alkylthio group, an aryloxy group and an arylalkoxy group, more preferably an alkyl group, an alkoxy group, an aryloxy group and an arylalkoxy group.

In Formula (13), aa and bb each independently represent an integer of 0 to 3. a
a and bb are preferably 2 or less from the viewpoint of synthesis. More preferably, aa and bb are 0. When aa is 2 or more, the plurality of R ₃₃ may be the same or different. When bb is 2 or more, a plurality of R ₃₄ may be the same or different.

〔ここで、Ｒ₉およびＲ₁₀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、アルキルシリル基、アリール基、アリールオキシ基、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、アリールアルキルシリ
ル基、アリールアルケニル基、アリールアルキニル基、1価の複素環基またはシ
アノ基を表す。ａおよびｂは、それぞれ独立に０〜３の整数を表す。Ｒ₉および
Ｒ₁₀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。〕
The divalent condensed polycyclic aromatic compound group is an atomic group obtained by removing two hydrogen atoms from a condensed polycyclic aromatic compound. Here, the condensed polycyclic aromatic compound represented by Ar ₆ is preferably an aromatic compound in which the number of carbon atoms contained in the ring is usually about 6 to 60, and 2 to 5 benzene rings are condensed. Specifically, naphthalene, anthracene, phenanthrene, pyrene, perylene, naphthacene, pentacene, chrysene, coronene and the like are preferable, and naphthalene and anthracene are preferable. From the viewpoint of solubility, it preferably has at least one substituent.
Of the divalent condensed polycyclic aromatic compound group, a group represented by the following formula (7) is preferable.

[Wherein R ₉ and R ₁₀ are each independently an alkyl group, an alkoxy group,
Alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylsilyl group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group or cyano group . a and b each independently represents an integer of 0 to 3. When a plurality of R ₉ and R ₁₀ are present, they may be the same or different. ]

R ₉ and R ₁₀ are preferably an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylalkyl group, and an arylalkoxy group, and more preferably an alkyl group, an alkoxy group, an alkylthio group, and an aryloxy group. Group, an arylalkoxy group, more preferably an alkoxy group, an aryloxy group, and an arylalkoxy group.

In Formula (7), it is preferable that either a or b is not 0 from the viewpoint of solubility. More preferably, a and b are each independently 1-2.

The divalent condensed polycyclic heterocyclic group is an atomic group obtained by removing two hydrogen atoms from a condensed polycyclic heterocyclic compound. Here, in the condensed polycyclic heterocyclic compound represented by Ar ₆ , among organic compounds having a cyclic structure in which two or more rings are condensed, not only carbon atoms but also oxygen, sulfur, One containing a heteroatom such as nitrogen, phosphorus or boron in the ring. The number of carbon atoms contained in the ring is preferably about 6 to 60, more preferably 6
~ 30. Specifically, quinoline, quinoxaline, acridine, phenanthroline, benzoxazole, benzothiazole, benzoxiadiazole, benzothiadiazole, dibenzofuran, dibenzothiophene, carbazole, etc., quinoline, benzoxadiazole, benzothiadiazole, carbazole preferable. From the viewpoint of solubility, it preferably has at least one substituent.

〔式中、Ｒ₂₀およびＲ₂₁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、アルキルシリル基、アリール基、アリールオキシ基、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、アリールアルキルシリ
ル基、アリールアルケニル基、アリールアルキニル基、1価の複素環基またはシ
アノ基を表す。ｏおよびｐは、それぞれ独立に０〜４の整数を表す。Ｒ₂₀およ
びＲ₂₁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。
Ｘ₂は、Ｏ、Ｓ、Ｎ−Ｒ₂₂、またはＳｉＲ₂₃Ｒ₂₄を表す。Ｘ₃およびＸ₄
は、それぞれ独立にＮまたはＣ−Ｒ₂₅を表す。Ｒ₂₂、Ｒ₂₃、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、アリールアルキ
ル基または１価の複素環基を表す。〕 Of the divalent monocyclic heterocyclic group, a group represented by the following formula (11) is preferable.

[Wherein, R ₂₀ and R ₂₁ each independently represents an alkyl group, an alkoxy group,
Alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylsilyl group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group or cyano group . o and p each independently represent an integer of 0 to 4. When a plurality of R ₂₀ and R ₂₁ are present, they may be the same or different.
X ₂ represents O, S, N—R ₂₂ , or SiR ₂₃ R ₂₄ . X ₃ and X ₄
Each independently represents N or C—R ₂₅ . R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ each independently represent a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. ]

R ₂₀ and R ₂₁ are preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, and a cyano group, and more preferably an alkoxy group, an aryloxy group, and an arylalkoxy group. , A cyano group.

