JP2009149846A - Composition containing amine compound and acceptor compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition excellent in positive hole injectability and element life when used as a material of an organic electroluminescent element. <P>SOLUTION: The composition comprises a compound represented by the formula (1), a compound having its residue or a compound containing a repeating unit, and an acceptor compound, wherein A ring, B ring and C ring each represents a monocyclic aromatic ring or a condensed aromatic ring; R<SP>1</SP>and R<SP>4</SP>each represents a monovalent group; R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>and R<SP>6</SP>each represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an alkeneyl group or an alkynyl group; A ring, B ring, C ring, R<SP>1</SP>and R<SP>4</SP>may have a substituent; an aryl group, an arylalkyl group, an alkenyl group and an alkynyl group represented by R<SP>5</SP>and R<SP>6</SP>may have a substituent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a composition comprising an amine compound and an acceptor compound.

  A composition containing an amine compound and an acceptor compound is useful as a material for an organic electroluminescence device, and various studies have been made. Specific examples thereof include a composition of triarylamine polymer and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (Patent Document 1), triphenylamine and Examples include a composition with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (Patent Document 2).

Special table 2005-531915 gazette JP 2007-208102 A

  However, even when the composition is used as a material for an organic electroluminescence device, the hole injection property and the device life are not sufficient.

  Therefore, an object of the present invention is to provide a composition excellent in hole injecting property and device life when used as a material for an organic electroluminescent device.

（式中、Ａ環、Ｂ環及びＣ環はそれぞれ独立に、単環の芳香環又は縮合した芳香環を表し、Ｒ¹及びＲ⁴はそれぞれ独立に、１価の基を表し、Ｒ²、Ｒ³、Ｒ⁵及びＲ⁶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、アルケニル基又はアルキニル基を表す。Ａ環、Ｂ環、Ｃ環、Ｒ¹及びＲ⁴は、置換基を有していてもよい。Ｒ²、Ｒ³、Ｒ⁵及びＲ⁶で表されるアリール基、アリールアルキル基、アルケニル基、アルキニル基は、置換基を有していてもよい。）
で表される化合物、その残基を有する化合物、又は下記式（２）：

（式中、Ａ環、Ｂ環、Ｃ環、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は、前記と同じ意味を有する。但し、Ａ環及びＣ環は、それぞれ結合手を有する。）
で表される繰り返し単位を含む化合物と、アクセプタ性化合物とを含む組成物、並びにこの組成物を用いてなる層を有する有機電界発光素子を提供する。 The present invention firstly has the following formula (1):

(In the formula, A ring, B ring and C ring each independently represent a monocyclic aromatic ring or a condensed aromatic ring, R ¹ and R ⁴ each independently represent a monovalent group, R ² , R ³ , R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an alkenyl group or an alkynyl group, A ring, B ring, C ring, R ¹ and R ⁴ are (The aryl group, arylalkyl group, alkenyl group and alkynyl group represented by R ² , R ³ , R ⁵ and R ⁶ may have a substituent.)
Or a compound having a residue thereof, or the following formula (2):

(In the formula, A ring, B ring, C ring, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as described above, provided that A ring and C ring are bonded to each other. Holding hand.)
The organic electroluminescent element which has a layer using the composition containing the compound containing the repeating unit represented by these and an acceptor compound, and this composition is provided.

  When the composition of the present invention is used as a material for an organic electroluminescence device (particularly, a material for a buffer layer), it has excellent hole injection properties and device lifetime. Therefore, the composition of the present invention is particularly useful as a material for an organic electroluminescent device.

Hereinafter, the present invention will be described in detail.
<Composition>
The composition of this invention contains the compound represented by the said Formula (1), the compound which has the residue, or the compound containing the repeating unit represented by the said Formula (2), and an acceptor compound. The compound represented by the formula (1), the compound having a residue thereof, the compound containing a repeating unit represented by the formula (2), and the acceptor compound may be used alone or in combination of two or more. You may use together.

-Description of Formula (1)-
In the formula (1), A ring, B ring and C ring each independently represent a monocyclic aromatic ring or a condensed aromatic ring. Moreover, A ring, B ring, and C ring may have a substituent, respectively.

  Examples of such an aromatic ring include a monocyclic aromatic ring and a condensed aromatic ring. Examples of the monocyclic aromatic ring include a benzene ring. Examples of the condensed aromatic ring include aromatic hydrocarbon rings such as naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, perylene ring, tetracene ring, pentacene ring, fluorene ring; pyridine ring, pyrimidine ring, pyridazine ring, Pyrazine ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, acridine ring, phenanthroline ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, thiophene oxide ring, benzothiophene oxide ring, dibenzothiophene oxide ring, furan ring, benzofuran Heteroaromatic rings such as ring, pyrrole ring, indole ring, dibenzopyrrole ring, silole ring, benzosilol ring, dibenzosilole ring, borol ring, benzovolol ring, dibenzoborol ring, etc., heat resistance, fluorescence intensity, From the viewpoint of the child characteristics, aromatic hydrocarbon ring is preferable. As the aromatic ring, a monocyclic aromatic ring which may have a substituent is particularly preferable.

  Examples of the substituent that the A ring, B ring and C ring may have include, for example, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, Arylalkoxy group, arylalkylthio group, alkenyl group, alkynyl group, disubstituted amino group, trisubstituted silyl group, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, substituted carboxyl Group, heteroaryloxy group, and heteroarylthio group.

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

  The alkyl group may be linear, branched or cyclic. The carbon number of such an alkyl group is usually about 1 to 30, and preferably about 3 to 15 from the viewpoint of solubility in an organic solvent. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a pentyl group, an isoamyl group, and a hexyl group. Cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl Group and perfluorooctyl group. From the viewpoint of solubility in organic solvents and ease of synthesis, pentyl group, isoamyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, 3, 7 -A dimethyloctyl group is preferred.

  The alkoxy group may be linear, branched or cyclic. The number of carbon atoms of such an alkoxy group is usually about 1 to 30, and preferably about 3 to 15 from the viewpoint of solubility in an organic solvent. Examples of such alkoxy groups include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, pentyloxy group, hexyloxy Group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, par A fluorobutoxy group, a perfluorohexyl group, a perfluorooctyl group, a methoxymethyloxy group, and a 2-methoxyethyloxy group can be mentioned. From the viewpoint of solubility in an organic solvent and ease of synthesis, a pentyloxy group, Hexyloxy group, octyloxy group, 2- Ethylhexyl group, decyloxy group, 3,7-dimethyl octyloxy group are preferable.

  The alkylthio group may be linear, branched or cyclic. Such an alkylthio group usually has about 1 to 30 carbon atoms, and preferably about 3 to 15 from the viewpoint of solubility in an organic solvent. Examples of such an alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an i-propylthio group, a butylthio group, an i-butylthio group, an s-butylthio group, a t-butylthio group, a pentylthio group, a hexylthio group, and a cyclohexylthio group. Group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, trifluoromethylthio group, and so on. From the viewpoint of ease of operation, a pentylthio group, a hexylthio group, an octylthio group, a 2-ethylhexylthio group, a decylthio group, and a 3,7-dimethyloctylthio group are preferable.

The aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and has a condensed ring, two or more independent benzene rings or condensed rings bonded directly or through a group such as vinylene. Also included. The carbon number of such an aryl group is usually about 6 to 60, preferably about 6 to 30. Examples of such aryl group include a phenyl group, C ₁ -C ₁₂ alkoxyphenyl group (C ₁ -C _12, the number of carbon atoms of the organic groups shown immediately after the C ₁ -C ₁₂ (here, alkoxyphenyl group The number of carbon atoms in the alkoxy group is ₁ to _{12. The same} applies to the following.), C1-C12 alkylphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, but pentafluorophenyl group, solubility in organic solvents, from the viewpoint of easiness of synthesis, C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C _{A 12} alkylphenyl group is preferred. As the C ₁ -C ₁₂ alkoxyphenyl group, for example, methoxyphenyl group, ethoxyphenyl group, propyloxyphenyl group, i- propyl group, a butoxyphenyl group, i- butoxyphenyl, s- butoxyphenyl T-butoxyphenyl group, pentyloxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group, 3 , 7-dimethyloctyloxyphenyl group, lauryloxyphenyl group. Further, as the C ₁ -C ₁₂ alkylphenyl group, for example, methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, i- propylphenyl group, butylphenyl group, i -Butylphenyl group, s-butylphenyl group, t-butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group It is done.