In Formula (11), o and p each independently represent an integer of 0 to 4. From the viewpoint of synthesis, 3 or less is preferable. More preferably, o and p are each independently 0-2.
R _{22 to} R ₂₅ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
An aryl group having 6 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms, or a monovalent heterocyclic group having 4 to 60 carbon atoms is shown. When X ₂ is a group represented by SiR ₂₃ R ₂₄ , R ₂₃ and R ₂₄ are preferably an aryl group.

Examples of the central 5-membered ring of the repeating unit represented by the formula (11) include oxadiazole, triazole, thiophene, furan, silole and the like.

〔式中、Ａｒ₇およびＡｒ₈は、それぞれ独立に、置換基を有していても良いア
リーレン基もしくは２価の複素環基を表す。
Ｒ₁₉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
リール基、アリールオキシ基、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、アリールアルキルシリル基、アリールアルケニル基、アリール
アルキニル基、1価の複素環基またはシアノ基を表す。ｇは、０〜２の整数を表
す。Ｒ₁₉が2つある場合、それらは同一でも異なっていてもよい。Ｘ₁は、Ｏ
またはＳを表す。〕
Among the divalent condensed polycyclic heterocyclic groups, a group represented by the following formula (10) is preferable.

[Wherein, Ar ₇ and Ar ₈ each independently represent an arylene group or divalent heterocyclic group which may have a substituent.
R ₁₉ is an alkyl group, alkoxy group, alkylthio group, alkylsilyl group, aryl group, aryloxy group, arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylsilyl group, arylalkenyl group, arylalkynyl group, 1 Represents a valent heterocyclic group or a cyano group. g represents the integer of 0-2. If R ₁₉ is two, they may be the same or different. X ₁ is O
Or represents S. ]

R ₁₉ is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group or a cyano group, more preferably an alkyl group, an aryl group, an arylalkyl group or a cyano group. .

In formula (10), X ₁ is preferably S.

Ar ₇ and Ar ₈ in the formula (10) are, for example, a phenylene group, a thienylene group, a naphthalenediyl group, or the like. More specific examples of the repeating unit structure containing Ar ₇ and Ar ₈ include the following structures.

〔ここで、Ｒ₃₇、Ｒ₃₈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、アルキルシリル基、アリール基、アリールオキシ基、
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
キルシリル基、アリールアルケニル基、アリールアルキニル基、1価の複素環基
またはシアノ基を表す。ｉおよびｊは、それぞれ独立に０〜４の整数を表す。ｋ
は０〜５の整数を表す。ｈは１または２を表す。Ｒ₃₇、Ｒ₃₈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。〕 The divalent aromatic amine group is an atomic group remaining after removing two hydrogen atoms from the aromatic ring of the aromatic amine. Here, as the aryl group to be an aromatic ring, a phenyl group,
Examples include naphthyl group, anthryl group, phenanthrenyl group and the like.
The divalent aromatic amine group is preferably a group represented by the following formula (14).

[Wherein R ₃₇ , R ₃₈ and R ₃₉ are each independently an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an aryl group, an aryloxy group,
An arylsilyl group, arylalkyl group, arylalkoxy group, arylalkylsilyl group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group or cyano group is represented. i and j each independently represents an integer of 0 to 4. k
Represents an integer of 0 to 5. h represents 1 or 2. When there are a plurality of R ₃₇ , R ₃₈ and R ₃₉ , they may be the same or different. ]

R ₃₇ , R ₃₈ and R ₃₉ are preferably an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylalkyl group or an arylalkoxy group, more preferably an alkyl group, an alkoxy group or an alkylthio group. , An aryloxy group and an arylalkoxy group, more preferably an alkyl group and an alkoxy group.

In Formula (14), i and j each independently represent an integer of 0 to 4. Preferably, it is 0-2. k represents an integer of 0 to 5. Preferably it is 0-2, More preferably, it is 1. The substitution position of R ₃₉ is preferably the p-position of the N atom from a synthetic viewpoint. Also, two benzene rings adjacent to one N may be connected by a carbon-carbon single bond to form a carbazole ring. In this case, it is preferable in the synthesis that a carbazole ring formed by linking is included in the main chain.

〔式中、Ｒ₄₀、Ｒ₄₁、Ｒ₄₂、Ｒ₄₃およびＲ₄₄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、アルキルシリル基、アリール基、アリ
ールオキシ基、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
、アリールアルキルシリル基、アリールアルケニル基、アリールアルキニル基、
1価の複素環基またはシアノ基を表す。ｃｃ、ｄｄおよびｅｅは、それぞれ独立
に０〜４の整数を表す。ｆｆおよびｇｇは、それぞれ独立に０〜５の整数を表す
。Ｒ₄₀、Ｒ₄₁、Ｒ₄₂、Ｒ₄₃およびＲ₄₄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。〕 Of the divalent aromatic amine groups, a group represented by the following formula (15) is preferable.

[Wherein, R ₄₀ , R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ are each independently an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an aryl group, an aryloxy group, an arylsilyl group, an arylalkyl group. , Arylalkoxy group, arylalkylsilyl group, arylalkenyl group, arylalkynyl group,
Represents a monovalent heterocyclic group or cyano group. cc, dd and ee each independently represents an integer of 0 to 4. ff and gg each independently represents an integer of 0 to 5. When there are a plurality of R ₄₀ , R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ ,
They may be the same or different. ]

As R ₄₀ to R _44, preferably an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, more preferably an alkyl group, an alkoxy group, an alkylthio group, an aryloxy Group, an arylalkoxy group, more preferably an alkyl group or an alkoxy group.

In formula (15), cc, dd, and ee each independently represent an integer of 0 to 4.
Preferably, it is 0-2. ff and gg represent an integer of 0 to 5. Preferably 0
2, more preferably 1. The substitution position of R ₄₃ and R ₄₄ is preferably the p-position of the N atom from a synthetic viewpoint. Also, two benzene rings adjacent to one N may be connected by a carbon-carbon single bond to form a carbazole ring.

At least one repeating unit represented by the above formula (1) and the above formulas (5) to (
An embodiment of the present invention also includes at least one selected from the repeating units represented by 15) and a total of two or more types.
When the aromatic compound group, heterocyclic compound group, or vinylene group constituting the repeating unit of the polymer compound of the present invention has a substituent, adjacent substituents may be linked to form a ring. When these substituents contain an alkyl group, the alkyl chain may be interrupted by a group containing a hetero atom.

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

また、該高分子化合物は、ランダム、ブロックまたはグラフト共重合体であっ
てもよいし、それらの中間的な構造を有する高分子、例えばブロック性を帯びた
ランダム共重合体であってもよい。蛍光の量子収率の高い高分子化合物を得る観
点からは繰り返しの規則性は低い方が好ましく、例えば、交互共重合体よりもラ
ンダム共重合体が好ましい。さらに完全なランダム共重合体よりも、ブロック性
を帯びたランダム共重合体や不均一なサイズのブロックからなるブロック共重合
体、あるいはグラフト共重合体がより好ましい。主鎖に枝分かれがあり、末端部
が３つ以上ある場合も含まれる。また、規則正しく成長したデンドリマーや、ラ
ンダムな分岐が起こっている構造も含まれる。 The polymer compound has the formula (
It may contain a repeating unit other than the repeating units represented by 1) to formula (15). Moreover, the repeating unit shown by Formula (1)-Formula (15) and another repeating unit may be connected by the nonconjugated unit, and those nonconjugated parts may be contained in the repeating unit. Good. Examples of the binding structure include those shown below, combinations of the following and vinylene groups, and combinations of two or more of the following. Here, R is the same group as R _1, and Ar represents a hydrocarbon group having 6 to 60 carbon atoms.

The polymer compound may be a random, block or graft copolymer, or may be a polymer having an intermediate structure thereof, for example, a random copolymer having a block property. From the viewpoint of obtaining a polymer compound having a high fluorescence quantum yield, it is preferable that the regularity of repetition is low. For example, a random copolymer is more preferable than an alternating copolymer. Furthermore, a random copolymer having a block property, a block copolymer composed of non-uniformly sized blocks, or a graft copolymer is more preferable than a complete random copolymer. The case where the main chain is branched and there are three or more terminal portions is also included. Also included are regularly grown dendrimers and structures with random branching.

Moreover, since the light emission from a thin film is utilized, the polymer compound having fluorescence in a solid state is preferably used.
Examples of the good solvent for the polymer compound include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, and n-butylbenzene. Although depending on the structure and molecular weight of the polymer compound, it can usually be dissolved in these solvents in an amount of 0.1% by weight or more.

The polymer compound has a number average molecular weight of 10 ³ to 10 ⁸ in terms of polystyrene,
More preferably 10 ⁴ -10 ^7, and more preferably, 2 × 10 ⁴ to 10
⁶ .

When these polymer compounds are used as light-emitting materials for polymer LEDs, the purity affects the light-emitting properties, so the monomers before polymerization must be 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.