The carbon number of the aryloxy group is usually about 6 to 60, and preferably about 6 to 30. Examples of such an aryloxy group include a phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyl group there may be mentioned, solubility in organic solvents, from the viewpoint of easiness of synthesis, C ₁ -C ₁₂ alkoxy phenoxy group, a C ₁ -C ₁₂ alkylphenoxy group are preferable. Examples of the C _{1 to} C ₁₂ alkoxyphenoxy group include a methoxyphenoxy group, an ethoxyphenoxy group, a propyloxyphenoxy group, an i-propyloxyphenoxy group, a butoxyphenoxy group, an i-butoxyphenoxy group, and an s-butoxyphenoxy group. T-butoxyphenoxy group, pentyloxyphenoxy group, hexyloxyphenoxy group, cyclohexyloxyphenoxy group, heptyloxyphenoxy group, octyloxyphenoxy group, 2-ethylhexyloxyphenoxy group, nonyloxyphenoxy group, decyloxyphenoxy group, 3 , 7-dimethyloctyloxyphenoxy group, lauryloxyphenoxy group. Further, examples of the C ₁ -C ₁₂ alkylphenoxy group include, for example, methylphenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-trimethylphenoxy group, methylethylphenoxy group, i-propylphenoxy group. Group, butylphenoxy group, i-butylphenoxy group, s-butylphenoxy group, t-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group Group, dodecylphenoxy group.

The carbon number of the arylthio group is usually about 6 to 60, and preferably about 6 to 30. Such an arylthio group, for example, phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group, pentafluorophenyl thio group It is done. Among these, C ₁ -C ₁₂ alkoxyphenylthio groups and C ₁ -C ₁₂ alkylphenylthio groups are preferred from the viewpoints of solubility in organic solvents and ease of synthesis.

The carbon number of the arylalkyl group is usually about 7 to 60, preferably about 7 to 30. Such arylalkyl groups, such as phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ An alkyl group, a 1-naphthyl-C ₁ -C ₁₂ alkyl group, and a 2-naphthyl-C ₁ -C ₁₂ alkyl group can be mentioned. From the viewpoint of solubility in organic solvents and ease of synthesis, 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 carbon number of the arylalkoxy group is usually about 7 to 60, preferably about 7 to 30. Examples of such an arylalkoxy group include phenyl-C ₁ -C ₁ such as phenylmethoxy group, phenylethoxy group, phenylbutoxy group, phenylpentyloxy group, phenylhexyloxy group, phenylheptyloxy group, and phenyloctyloxy group. 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 group, 2 - Although naphthyl -C ₁ -C ₁₂ alkoxy group, solubility in organic solvents, from the viewpoint of easiness of synthesis, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ ~ C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkoxy groups are preferred.

The carbon number of the arylalkylthio group is usually about 7 to 60, preferably about 7 to 30. Such an arylalkylthio group, for example, phenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ Alkylthio group, 1-naphthyl-C ₁ -C ₁₂ alkylthio group, 2-naphthyl-C ₁ -C ₁₂ alkylthio group can be mentioned. From the viewpoint of solubility in organic solvents and ease of synthesis, C _1- C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group are preferable.

  The carbon number of the alkenyl group is usually about 2 to 30, preferably about 2 to 15. Examples of such an alkenyl group include a vinyl group, a 1-propylenyl group, a 2-propylenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, and a cyclohexenyl group. Such alkenyl groups also include dienyl groups and trienyl groups such as 1,3-butadienyl group, cyclohexa-1,3-dienyl group, and 1,3,5-hexatrienyl group.

  The alkynyl group usually has about 2 to 30 carbon atoms, preferably about 2 to 15 carbon atoms. Examples of such alkynyl group include ethynyl group, 1-propynyl group, 2-propylenyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, and cyclohexylethynyl group. Such alkynyl groups also include diynyl groups such as 1,3-butadiynyl groups.

Examples of the disubstituted amino group include an amino group substituted with two groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. In such a disubstituted amino group, the alkyl group, aryl group, arylalkyl group, and monovalent heterocyclic group each may have a substituent. Moreover, carbon number of such a disubstituted amino group is about 2-60 normally, without including the carbon number of the substituent which an alkyl group etc. have, Preferably it is about 2-30. Examples of such disubstituted amino groups include dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di-t-butylamino, dipentylamino, and dihexylamino. Group, dicyclohexylamino group, diheptylamino group, dioctylamino group, di-2-ethylhexylamino group, dinonylamino group, didecylamino group, di-3,7-dimethyloctylamino group, dilaurylamino group, dicyclopentylamino group, Dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group phenylamino group, diphenylamino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino group, di -1-Naphthyl Amino group, di-2-naphthylamino group, di-pentafluorophenyl group, dipyridyl amino group, di pyridazinylamino group, di pyrimidyl amino group, Jipirajiruamino group, di Agile amino group, di (phenyl -C It includes ₁ -C ₁₂ alkyl) amino Motoji (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino group .

Examples of the trisubstituted silyl group include a silyl group substituted with three groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. The carbon number of such a trisubstituted silyl group is usually about 3 to 90, preferably about 3 to 45. In such a trisubstituted silyl group, the alkyl group, aryl group, arylalkyl group, and monovalent heterocyclic group may have a substituent. Examples of such trisubstituted silyl groups include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, t-butyl. Silyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl- dimethylsilyl group, lauryldimethylsilyl group, a phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group, 1-naphthyl -C ₁ -C ₁₂ Rukirushiriru group, 2-naphthyl -C ₁ -C ₁₂ alkylsilyl group, a phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzylsilyl group, diphenylmethylsilyl group, Examples thereof include t-butyldiphenylsilyl group and dimethylphenylsilyl group.

  The carbon number of the acyl group is usually about 2-30, preferably about 2-15. Examples of such an acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

  The carbon number of the acyloxy group is usually about 2 to 30, preferably about 2 to 15. Examples of such an acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

（式中、Ｍｅはメチル基を表す。以下、同様である。） The carbon number of the imine residue is usually about 2 to 30, preferably about 2 to 15. Examples of such an imine residue include groups represented by the structural formulas shown below. In the structural formula shown below, the wavy line represents syn or anti, but may be syn or anti.

(In the formula, Me represents a methyl group. The same applies hereinafter.)

  The carbon number of the amide group is usually about 2-30, preferably about 2-15. Examples of such amide groups include formamide, acetamide, propioamide, butyroamide, benzamide, trifluoroacetamide, pentafluorobenzamide, diformamide, diacetamide, dipropioamide, dibutyroamide, Examples thereof include a benzamide group, a ditrifluoroacetamide group, and a dipentafluorobenzamide group.

As said acid imide group, the residue obtained by remove | excluding the hydrogen atom couple | bonded with the nitrogen atom from acid imide is mentioned. The carbon number of such an acid imide group is usually about 4 to 30, preferably about 4 to 15. Examples of such acid imide groups include groups represented by the structural formulas shown below.

The monovalent heterocyclic group refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound. The carbon number of such a monovalent heterocyclic group is usually about 2 to 30, preferably about 2 to 15. In such a monovalent heterocyclic group, the heterocyclic ring may have a substituent, but the carbon number does not include the carbon number of the substituent on the heterocyclic ring. In addition, here, the heterocyclic compound is an organic compound having a cyclic structure in which not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus and boron are present in the ring. This includes things. Examples of such a monovalent heterocyclic group, for example, thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, piperidyl group, quinolyl group, An isoquinolyl group is mentioned. Among these, a monovalent aromatic heterocyclic group is preferable, and a thienyl group, a C _{1 to} C ₁₂ alkyl thienyl group, a pyridyl group, and a C _{1 to} C ₁₂ alkyl pyridyl group are particularly preferable.