Next, a method for producing the polymer compound of the present invention will be described.
Examples of the method for producing the polymer compound of the present invention include a method described in JP-A-5-202355, when the main chain has a vinylene group. That is, polymerization by a Wittig reaction of a compound having an aldehyde group and a compound having a phosphonium base, or a compound having an aldehyde group and a phosphonium base, a compound having a vinyl group and a compound having a halogen group, or a vinyl group Polymerization of a compound having a halogen group by Heck reaction, Horner-Wadswo of a compound having an aldehyde group and a compound having an alkylphosphonate group, or a compound having an aldehyde group and an alkylphosphonate group
Polymerization by the rth-Emmons method, polycondensation of a compound having two or more methyl halide groups by dehydrohalogenation method, polycondensation of a compound having two or more sulfonium bases by a sulfonium salt decomposition method, aldehyde A method such as polymerization by a Knoevenagel reaction of a compound having a group and a compound having an acetonitrile group, or a compound having an aldehyde group and an acetonitrile group, McMur of a compound having two or more aldehyde groups
A method such as polymerization by ry reaction is exemplified.

In the case where the main chain does not have a vinylene group, for example, from the corresponding monomer, S
A method of polymerizing by an uzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a Ni (0) catalyst, a method of polymerizing by an oxidizing agent such as FeCl _3, a method of electrochemical oxidative polymerization, or an appropriate desorption Examples thereof include a method by decomposition of an intermediate polymer having a leaving group.
Among these, polymerization by Wittig reaction, polymerization by Heck reaction, H
Polymerization by the orner-Wadsworth-Emmons method, Knoeven
Polymerization by agel reaction, polymerization by Suzuki coupling reaction, polymerization by Grignard reaction, and polymerization by Ni (0) catalyst are preferred because the structure can be easily controlled.

Specifically, a compound that has a plurality of reactive substituents, which is a monomer, is dissolved in an organic solvent as necessary, and reacted, for example, with an alkali or a suitable catalyst at a temperature not lower than the melting point of the organic solvent and not higher than the boiling point. Can do. For example, “Organic Reactions”, Vol. 14, pages 270-490, John Wiley & Sons, Inc.
. ), 1965, “Organic Reactions.
ctions) ", 27, 345-390, John Wiley & Sons, Inc., 1982," Organic Synthesis ", Collective Volume VI (407). 411, John Wiley & Sons, Inc.,
1988, Chemical Review (Chem. Rev.), 95, 2457
Page (1995), Journal of Organometallic Chemistry (J
. Organomet. Chem. ), 576, 147 (1999),
Journal of Practical Chemistry (J. Prakt. Chem
. , 336, 247 (1994), Macromolecular Chemistry Macromolecular Symposium (Makromol. Chem., Ma)
cromol. Symp. ), Vol. 12, p. 229 (1987), etc., can be used.

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.

More specifically, the reaction conditions are described as follows: Wittig reaction, Horner
In the case of a reaction, Knoevengel reaction, etc., the reaction is carried out using an alkali equivalent to or more, preferably 1 to 3 equivalents, relative to the functional group of the monomer. Although it does not specifically limit as an alkali, For example, potassium-t-butoxide, sodium-t-
Metal alcoholates such as butoxide, sodium ethylate, and lithium methylate, hydride reagents such as sodium hydride, amides such as sodium amide, and the like can be used. As the solvent, N, N-dimethylformamide,
Tetrahydrofuran, dioxane, toluene and the like are used. The reaction can be allowed to proceed at a reaction temperature of usually from room temperature to about 150 ° C. The reaction time is, for example, 5 minutes to 40 hours, but may be a time for which the polymerization proceeds sufficiently, and it is not necessary to leave for a long time after the reaction is completed.
It's time. If the reaction concentration is too dilute, the reaction efficiency is poor. If the concentration is too high, it becomes difficult to control the reaction. Therefore, the concentration may be appropriately selected within the range of about 0.01 wt% to the maximum concentration to be dissolved. The range is from 1 wt% to 20 wt%. In the case of the Heck reaction, a palladium catalyst is used in the presence of a base such as triethylamine.
The monomer is reacted. A relatively high boiling point solvent such as N, N-dimethylformamide or N-methylpyrrolidone is used, the reaction temperature is about 80 to 160 ° C., and the reaction time is about 1 to 100 hours.

In the case of the Suzuki coupling reaction, for example, palladium [tetrakis (triphenylphosphine)], palladium acetates and the like are used as a catalyst.
An inorganic base such as potassium carbonate, sodium carbonate or barium hydroxide, an organic base such as triethylamine, or an inorganic salt such as cesium fluoride is added in an amount equal to or greater than the monomer, preferably 1 to 10 equivalents. An inorganic salt may be used as an aqueous solution and reacted in a two-phase system. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. 50 ~ depending on the solvent
A temperature of about 160 ° C. is preferably used. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 1 hour to 200 hours.

In the case of the Grignard reaction, a halide and metal Mg are reacted in an ether solvent such as tetrahydrofuran, diethyl ether or dimethoxyethane to form a Grignard reagent solution, which is mixed with a separately prepared monomer solution, and nickel or palladium. An example is a method in which a catalyst is added while paying attention to excess reaction, and then reacted while heating at reflux. The Grignard reagent is used in an equivalent amount or more, preferably 1 to 1.5 equivalents, more preferably 1 to 1.2 equivalents, relative to the monomer. Also in the case of polymerizing by a method other than these, the reaction can be carried out according to a known method.

Next, the polymer LED of the present invention will be described. The polymer LED of the present invention is a polymer light emitting device having a light emitting layer between electrodes composed of an anode and a cathode, wherein the light emitting layer contains the polymer compound of the present invention.
The polymer LED of the present invention includes a polymer LED provided with an electron transport layer between the cathode and the light emitting layer, and a polymer LED provided with a hole transport layer between the anode and the light emitting layer.
And 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.
The polymer LED of the present invention includes an element in which a layer containing a conductive polymer is provided between at least one electrode and a light emitting layer adjacent to the electrode; between at least one electrode and the light emitting layer. In addition, an element in which an insulating layer having a thickness of 2 nm or less is provided adjacent to the electrode.

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

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

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

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

In the present invention, polymer LE provided with a charge injection layer (electron injection layer, hole injection layer)
Examples of D include a polymer LED provided with a charge injection layer adjacent to the cathode, and a polymer LED provided with a charge injection layer adjacent to the anode.
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 / electron 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 / electron 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 2 nm to 50 nm.
nm is preferred.

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

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

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

When forming a polymer LED, when using these organic solvent-soluble polymer compounds to form a film from a solution, it is only necessary to remove the solvent by drying after applying this solution. The same technique can be applied even when the materials are mixed, which 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 5 nm to 200 nm
It is.

In the polymer LED of the present invention, a light emitting material other than the polymer compound may be mixed and used in the light emitting layer. In the polymer LED of the present invention, a light emitting layer containing a light emitting material other than the polymer compound may be laminated with a light emitting layer containing the polymer compound.
As the light emitting material, known materials can be used. For low molecular weight compounds, for example,
Naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine series, xanthene series, coumarin series, cyanine series pigments, 8
-A metal complex of hydroxyquinoline or a derivative thereof, an aromatic amine, tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used.
Specifically, known ones such as those described in JP-A-57-51781 and 59-194393 can be used.
In addition, the light emitting layer should just contain the high molecular compound of this invention, and may be mixed with the well-known high molecular or low molecular charge transport material. As the charge transport material, those used for the following hole transport layer and electron transport layer may be used. Furthermore, an organic material or an inorganic material that does not have a light emission or charge transport function may be mixed in the light emitting layer as long as the light emitting function is not impaired.

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, 63
JP-A-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209988, JP-A-3-37992, JP-A-3-15218.
The thing etc. which are described in No. 4 gazette are illustrated.

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 group in a side chain or a main chain, polyaniline or a derivative thereof, polythiophene Or a polymer hole transport material such as 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 Alternatively, a derivative thereof, 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.

Polysilane or its derivatives include chemical reviews (Chem. R).
ev. ) 89, 1359 (1989), British Patent GB2300196, and the like. 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 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.
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, 63-175860,
JP-A-2-135359, JP-A-2-135361, JP-A-2-20998
Examples described in JP-A-8, JP-A-3-37992, and JP-A-3-152184 are exemplified.

Of these, oxadiazole derivatives, benzoquinone or its derivatives,
Anthraquinone or a derivative thereof, or a metal complex of 8-hydroxyquinoline or a derivative thereof, polyquinoline or a derivative thereof, polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof is preferable, and 2- (4-biphenylyl) -5- (4-t More preferred are -butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline.

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.
nm.

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

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

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

As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression-bonded, or the like is used. Further, a layer made of a conductive polymer or a layer made of a metal oxide, a metal fluoride, an organic insulating material or the like having an average film thickness of 2 nm or less may be provided between the cathode and the organic material layer. A protective layer for protecting the polymer LED may be attached. In order to 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, and a method in which the cover is bonded to the element substrate with a heat effect resin or a photo-curing resin and sealed is preferable. Used for. If a space is maintained using a spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, the cathode can be prevented from being oxidized, and moisture adsorbed in the manufacturing process by installing a desiccant such as barium oxide in the space. It becomes easy to suppress giving an image to an element. Among these, it is preferable to take any one or more measures.