  Examples of the substituted carboxyl group include a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group. The carbon number of such a substituted carboxyl group is usually about 2 to 30, preferably about 2 to 15. Examples of such a substituted carboxyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an i-propoxycarbonyl group, a butoxycarbonyl group, an i-butoxycarbonyl group, a t-butoxycarbonyl group, a pentyloxycarbonyl group, Hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxy Carbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perf Oro octyloxy group, phenoxycarbonyl group, naphthoxycarbonyl group, and pyridyloxycarbonyl group. In such a substituted carboxyl group, the alkyl group, aryl group, arylalkyl group, and monovalent heterocyclic group may have a substituent. Further, the carbon number of the substituted carboxyl group does not include the carbon number of the substituent such as an alkyl group.

The heteroaryloxy group (i.e., group (wherein represented by Q ¹ -O-, Q ¹ represents a monovalent heterocyclic group)) the number of carbon atoms of is usually about 2 to 30, preferably It is about 2-15. In such a heteroaryloxy group, the monovalent heterocyclic group may have a substituent, but the carbon number of the heteroaryloxy group depends on the number of substituents on the monovalent heterocyclic group. Carbon number is not included. Such heteroaryl group, for example, thienyloxy group, C ₁ -C ₁₂ alkyl thienyl group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C ₁ -C ₁₂ alkyl pyridyl group, imidazolyloxy group , A pyrazolyloxy group, a triazolyloxy group, an oxazolyloxy group, a thiazoleoxy group, and a thiadiazoleoxy group. Q ¹ is preferably a monovalent aromatic heterocyclic group.

The heteroarylthio group (i.e., group (wherein represented by Q ² -S-, Q ² represents a monovalent heterocyclic group)) the number of carbon atoms of is usually about 2 to 30, preferably It is about 2-15. In such a heteroarylthio group, the monovalent heterocyclic group may have a substituent, but the number of carbon atoms of the heteroarylthio group depends on the number of substituents on the monovalent heterocyclic group. Carbon number is not included. Such heteroarylthio group, thienylmercapto group, C ₁ -C ₁₂ alkyl thienylmercapto group, pyrrolyl mercapto group, a furyl mercapto group, pyridyl mercapto group, C ₁ -C ₁₂ alkyl pyridyl mercapto group, imidazolylmethyl mercapto group , Pyrazolyl mercapto group, triazolyl mercapto group, oxazolyl mercapto group, thiazole mercapto group, thiadiazole mercapto group. Q ² is preferably a monovalent aromatic heterocyclic group.

In the formula (1), R ¹ and R ⁴ each independently represents a monovalent group.

  In this specification, examples of the monovalent group include an alkyl group, an aryl group, an arylalkyl group, an alkenyl group, an alkynyl group, a trisubstituted silyl group, an acyl group, a monovalent heterocyclic group, and a substituted carboxyl group. Can be mentioned.

  These alkyl groups, aryl groups, arylalkyl groups, alkenyl groups, alkynyl groups, trisubstituted silyl groups, acyl groups, monovalent heterocyclic groups and substituted carboxyl groups have A ring, B ring and C ring. Examples thereof may be the same as those described and exemplified as the substituents that may be present.

From the viewpoint of the stability of the compound, R ¹ and R ⁴ are preferably each independently an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and more preferably an aryl group.

In the formula (1), R ² , R ³ , R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an alkenyl group or an alkynyl group.

The alkyl group represented by R ² , R ³ , R ⁵ and R ⁶ may be linear, branched or cyclic, but has no substituent. The carbon number of such an alkyl group is usually about 1 to 30, and preferably about 3 to 15 from the viewpoint of solubility in an organic solvent. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a pentyl group, an isoamyl group, and a hexyl group. Cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl Group and perfluorooctyl group. From the viewpoint of solubility in organic solvents and ease of synthesis, pentyl group, isoamyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, 3, 7 -A dimethyloctyl group is preferred.

The aryl group, arylalkyl group, alkenyl group and alkynyl group represented by R ² , R ³ , R ⁵ and R ⁶ are exemplified as the substituents that the A ring, B ring and C ring may have. The thing similar to a thing is mentioned.

In the formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are particularly preferably an aryl group which may have a substituent.

Specific examples of the compound represented by the formula (1) are given below.

  The compound having a residue of the compound represented by the formula (1) is a compound having a residue that is a remaining atomic group obtained by removing one or more hydrogen atoms from the compound represented by the formula (1). It is.

Specific examples of the compound having a residue of the compound represented by the formula (1) are given below.

-Explanation of Formula (2)-
In the formula (2), A ring, B ring and C ring each independently represent a monocyclic aromatic ring or a condensed aromatic ring, R ¹ and R ⁴ each independently represent a monovalent group, R ² , R ³ , R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an alkenyl group or an alkynyl group. The A ring, B ring, C ring, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as those described and exemplified in the section of the formula (1). However, it has a bond on A ring and C ring. In addition, it is preferable that the position of the said bond is a position where conjugation in a molecule | numerator connects from a viewpoint of the electroconductivity of the compound obtained.

  The compound containing the repeating unit represented by the formula (2) may be a compound consisting only of the repeating unit represented by the formula (2) or a compound containing another repeating unit. Here, the “repeating unit” means a unit that is repeatedly contained in a molecule two or more times.

Specific examples of the repeating unit represented by the formula (2) are given below.

（式中、Ａｒ¹はアリーレン基又は２価の複素環基を表す。Ｒ⁷及びＲ⁸はそれぞれ独立に、水素原子、アルキル基、アリール基、１価の複素環基又はシアノ基を表す。ｎは０又は１を表す。Ａｒ¹、Ｒ⁷及びＲ⁸は、置換基を有していてもよい。） Furthermore, from the viewpoint of excellent device characteristics such as lifetime when used in an organic electroluminescent device, the compound containing the repeating unit represented by the formula (2) further includes a repeating unit represented by the following formula (3). It is preferable to include.

(In the formula, Ar ¹ represents an arylene group or a divalent heterocyclic group. R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. n represents 0 or 1. Ar ¹ , R ⁷ and R ⁸ may have a substituent.

Such an arylene group in Ar ¹ usually has 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms. Examples of the arylene group in Ar ¹ include a phenylene group (for example, the following formulas 1 to 3), a naphthalenediyl group (for example, the following formulas 4 to 13), an anthracenylene group (for example, the following formulas 14 to 19), Examples include biphenylene groups (for example, the following formulas 20 to 25), triphenylene groups (for example, the following formulas 26 to 28), and condensed ring compound groups (for example, the following formulas 29 to 38). In the formulas shown below, each R is independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, or an arylalkylthio group. Represents an alkenyl group, an alkynyl group, a heteroaryloxy group or a heteroarylthio group. The carbon number of the arylene group does not include the carbon number when R is a substituent. R represents a hydrogen atom or a substituent, and the substituent has the same meaning as described and exemplified as the substituent which the A ring, the B ring and the C ring may have. It is.

  In the present specification, the divalent heterocyclic group refers to a remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound. The carbon number of such a divalent heterocyclic group is usually 4 to 60, preferably 4 to 20. Here, the heterocyclic compound is an organic compound having a cyclic structure, in which the atoms constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus and boron in the ring. Say things.