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

The polymer compound of the present invention is used as a dye for laser, a material for organic solar cell, an organic semiconductor for organic transistor, a material for conductive thin film, a material for polymer electronic device (electronic device including polymer). You can also.

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

Example 1
<Synthesis of N, N-bis (4-bromophenyl) -N ', N'-diphenyl-1,4-phenylenediamine>
Palladium acetate (0.09 g, 0.4 mmol), tris (2-methylphenyl) phosphine (0.268 g, 0.85 mmol) and 20 ml of toluene were placed in a reaction vessel and stirred at room temperature for 30 minutes. When a yellow homogeneous solution was obtained, tris (4-bromophenyl) amine (9.64 g, 20 mmol), sodium t-
Butoxide (2.75 g, 28 mmol) and 70 ml of toluene were added and heated to reflux. When refluxing began, bis (4-bromophenyl) amine (3.32 g
, 19.6 mmol) was dissolved in 50 ml of toluene and added dropwise. After dropping, 9
Heated to reflux for hours. After cooling to room temperature, it was treated with hydrochloric acid, extracted with toluene and dried. When toluene was distilled off, a dark brown oil was obtained. This was purified by a silica gel column using a mixed solvent of toluene: cyclohexane = 1: 10 as a developing solvent to obtain a white solid (3.16 g, 28%).

<Synthesis of Polymer Compound 1>
N, N-bis (4-bromophenyl) -N ′, N′-diphenyl-1,4-phenylenediamine 0.64 g, 2,7 dibromo-9,9-dioctylfluorene
44 g and 2,2′-bipyridyl 1.38 g were tetrahydrofuran (dehydrated)
After dissolving in 100 ml, the inside of the system was replaced with nitrogen gas by bubbling with nitrogen gas. To this solution, 2.5 g of bis (1,5-cyclooctadiene) nickel (0) was added, stirred for about 10 minutes at room temperature, then warmed and reacted at 60 ° C. for 3 hours.
After cooling this reaction solution, a mixed solution of 150 ml of methanol / 150 ml of ion-exchanged water was added and stirred for about 1 hour. The solution was allowed to stand at room temperature overnight, and then the produced precipitate was collected by filtration. Next, this precipitate was dried and then dissolved in toluene. The insoluble material was removed by filtration and then purified on a silica gel / alumina column. By pouring this toluene solution into methanol,
Reprecipitation was purified. The produced precipitate was collected and dried under reduced pressure to obtain 0.8 g of a polymer.
The resulting polymer is referred to as polymer compound 1.

該高分子化合物１のポリスチレン換算の数平均分子量は、３．７×１０⁴であっ
た。仕込みから推定される高分子化合物１に含まれる繰り返し単位の構造を下記
に示す。

The number average molecular weight in terms of polystyrene of the polymer compound 1 was 3.7 × 10 ^4. The structure of the repeating unit contained in the polymer compound 1 estimated from the preparation is shown below.

Example 2
<Synthesis of N, N-bis (4-bromophenyl) -N '-(3-methylphenyl) -N'-phenylbenzidine>
Bis (4-bromophenyl) amine (1.29 g, 3.9 mmol), N- (4′-iodobiphenyl-4-yl) -N- (m-tolyl) aniline (2.0 g, 4.3 m)
mol), 1,10-phenanthroline (0.052 g, 0.29 mmol),
Copper (I) chloride (0.028 g, 0.29 mmol), potassium hydroxide (1.71)
g, 30.4 mmol) and 10 ml of toluene are placed in a light-shielded reaction vessel, placed in an oil bath and heated to reflux at 125 ° C. for 12 hours. After cooling to room temperature, the mixture is separated with toluene and water, and the organic layer is extracted and dried over sodium sulfate. Concentrate the organic layer to 200 ml, add celite and activated alumina, stir at 75 ° C. for 2 hours, and decolorize. A yellowish transparent glassy solid (2.38 g, 50%) is obtained by a silica gel column using a mixed solvent of toluene: cyclohexane = 1: 5 as a developing solvent.

<Synthesis of Polymer Compound 2>
N, N-bis (4-bromophenyl) -N ′-(3-methylphenyl) -N′-phenylbenzidine 0.30 g, 2,7 dibromo-9,9-dioctylfluorene 0.5
9 g and 2,5′-bipyridyl 0.55 g were added to tetrahydrofuran (dehydrated) 4
After dissolving in 0 ml, the system was bubbled with nitrogen gas to replace the system with nitrogen gas. To this solution, 0.97 g of bis (1,5-cyclooctadiene) nickel (0) was added, stirred at room temperature for about 10 minutes, then warmed and reacted at 60 ° C. for 3 hours.
After cooling the reaction solution, a mixed solution of methanol 50 ml / ion exchanged water 50 ml was added and stirred for about 1 hour. The produced precipitate was collected by filtration.
Next, this precipitate was dried and then dissolved in toluene. The insoluble material was removed by filtration and then purified with an alumina column. The toluene solution was poured into methanol for purification by reprecipitation. The produced precipitate was collected and dried under reduced pressure to obtain 0.35 g of a polymer. The resulting polymer is referred to as polymer compound 2.
The number average molecular weight in terms of polystyrene of the polymer compound 2 was 4.3 × 10 ⁴ . The structure of the repeating unit contained in the polymer compound 2 estimated from the preparation is shown below.

Example 3
<Synthesis of N, N-bis (4-bromophenyl) -N ′, N′-bis (4-butylphenyl) -1,4-phenylenediamine>
Under an inert atmosphere, a 300 mL three-necked flask was charged with 0.24 g (0.27 mmol) of tris (dibenzylideneacetone) dipalladium, 0.22 g (0.4 mmol) of diphenylphosphinoferrocene, 2.5 mg of sodium tertiary butoxide.
Add 6 g (26.7 mmol) and 125 mL of toluene and stir at room temperature for 10 minutes. Subsequently, 12.9 g of tris- (4-bromophenyl) amine (26
. 7 mmol) and stir at room temperature for 10 minutes. Thereafter, 5 g (17.8 mmol) of bis (4-butylphenyl) amine was added, and the temperature was raised to 125 ° C.
Reflux for 9 hours. After completion of the reaction, the reaction solution is filtered to remove insolubles, then passed through a silica gel short column, and further purified with a silica gel column using cyclohexane as a developing solvent to obtain a white powder (2.96 g, 24%). .

<Synthesis of Polymer Compound 3>
N, N-bis (4-bromophenyl) -N ′, N′-bis (4-butylphenyl) -1,4-phenylenediamine 0.21 g, 2,7 dibromo-9,9-dioctylfluorene 0.38 g 390 mg of 2,2′-bipyridyl was dissolved in 28 ml of dehydrated tetrahydrofuran, and 690 mg of bis (1,5-cyclooctadiene) nickel (0) was added to this solution under a nitrogen atmosphere.
The temperature was raised to 0 ° C. and reacted for 3 hours. After the reaction, this reaction solution is cooled to room temperature, and 2
The solution was dropped into a mixed solution of 5% aqueous ammonia 10 ml / methanol 120 ml / ion exchanged water 50 ml and stirred for 1 hour, and then the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 50 ml of toluene. To this solution was added 30 ml of 1N hydrochloric acid and stirred at room temperature for 3 hours. After removing the aqueous layer, 30 ml of 4% aqueous ammonia was added and stirred at room temperature for 3 hours to remove the aqueous layer. The remaining toluene solution was reprecipitated by vaporizing with 150 ml of methanol, and insoluble matters were removed by filtration. Thereafter, the product was again dissolved in toluene and purified through an alumina column (activated alumina 10 g). The recovered toluene solution was dropped into 200 ml of methanol and stirred for 30 minutes, and the deposited precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained polymer was 300 mg. The resulting polymer is referred to as polymer compound 3.
The number average molecular weight in terms of polystyrene of the polymer compound 3 was 4.8 × 10 ⁴ . The structure of the repeating unit contained in the polymer compound 3 estimated from the preparation is shown below.

Example 4
<Synthesis of N, N-bis (4-bromophenyl) -N ′, N′-bis (4-methylphenyl) -1,4-phenylenediamine>
Under an inert atmosphere, in a 500 mL three-necked flask, 0.35 g (0.38 mmol) of tris (dibenzylideneacetone) dipalladium, 0.32 g (0.57 mmol) of diphenylphosphinoferrocene, sodium tertiary butoxide 7.
Add 31 g (76 mmol) and 178 mL of toluene and stir at room temperature for 10 minutes. Subsequently, 12.2 g of tris- (4-bromophenyl) amine (25.
3 mmol), and further stirred at room temperature for 10 minutes. Thereafter, 5 g (17.8 mmol) of p-tolyldiphenylamine is added, heated to 125 ° C. and refluxed for 9 hours. After completion of the reaction, the reaction solution is filtered to remove insolubles, then passed through a silica gel short column, and further purified with a silica gel column using cyclohexane as a developing solvent to obtain a white powder (1.20 g, 8%). .