Examples of such a divalent heterocyclic group include the following. In the formulas shown below, R has the same meaning as described above.
Examples of the divalent heterocyclic group containing nitrogen as a hetero atom include a pyridine-diyl group (for example, the following formulas 39 to 44), a diazaphenylene group (for example, the following formulas 45 to 48), and a quinoline diyl group (for example, the following Formulas 49 to 63), quinoxaline diyl groups (for example, the following formulas 64-68), acridine diyl groups (for example, the following formulas 69 to 72), bipyridyldiyl groups (for example, the following formulas 73 to 75), phenanthroline diyl groups (for example And the following formulas 76 to 78).
Examples of the group containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom and having a fluorene structure include groups represented by the following formulas 79 to 98. Among these, it is desirable to have an aromatic amine monomer such as carbazole or triphenylaminediyl group represented by the following formulas 82 to 84 containing a nitrogen atom.
Examples of the 5-membered heterocyclic group containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom include groups represented by the following formulas 94 to 98.
Examples of the 5-membered condensed heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a hetero atom include, for example, groups represented by the following formulas 99 to 109, benzothiadiazole-4,7-diyl group, benzooxadiazole A -4,7-diyl group is mentioned.
A 5-membered heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom and bonded to the α-position of the heteroatom to form a dimer or an oligomer includes, for example, the following formulas 110 to 111: And the group represented.
Examples of the group bonded to the phenyl group at the α-position of the hetero atom in a 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a hetero atom include groups represented by the following formulas 112 to 118: Is mentioned.
Examples of a tricyclic group in which a condensed heterocyclic group containing nitrogen, oxygen, sulfur or the like as a hetero atom and a benzene ring or a monocyclic heterocyclic group are bonded include, for example, groups represented by the following formulas 120 to 125 Is mentioned.

（式中、Ｒは水素原子又は置換基を表す。）

(In the formula, R represents a hydrogen atom or a substituent.)

In the formula (3), the alkyl group, aryl group and monovalent heterocyclic group represented by R ⁷ and R ⁸ are exemplified as the substituents that the A ring, B ring and C ring may have. The same as described above.

（式中、Ｃ⁴環及びＣ⁵環はそれぞれ独立に、置換基を有していてもよい芳香族炭化水素環を表し、２つの結合手はそれぞれＣ⁴環又はＣ⁵環上に存在し、Ｒｗ及びＲｘはそれぞれ独立に、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、２置換アミノ基、３置換シリル基、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、置換カルボキシル基、ヘテロアリールオキシ基又はヘテロアリールチオ基を表す。Ｒｗ及びＲｘは、置換基を有していてもよい。）
で表されるものであることが好ましい。 In the repeating unit represented by the formula (3), it is preferable that n is 0 and Ar ¹ is an arylene group. As the repeating unit represented by the formula (3), the following formula (4-1):

(In the formula, each of C ⁴ ring and C ⁵ ring independently represents an aromatic hydrocarbon ring which may have a substituent, and two bonds are present on C ⁴ ring or C ⁵ ring, respectively. , Rw and Rx are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, alkenyl group, alkynyl group, 2 Rw represents a substituted amino group, a trisubstituted silyl group, an acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a substituted carboxyl group, a heteroaryloxy group, or a heteroarylthio group. And Rx may have a substituent.)
It is preferable that it is represented by these.

  The aromatic hydrocarbon ring means a benzene ring or a condensed aromatic hydrocarbon ring. Such an aromatic hydrocarbon ring has about 6 to 30 carbon atoms, preferably about 6 to 15 carbon atoms. The carbon number of the aromatic hydrocarbon ring does not include the carbon number of the substituent. Examples of such aromatic hydrocarbon rings include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, naphthacene ring, triphenylene ring, pyrene ring, chrysene ring, pentacene ring, perylene ring, pentalene ring, indene. And a ring, an azulene ring, a biphenylene ring, a fluorene ring, and an acenaphthylene ring.

  Alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, alkenyl group, alkynyl group, disubstituted amino group, trisubstituted silyl group in Rw and Rx , Acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, substituted carboxyl group, heteroaryloxy group, heteroarylthio group include A ring, B ring and C ring. The thing similar to what was demonstrated and illustrated as a substituent which you may have is mentioned. Rw and Rx are preferably alkyl groups.

  Examples of the repeating unit represented by the formula (4-1) include repeating units represented by the following formulas 1A-0 to 1A-13. In addition, such a repeating unit includes an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an alkenyl group, an alkynyl group, and a disubstituted amino group. Group consisting of 3-substituted silyl group, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, substituted carboxyl group, heteroaryloxy group, heteroarylthio group, halogen atom, etc. It may have at least one substituent selected from In the following formulas 1A-0 to 1A-13, the bond in the aromatic hydrocarbon can take any position.

  Among these repeating units, repeating units represented by Formulas 1A-0, 1A-1, 1A-2, and 1A-3 are preferable, and repeating units represented by Formula 1A-0 are particularly preferable.

（式中、Ａｒ²、Ａｒ³、Ａｒ⁴及びＡｒ⁵はそれぞれ独立に、アリーレン基又は２価の複素環基を表す。Ａｒ⁶、Ａｒ⁷及びＡｒ⁸はそれぞれ独立に、アリール基又は１価の複素環基を表す。Ｂ及びｂはそれぞれ独立に、０又は正の整数を表す。Ａｒ²、Ａｒ³、Ａｒ⁴、Ａｒ⁵、Ａｒ⁶、Ａｒ⁷及びＡｒ⁸は置換基を有していてもよい。）

（式中、Ｄ環及びＥ環はそれぞれ独立に、芳香環を表す。Ｙ¹は−Ｏ−、−Ｓ−又は−Ｃ（＝Ｏ）−を表す。Ｒ²⁰は１価の基を表す。Ｄ環及びＥ環は、それぞれ結合手を有する。Ｄ環、Ｅ環、Ｙ¹及びＲ²⁰は、置換基を有していてもよい。）

（式中、Ｙ²は−Ｏ−又は−Ｓ−を表す。） Moreover, the compound containing the repeating unit represented by the formula (2) is represented by the following formulas (5-1), (5-2), and (5-3) from the viewpoint of improving heat resistance and improving charge transportability. It is preferable to further include at least one type of repeating unit selected from the group consisting of repeating units represented by: more preferably two or more types of repeating units.

(In the formula, Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ each independently represent an arylene group or a divalent heterocyclic group. Ar ⁶ , Ar ⁷ and Ar ⁸ each independently represent an aryl group or a monovalent group. And B and b each independently represent 0 or a positive integer, Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ and Ar ⁸ have a substituent. May be.)

(In the formula, D ring and E ring each independently represent an aromatic ring. Y ¹ represents —O—, —S— or —C (═O) —. R ²⁰ represents a monovalent group. D ring and E ring each have a bond. D ring, E ring, Y ¹ and R ²⁰ may have a substituent.)

(In the formula, Y ² represents —O— or —S—.)

In the repeating unit represented by the formula (5-1), Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are each independently an arylene group from the viewpoint of device characteristics such as device lifetime, and Ar ⁶ , Ar ⁷ In addition, it is preferable that Ar ⁸ and each independently represent an aryl group. In addition, it is preferable that Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are each independently an unsubstituted phenylene group, an unsubstituted biphenylene group, an unsubstituted naphthylene group, or an unsubstituted anthracenediyl group. Furthermore, from the viewpoints of solubility in organic solvents, device characteristics, and the like, it is preferable that Ar ⁶ , Ar ⁷ and Ar ⁸ are each independently an aryl group having a substituent, and aryl having three or more substituents What is a group is more preferable. Furthermore, it is more preferable that Ar ⁶ , Ar ⁷ and Ar ⁸ are a phenyl group having 3 or more substituents, a naphthyl group having 3 or more substituents, or an anthracenyl group having 3 or more substituents. More preferably, Ar ⁶ , Ar ⁷ and Ar ⁸ are phenyl groups having three or more substituents.

Among these repeating units, Ar ⁶ , Ar ⁷ and Ar ⁸ are each independently a group represented by the following formula (5-4) and preferably have B + b ≦ 3, and B + b = 1. More preferred are those with B = 1 and b = 0.

  In the formula (5-4), Re, Rf and Rg are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, aryl An alkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a silyloxy group, a substituted silyloxy group, a monovalent heterocyclic group, or a halogen atom is represented. Moreover, the hydrogen atom contained in Re, Rf, and Rg may be substituted with a fluorine atom. Further, Rh and Ri are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl. Represents a group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a silyloxy group, a substituted silyloxy group, a monovalent heterocyclic group or a halogen atom. Moreover, the hydrogen atom contained in Rh and Ri may be substituted with a fluorine atom.

  In the formula (5-4), Re and Rf are each independently an alkyl group having 3 or less carbon atoms, an alkoxy group having 3 or less carbon atoms, or an alkylthio group having 3 or less carbon atoms, and Rg is the number of carbon atoms. It is preferable that they are a 1-30 alkyl group, a C1-C30 alkoxy group, and a C1-C30 alkylthio group.

In the repeating unit represented by the formula (5-1), Ar ³ is preferably a group represented by the following formula (5-5) or (5-6).

  In the formulas (5-5) and (5-6), the benzene ring contained in the structure is preferably an unsubstituted benzene ring, but each may independently have 1 or more and 4 or less substituents. Good. These substituents may be the same as or different from each other. In addition, other aromatic hydrocarbon rings or heterocyclic rings may be condensed with such a benzene ring.

（式中、Ｒは、前記と同じ意味を有する。） Examples of the repeating unit represented by the formula (5-1) include those represented by the following formulas 133 to 140.

(In the formula, R has the same meaning as described above.)

  In the case where R in the above formula is a substituent containing an alkyl group, an alkyl group having 3 or more carbon atoms is preferably contained in order to enhance the solubility of the polymer compound in an organic solvent. Furthermore, among the structures represented by the above formulas 133 to 140, the structures represented by the above formulas 133, 134, and 137 are preferable from the viewpoint of adjusting the emission wavelength.

（式中、Ｒｅ、Ｒｆ、Ｒｇ、Ｒｈ及びＲｉは、前記と同じ意味を有する。） More preferable examples of the repeating unit represented by the formula (5-1) include those represented by the following formulas 141 to 143.

(In the formula, Re, Rf, Rg, Rh and Ri have the same meaning as described above.)

Particularly preferred examples of the repeating unit represented by the formula (5-1) include those represented by the following formulas (22) to (24) from the viewpoint of heat resistance and the like.

  In the formula (5-2), the D ring and the E ring each independently represent an aromatic ring. A substituent may be present on the D ring and the E ring. The aromatic ring is preferably an aromatic hydrocarbon ring, particularly preferably a benzene ring, from the viewpoint of the stability of the compound.

In the formula (5-2), Y ¹ is preferably —CH ₂ —. Further, the monovalent group represented by R ²⁰ is the same as described and exemplified as the monovalent group represented by R ¹ and R ⁴ .

（式中、Ｙ¹及びＲ²⁰は、前記と同じ意味を有する。） Examples of the repeating unit represented by the formula (5-2) include those represented by the following formula (5-7).

(In the formula, Y ¹ and R ²⁰ have the same meaning as described above.)

Specific examples of the repeating unit represented by the formula (5-3) include the following.

  Among the compounds containing the repeating unit represented by the formula (2), those which are conjugated polymers from the viewpoint of device properties such as charge transportability when formed into a thin film and lifetime when used in an organic electroluminescent device. Is preferred. Here, the conjugated polymer means a polymer in which delocalized π electron pairs exist along the main chain skeleton of the polymer. As this delocalized π electron pair, an unpaired electron or a lone electron pair may participate in resonance instead of a double bond.

（式中、Ｒは前記と同じ意味を有する。Ａｒは芳香族炭化水素環又は複素環を表す。） In the compound containing the repeating unit represented by the formula (2), it may be linked with a non-conjugated unit within a range not impairing the light emission property and the charge transporting property, and the repeating unit contains the non-conjugated unit. It may be. Examples of the non-conjugated unit include a structure represented by the following formula and a combination of two or more of the structures represented by the following formula.

(In the formula, R has the same meaning as described above. Ar represents an aromatic hydrocarbon ring or a heterocyclic ring.)

  Further, the compound containing the repeating unit represented by the formula (2) may be a random, block or graft copolymer, or a polymer having an intermediate structure thereof, for example, a block property. It may be a random copolymer. From the viewpoint of obtaining a compound having a high fluorescence or phosphorescence quantum yield, a random copolymer having a block property and a block or graft copolymer are preferable to a complete random copolymer. Furthermore, the compound containing the repeating unit represented by the formula (2) includes those having a branched main chain and having three or more terminal portions, and dendrimers.

  In the compound containing the repeating unit represented by the formula (2), the ratio of the repeating unit represented by the formula (2) is preferably 10 to 100 mol% with respect to all repeating units. More preferably, it is -70 mol%.

（式中、ｎは、各繰り返し単位のモル比を表す数である。） Examples of the compound containing the repeating unit represented by the formula (2) are listed below.

(In the formula, n is a number representing the molar ratio of each repeating unit.)

  Among the compounds of the present invention, among the compounds represented by the formula (1), the compounds having a residue thereof, and the compounds containing the repeating unit represented by the formula (2), an organic electroluminescent device can be formed by a coating method. Therefore, a compound containing a repeating unit represented by the formula (2) is preferable.

The compound represented by the formula (1) and the compound having a residue thereof preferably have a molecular weight of 300 to 5000, more preferably 1000 to 3000, and still more preferably 1000 to 2000.
The compound containing the repeating unit represented by the formula (2) preferably has a polystyrene-equivalent number average molecular weight of 2 × 10 ³ or more, more preferably 2 × 10 ³ to 1 × 10 ⁸ , It is particularly preferably 1 × 10 ⁴ to 1 × 10 ⁶ .

-Acceptor compound-
Examples of the acceptor compound include quinone compounds, transition metal complex compounds, organic closed-shell anionic compounds, fluorene compounds having a cyano group and a nitro group, tetracyanoethylene, tetracyanobutadiene, lithium hexafluoroarsenate, triphosphate phosphate. Examples include chloride, fluoranyl, chloranil, bromanyl and the like. These acceptor compounds may be used alone or in combination of two or more. In the following description, the redox half-wave potential E ¹ _1/2 may be simply referred to as “E ¹ _1/2 ”.

Examples of the quinone compound include a p-benzoquinone derivative, a tetracyanoquinodimethane derivative, a 1,4-naphthoquinone derivative, a diphenoquinone derivative, and the like, and the value of the redox half-wave potential E ¹ _1/2 is large. From this viewpoint, p-benzoquinone derivatives and tetracyanoquinodimethane derivatives are preferred.

Examples of the p-benzoquinone derivative include 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) [E ¹ _1/2 = + 0.56 (V)], 2,3-dibromo-5,6. -Dicyano-p-benzoquinone (DBDQ) [E ¹ _1/2 = + 0.53 (V)], 2,3-diiodo-5,6-dicyano-p-benzoquinone (DIDQ) [E ¹ _1/2 = + 0 .51 (V)], 2,3-dicyano-p-benzoquinone (Q (CN) ₂ ) [E ¹ _1/2 = + 0.34 (V)] and the like.

Examples of the tetracyanoquinodimethane derivative include 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) [E ¹ _1/2 = + 0.60 ( V)], 2,3,5-trifluoromethyl-7,7,8,8-tetracyanoquinodimethane (CF3-TCNQ) [E ¹ _1/2 = + 0.43 (V)], 2,5 -Difluoro-7,7,8,8-tetracyanoquinodimethane (F2-TCNQ) [E ¹ _1/2 = + 0.40 (V)], 2-monofluoro-7,7,8,8-tetra Cyanoquinodimethane (F-TCNQ) [E ¹ _1/2 = + 0.32 (V)], 11, 11, 12, 12-tetracyanonaphth-2,6-quinodimethane (TNAP) [E ¹ _1/2 = + 0.26 (V)], 7,7,8,8- tetracyanoquinodimethane _{^{(TCNQ) [E 1 1/2 =}} + 0.22 V)], decyl-7,7,8,8-tetracyanoquinodimethane ^{(C10-TCNQ) [E 1} 1/2 = + 0.20 (V)] and the like.