<Synthesis of Polymer Compound 4>
N, N-bis (4-bromophenyl) -N ′, N′-bis (4-methylphenyl) -1,4-phenylenediamine 0.18 g, 2,7 dibromo-9,9-dioctylfluorene 0.38 g 390 mg of 2,2′-bipyridyl was dissolved in 28 ml of dehydrated tetrahydrofuran, and 690 mg of bis (1,5-cyclooctadiene) nickel (0) was added to this solution under a nitrogen atmosphere.
The temperature was raised to 0 ° C. and reacted for 3 hours. After the reaction, this reaction solution is cooled to room temperature, and 2
The solution was dropped into a mixed solution of 5% aqueous ammonia 10 ml / methanol 120 ml / ion exchanged water 50 ml and stirred for 1 hour, and then the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 50 ml of toluene. To this solution was added 30 ml of 1N hydrochloric acid and stirred at room temperature for 3 hours. After removing the aqueous layer, 30 ml of 4% aqueous ammonia was added and stirred at room temperature for 3 hours to remove the aqueous layer. The remaining toluene solution was reprecipitated by vaporizing with 150 ml of methanol, and insoluble matters were removed by filtration. Thereafter, the product was again dissolved in toluene and purified through an alumina column (activated alumina 10 g). The recovered toluene solution was dropped into 200 ml of methanol and stirred for 30 minutes, and the deposited precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained polymer was 270 mg. The resulting polymer is referred to as polymer compound 4.
The number average molecular weight in terms of polystyrene of the polymer compound 4 was 5.1 × 10 ⁴ . The structure of the repeating unit contained in the polymer compound 4 estimated from the preparation is shown below.

Comparative Example 1
<Synthesis of Polymer Compound 5>
After charging 0.82 g of 2,7-dibromo-9,9-dioctylfluorene and 0.56 g of 2,2′-bipyridyl into the reaction vessel, the inside of the reaction system was replaced with argon gas. To this, 15 ml of tetrahydrofuran (THF) (dehydrated) deaerated previously by bubbling with argon gas was added. Next, bis (1
, 5-cyclooctadiene) nickel (0) was added, and the mixture was stirred at room temperature for 10 minutes and then reacted at 60 ° C. for 8 hours. The reaction was performed in an argon gas atmosphere. After the reaction, this solution was cooled and then poured into a mixed solution of 25% aqueous ammonia 10 ml / ethanol 50 ml / ion exchanged water 50 ml and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried and then dissolved in chloroform. This solution was filtered to remove insoluble matters, poured into methanol, and reprecipitated to generate a precipitate. This was dried under reduced pressure to give a polymer 0.
35 g was obtained. This polymer is referred to as polymer compound 3.
The number average molecular weight in terms of polystyrene of the polymer compound 3 was 1.5 × 10 ⁵ . The structure of the repeating unit of the polymer compound 3 is shown below.

Example 5
<Evaluation of ionization potential>
The ionization potential was determined from the following equation from the measured oxidation potential (Eox).
Ip (eV) = Eox + Ag / AgCl reference electrode potential + standard hydrogen electrode potential = Eo
x + 0.196 + 4.5
The oxidation potential was measured as follows. The electrode was dipped in a chloroform solution of the polymer compound 1 and dried to form a thin film on the electrode to prepare a sample. Using a supporting electrolyte 0.1M tetra-n-butylammonium tetrafluoroborate in acetonitrile solution, cyclic voltammetry (working electrode,
Counter electrode: platinum, reference electrode: Ag / AgCl electrode, sweep speed: 50 mV / sec
) From the rising voltage of the voltammogram.
The ionization potentials of the polymer compounds 1, 2, 3, 4 thus obtained are
Each was 5.45, 5.55, 5.35, 5.31 (unit: eV). On the other hand, the ionization potential of the polymer compound 5 was 6.01 eV.
This indicates that the polymer compound of the present invention has excellent charge transport properties.

Claims (4)

  N, N-bis (4-bromophenyl) -N ', N'-diphenyl-1,4-phenylenediamine   N, N-bis (4-bromophenyl) -N '-(3-methylphenyl) -N'-phenylbenzidine   N, N-bis (4-bromophenyl) -N ′, N′-bis (4-butylphenyl) -1,4-phenylenediamine   N, N-bis (4-bromophenyl) -N ′, N′-bis (4-methylphenyl) -1,4-phenylenediamine