Examples of the 1,4-naphthoquinone derivative include 2,3-dicyano-5-nitro-1,4-naphthoquinone (DCNNQ) [E ¹ _1/2 = + 0.38 (V)], 2,3-dicyano-1 , 4-naphthoquinone (DCNQ) [E ¹ _1/2 = + 0.21 (V)] and the like.

  Examples of the diphenoquinone derivative include 3,3 ', 5,5'-tetrabromo-diphenoquinone (TBDQ) and the like.

Examples of the transition metal complex compounds include (TPP) ₂ Pd (dto) ₂ [E ¹ _1/2 = + 1.20 (V)], (TPP) ₂ Pt (dto) ₂ [E ¹ _1/2 = + 0.90 (V)], (TPP) ₂ Ni (dto) ₂ [E ¹ _1/2 = + 0.57 (V)], (TPP) ₂ Cu (dto) ₂ [E ¹ _1/2 = + 0 .08 (V)], (TBA) ₂ Cu (ox) ₂ [E ¹ _1/2 = + 1.28 (V)], etc., but the value of the redox half-wave potential E ¹ _1/2 is large. From this viewpoint, (TPP) ₂ Pd (dto) ₂ and (TBA) ₂ Cu (ox) ₂ are preferable.

  Examples of the organic closed-shell anionic compound include picrate and tosylate.

Examples of the fluorene-based compound having a cyano group and a nitro group include 9-dicyanomethylene-2,4,5,7-tetranitro-fluorenone (DTENF) [E ¹ _1/2 = + 0.23 (V)], 9-dicyanomethylene-2,4,7-trinitro-fluorenone (DTNF) [E ¹ _1/2 = + 0.01 (V)], 2,4,5,7-tetranitrofluorenone (TENF) [E ¹ _{1 / 2 = -0.13 (V)]} , 2,4,7- trinitrofluorenone _{^{(TNF) [E 1 1/2 =}} -0.42 (V)] and others as mentioned, redox half-wave potential From the viewpoint of the value of E ¹ _1/2 , 9-dicyanomethylene-2,4,5,7-tetranitro-fluorenone (DTENF) is preferred.

Examples of the acceptor compound include 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro, from the viewpoint of the magnitude of the redox half-wave potential E ¹ _1/2. -7,7,8,8-tetracyanoquinodimethane, tetracyanoethylene, tetracyanobutadiene, 2,3-dichloro-5,6-dicyano-p-benzoquinone, 9-dicyanomethylene-2,4,5 Those selected from the group consisting of 7-tetranitrofluorenone, lithium hexafluoroarsenate, phosphoric acid trichloride, fluoranyl, chloranil and bromanyl are preferred, and 2,3,5,6-tetrafluoro-7,7,8,8-tetra More preferred are cyanoquinodimethane and 2,3-dichloro-5,6-dicyano-p-benzoquinone.

The acceptor compound was measured with a saturated calomel electrode (SCE) in an acetonitrile solvent containing tetrabutylammonium tetrafluoroborate as a 0.1 mol / L supporting salt at a temperature of 20 ° C. and a voltage pulling rate of 10 mV / s. From the viewpoint of hole injection from the anode, it is preferable that the oxidation-reduction half-wave potential E ¹ _1/2 to be satisfied is E ¹ _1/2 ≧ + 0.20 [V], and +1.50 [ More preferably, the compound satisfies V] ≧ E ¹ _1/2 ≧ + 0.20 [V], and the compound satisfies +1.30 [V] ≧ E ¹ _1/2 ≧ + 0.20 [V]. Is particularly preferred.

  In the composition of the present invention, the proportion of the acceptor compound is 100% by weight of the compound represented by the formula (1), the compound having the residue, or the repeating unit represented by the formula (2). The amount is usually 0.1 to 100 parts by weight, preferably 10 to 50 parts by weight, and more preferably 10 to 30 parts by weight.

  The composition of the present invention may contain other components.

<Organic electroluminescent device>
The composition of this invention can be used for preparation of an organic electroluminescent element. When the composition of the present invention is used for producing an organic electroluminescence device, it is preferably used as a material for a layer such as a buffer layer. In addition, a thin film may be formed using the composition of the present invention and used as a layer such as a buffer layer. Here, the buffer layer is a layer that is disposed between the anode and the light emitting layer and is in electrical communication with an adjacent layer.

  The average film thickness of the thin film is usually 0.5 to 500 nm, preferably 20 to 70 nm.

  Examples of methods for forming a thin film using the composition of the present invention include dry methods such as vacuum deposition and laser transfer; casting methods, spin coating methods, bar coating methods, blade coating methods, roll coating methods, gravure methods, and the like. Examples include wet methods such as printing, screen printing, ink jet method, capillary coating method, nozzle coating method, spray coating method, etc., but any film forming method using a solution in which the composition of the present invention is dissolved or dispersed can be used. This is not the case. Here, the wet method is preferable from the viewpoint of simplicity of the film forming method.

  In the wet method, the thin film can be formed by preparing a coating solution and coating and drying the coating solution on a desired layer (or electrode). A resin may be contained as a binder in the coating solution, and the resin can be dissolved in a solvent or dispersed. The solvent may contain an antioxidant, a viscosity modifier and the like.

As the resin, a non-conjugated polymer or a conjugated polymer can be used.
Examples of the non-conjugated polymer resin include silicon resin, epoxy resin, alkyd resin, unsaturated polyester resin, melamine resin, polyurethane, ABS resin, vinyl acetate resin, ethyl cellulose, polyamide, phenoxy resin, ketone resin, and hydrocarbon resin. , Polyvinyl carbazole, polyolefin, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, and poly (N-vinyl carbazole).
Examples of the conjugated polymer resin include paraphenylene resin, polyacetylene, polyaniline, polythiophene, polyparaphenylene vinylene, polyoxadiazole, and polyazomethine.

  The solvent used in the coating solution dissolves the compound represented by the formula (1), the compound having a residue thereof, the compound containing the repeating unit represented by the formula (2), and the acceptor compound. Any stable material that can be dispersed is acceptable. Examples of such solvents include alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; organic chlorines such as chloroform and 1,2-dichloroethane; aromatic hydrocarbons such as benzene, toluene and xylene. Aliphatic hydrocarbons such as normal hexane and cyclohexane; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more.

  The drying temperature of the coating film is preferably equal to or higher than the boiling point of the solvent used.

Examples of the structure of an organic electroluminescence device using the composition of the present invention as a thin film material and using the thin film as a buffer layer include the following structures, preferably anode / buffer layer / light emitting layer / electron. Injection layer / cathode, anode / buffer layer / hole transport layer / light emitting layer / electron injection layer / cathode, and more preferably anode / buffer layer / hole transport layer / light emitting layer / electron injection layer / cathode. .
Anode / buffer layer / light emitting layer / cathode anode / buffer layer / hole transport layer / light emitting layer / cathode anode / buffer layer / hole transport layer / light emitting layer / electron transport layer / cathode anode / buffer layer / light emitting layer / electron Transport layer / cathode anode / buffer layer / light emitting layer / electron injection layer / cathode anode / buffer layer / hole transport layer / light emitting layer / electron injection layer / cathode anode / buffer layer / hole transport layer / light emitting layer / electron transport Layer / electron injection layer / cathode anode / buffer layer / light emitting layer / electron transport layer / electron injection layer / cathode

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The number average molecular weight and the weight average molecular weight were measured by the following methods.

  For the number average molecular weight and the weight average molecular weight, the number average molecular weight and the weight average molecular weight in terms of polystyrene were determined by GPC (manufactured by Shimadzu Corporation, trade name: LC-10Avp). The polymer to be measured was dissolved in tetrahydrofuran to a concentration of about 0.5% by weight, and 50 μL was injected into GPC. Tetrahydrofuran was used as the mobile phase of GPC, and flowed at a flow rate of 0.6 mL / min. As for the column, two TSKgel SuperHM-H (manufactured by Tosoh Corp.) and one TSKgel SuperH2000 (manufactured by Tosoh Corp.) were connected in series. A differential refractive index detector (manufactured by Shimadzu Corporation, trade name: RID-10A) was used as the detector.

で表される化合物（Ａ−１）６．２８ｇを得た。
−分析データ−
・LC-MS
APPI-MS, positive 377 （[M＋H]⁺、exact mass＝376）
・¹H-NMR(300MHz,CDCl₃)
δ3.91(6Ｈ, s), 6.72(2H, t),7.17-7.26(6H, ｍ), 7.31(2H, t), 7.96(2H, d), 9.42(2H, s)
・¹³C-NMR(300MHz,CDCl₃)
δ52.1,111.8, 114.1, 117.1, 124.4, 131.9, 134.5, 136.9, 148.7, 169.3。 <Synthesis Example 1> (Synthesis of Compound (A-4))
-Synthesis of Compound (A-1)-
In a 300 ml four-necked flask, 5.00 g of 1,4-dibromobenzene and 7.05 g of methyl anthranilate were added, 100 ml of dehydrated toluene was added, and nitrogen was bubbled for 1 hour. Thereafter, 0.19 g of tris (dibenzylideneacetone) dipalladium, 0.24 g of tri (t-butyl) phosphine tetrafluoroborate and 10.36 g of cesium carbonate were added, heated at 70 ° C. for 5 hours, and then refluxed for 20 hours. . The mixture was filtered while hot through a glass filter with 20 g of Celite, and the residue on the filter was washed with ethyl acetate. Next, the solvent was distilled off, washed with a saturated aqueous sodium hydrogen carbonate solution, deionized water and saturated brine in that order, and then dried over sodium sulfate. Then, the solvent was distilled off to obtain 5.49 g of a crude product. The aqueous phase was extracted three times with 100 ml of chloroform, washed with water and saturated brine in that order, and then dried over sodium sulfate. Thereafter, the solvent was distilled off to obtain 4.00 g of a crude product. The obtained crude products were combined, recrystallized with 30 ml of toluene, and represented by the following formula (A-1):

6.28 g of the compound represented by formula (A-1) was obtained.
-Analytical data-
・ LC-MS
APPI-MS, positive 377 ([M + H] ⁺ , exact mass = 376)
・¹ H-NMR (300 MHz, CDCl ₃ )
δ3.91 (6H, s), 6.72 (2H, t), 7.17-7.26 (6H, m), 7.31 (2H, t), 7.96 (2H, d), 9.42 (2H, s)
・¹³ C-NMR (300 MHz, CDCl ₃ )
δ 52.1, 111.8, 114.1, 117.1, 124.4, 131.9, 134.5, 136.9, 148.7, 169.3.

で表される化合物（Ａ−２）４．１４ｇを得た。
−分析データ−
・LC-MS
ESI, positive 999 （[M＋K]⁺、exact mass＝960）
・¹H-NMR(300MHz,CDCl₃)
δ0.88(12H,t), 1.30(24H, m), 1.60(8H, ｍ), 2.60(8H, ｔ), 4.74(2H, brs), 5.68 (2H, brs), 6.55-6.63(6H, m), 6.75(2H,m), 7.03-7.26(20H, m)
・¹³C-NMR(300MHz,CDCl₃)
δ14.4,22.9, 29.3, 31.6, 32.0, 35.8, 82.4, 118.8, 120.2, 122.0, 127.9, 128.4, 130.3, 136.1, 137.7, 142.3, 143.3, 144.0。 -Synthesis of Compound (A-2)-
In a 300 ml four-necked flask, 8.98 g of 1-bromo-4-n-hexylbenzene was taken and purged with nitrogen. Then, after dissolving in 90 ml of dehydrated THF and cooling to −78 ° C., n-butyllithium (1.6 M hexane solution) was added dropwise over 10 minutes. Next, after keeping the temperature for 2 hours, 2.00 g of compound (A-1) was dissolved in 20 ml of dehydrated THF and added dropwise. Thereafter, the temperature was gradually raised to room temperature, and after stirring for 5 hours, 100 ml of water was added dropwise at 0 ° C. It was then separated and the aqueous phase was extracted with 100 ml of ethyl acetate. After the oil phase was washed with water and saturated brine, the solvent was distilled off to obtain 8.86 g of a crude product (red orange solid). The obtained crude product was recrystallized with 50 ml of hexane, and the following formula (A-2):

4.14 g of a compound (A-2) represented by
-Analytical data-
・ LC-MS
ESI, positive 999 ([M + K] ⁺ , exact mass = 960)
・¹ H-NMR (300 MHz, CDCl ₃ )
δ0.88 (12H, t), 1.30 (24H, m), 1.60 (8H, m), 2.60 (8H, t), 4.74 (2H, brs), 5.68 (2H, brs), 6.55-6.63 (6H, m), 6.75 (2H, m), 7.03-7.26 (20H, m)
・¹³ C-NMR (300 MHz, CDCl ₃ )
δ 14.4, 22.9, 29.3, 31.6, 32.0, 35.8, 82.4, 118.8, 120.2, 122.0, 127.9, 128.4, 130.3, 136.1, 137.7, 142.3, 143.3, 144.0.

で表される化合物（Ａ−３）６．７８ｇを得た。
−分析データ−
・LC-MS
ESI, positive 963 （[M＋K]⁺、exact mass＝924）
・¹H-NMR(300MHz,THF-d₈)
δ0.90(12H,t), 1.34(24H, m), 1.55-1.62(8H, ｍ), 2.56(8H, ｔ), 6.37(2H, s), 6.63-6.70(6H, m), 6.87(8H, d), 6.98-7.01(10H, m),7.87(2H, s)
・¹³C-NMR(300MHz,THF-d₈)
δ13.7, 22.8, 29.5, 31.8, 32.0, 35.7, 56.2, 113.5, 115.2, 118.2, 126.8, 127.1, 127.3, 130.1, 130.4, 134.5, 140.4, 141.8, 144.6。 -Synthesis of Compound (A-3)-
In a 300 ml eggplant-shaped flask, 8.00 g of compound (A-2) was taken and purged with nitrogen. Then, it was dissolved in 80 ml of acetic acid and cooled to 0 ° C. After dropwise addition of 2.8 ml of concentrated hydrochloric acid, the mixture was warmed to room temperature, stirred for 5 hours, cooled again to 0 ° C., filtered and washed with water. Next, it was dissolved in 250 ml of toluene, basified with an aqueous sodium hydroxide solution, washed with a saturated aqueous sodium hydrogen carbonate solution, water and saturated brine in that order, and then dried over sodium sulfate. Thereafter, when the solvent was distilled off, 13.75 g of a crude product was obtained. The obtained crude product was recrystallized with 50 ml of toluene, and the following formula (A-3):

6.78 g of the compound represented by (A-3) was obtained.
-Analytical data-
・ LC-MS
ESI, positive 963 ([M + K] ⁺ , exact mass = 924)
・¹ H-NMR (300 MHz, THF-d ₈ )
δ0.90 (12H, t), 1.34 (24H, m), 1.55-1.62 (8H, m), 2.56 (8H, t), 6.37 (2H, s), 6.63-6.70 (6H, m), 6.87 ( 8H, d), 6.98-7.01 (10H, m), 7.87 (2H, s)
・¹³ C-NMR (300 MHz, THF-d ₈ )
δ 13.7, 22.8, 29.5, 31.8, 32.0, 35.7, 56.2, 113.5, 115.2, 118.2, 126.8, 127.1, 127.3, 130.1, 130.4, 134.5, 140.4, 141.8, 144.6.

で表される化合物（Ａ−４）１０．０９ｇを得た。
−分析データ−
・LC-MS
ESI, positive 1218 （[M＋H]⁺、exact mass＝1217）
・¹H-NMR(300MHz,THF-d₈)
δ0.62(12H,t), 0.69(6H, t), 1.00-1.34--17(28H, m), 1.27-1.37(12H, ｍ), 2.26-2.35(12H, m), 5.67(2H, s), 5.93(2H, d), 6.38-6.47(8H, d), 6.56-6.61(10H, m), 6.64(8H, d), 6.79(6H, d)
・¹³C-NMR(300MHz,THF-d₈)
δ15.5, 15.6, 24.6, 24.7, 31.3, 33.7, 33.9, 35.8, 37.6, 58.3, 116.0, 117.8, 121.2, 128.0, 129.1, 130.8, 138.5, 140.9, 142.2, 144.1, 145.0, 146.0。 -Synthesis of Compound (A-4)-
A 300 ml four-necked flask was purged with nitrogen, and 9.90 g of compound (A-3) and 4.94 g of 1-bromo-4-n-butylbenzene were taken and dissolved in 150 ml of dehydrated toluene. After bubbling with nitrogen for 20 minutes, 0.05 g of tris (dibenzylideneacetone) dipalladium, 0.03 g of tri (t-butyl) phosphine tetrafluoroborate and 0.30 g of sodium-t-butoxide were added and refluxed for 10 hours. Then, after cooling to 0 degreeC, 100 ml of water was added and liquid-separated, and the aqueous phase was extracted twice with 100 ml of toluene. The oil phases were combined, washed with water and saturated brine, and filtered through a glass filter with 60 g of silica gel. Then, after washing with toluene, the solvent was distilled off to obtain 16.52 g of a crude product. The obtained crude product was crystallized by adding 50 ml of hexane, added with 50 ml of methanol, and filtered. The obtained solid was recrystallized with 50 ml of hexane, and the following formula (A-4):

The compound (A-4) represented by these was obtained.
-Analytical data-
・ LC-MS
ESI, positive 1218 ([M + H] ⁺ , exact mass = 1217)
・¹ H-NMR (300 MHz, THF-d ₈ )
δ0.62 (12H, t), 0.69 (6H, t), 1.00-1.34--17 (28H, m), 1.27-1.37 (12H, m), 2.26-2.35 (12H, m), 5.67 (2H, s), 5.93 (2H, d), 6.38-6.47 (8H, d), 6.56-6.61 (10H, m), 6.64 (8H, d), 6.79 (6H, d)
・¹³ C-NMR (300 MHz, THF-d ₈ )
δ 15.5, 15.6, 24.6, 24.7, 31.3, 33.7, 33.9, 35.8, 37.6, 58.3, 116.0, 117.8, 121.2, 128.0, 129.1, 130.8, 138.5, 140.9, 142.2, 144.1, 145.0, 146.0.

で表される化合物（Ａ）９．５５ｇを得た。
−分析データ−
・LC-MS
APCI, positive 1346 （[M＋H]⁺、exact mass＝1345）
・¹H-NMR(300MHz,THF-d₈)
δ0.90(12H,t), 0.97(6H, t), 1.30-1.45(28H, m), 1.57-1.69(12H, m), 2.56-2.61(12H, m), 5.95(2H, s), 6.16(2H, brs), 6.70(4H, d), 6.76(8H, d), 7.01(8H, d), 7.02(2H, m), 7.05(2H, m), 7.12(4H, d)
・¹³C-NMR(300MHz,THF-d₈)
δ15.5, 15.6, 24.6, 24.7, 31.3, 33.6, 33.9, 35.7, 37.4, 37.6, 117.7, 129.4, 130.3, 132.0, 138.5, 142.7, 144.5。 <Synthesis Example 2> (Synthesis of Compound A)
In a 300 ml eggplant-shaped flask, 10.09 g of compound (A-4) was taken and purged with nitrogen. Then, it was dissolved in 100 ml of chloroform and cooled to 0 ° C. Next, a solution prepared by dissolving 2.87 g of N-bromosuccinimide (NBS) in 6 ml of DMF was added dropwise over 20 minutes. Thereafter, the cooling bath was removed, and the mixture was stirred for 7 hours, cooled to 0 ° C., dissolved in 0.29 g of NBS in 0.5 ml of DMF, and added dropwise. Further, after stirring for 2.5 hours, 100 ml of water was added dropwise, followed by liquid separation, and the aqueous phase was extracted with chloroform. In addition, the oil phase was washed with water and saturated saline, and then filtered through a glass filter covered with 50 g of silica gel, and the resulting solid was washed with toluene. Thereafter, when the solvent was distilled off, 12.48 g of a crude product was obtained. The crude product obtained from the aqueous phase and the oil phase was recrystallized in the order of 180 ml of hexane and 200 ml of hexane, and the following formula (A):

9.55 g of the compound (A) represented by
-Analytical data-
・ LC-MS
APCI, positive 1346 ([M + H] ⁺ , exact mass = 1345)
・¹ H-NMR (300 MHz, THF-d ₈ )
δ0.90 (12H, t), 0.97 (6H, t), 1.30-1.45 (28H, m), 1.57-1.69 (12H, m), 2.56-2.61 (12H, m), 5.95 (2H, s), 6.16 (2H, brs), 6.70 (4H, d), 6.76 (8H, d), 7.01 (8H, d), 7.02 (2H, m), 7.05 (2H, m), 7.12 (4H, d)
・¹³ C-NMR (300 MHz, THF-d ₈ )
δ 15.5, 15.6, 24.6, 24.7, 31.3, 33.6, 33.9, 35.7, 37.4, 37.6, 117.7, 129.4, 130.3, 132.0, 138.5, 142.7, 144.5.

<Synthesis Example 3> (Synthesis of Polymer Compound 1)
Under nitrogen atmosphere, compound (A) 1.01 g, 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-di-n-octylfluorene 0.40 g, dichlorobis (triphenylphosphine) ) 0.5 mg of palladium, 0.10 g of trioctylmethylammonium chloride (manufactured by Aldrich, trade name: Aliquat 336) and 15 ml of toluene were mixed and heated to 90 ° C. To this reaction solution, 4.1 ml of a 17.5% by weight aqueous sodium carbonate solution was added dropwise and refluxed for 2 hours. After the reaction, 10 mg of phenylboric acid was added, and the mixture was further refluxed for 4.5 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 80 ° C. for 3 hours. After cooling, the mixture was washed twice with 10 ml of water, twice with 10 ml of a 3% by weight aqueous acetic acid solution and twice with 10 ml of water, and the resulting solution was dropped into 120 mL of methanol and filtered to obtain a precipitate. This precipitate was dissolved in 25 mL of toluene and purified by passing through a column in which activated alumina was spread on silica gel. The obtained toluene solution was dropped into 120 ml of methanol and stirred, and then the obtained precipitate was collected by filtration and dried to obtain 0.89 g of the polymer compound 1. The number average molecular weight in terms of polystyrene of the polymer compound 1 was 1.0 × 10 ⁵ , and the weight average molecular weight in terms of polystyrene was 3.0 × 10 ⁵ . In addition, it is estimated from the charged raw material that the polymer compound 1 includes a repeating unit represented by the following formula.

<Synthesis Example 4> (Synthesis of Polymer Compound 2)
Under a nitrogen atmosphere, 1.0 g of compound (A), 0.55 g of bis [1,5-cyclooctadiene] nickel complex, 0.31 g of 2,2′-bipyridyl, and 35 ml of THF are mixed, and at 60 ° C. for 3 hours. Heated to reflux. After cooling to room temperature, the reaction solution was added dropwise to a mixed solution of 40 ml of methanol and 20 ml of an aqueous ammonia solution, and stirred at room temperature for 0.5 hours. The precipitated solid was collected by filtration and dried under reduced pressure. The obtained crude product was dissolved in 50 ml of toluene, passed through a radiolite column, and purified by alumina column chromatography. The obtained toluene solution was washed with an aqueous hydrochloric acid solution, an aqueous ammonia solution and ion-exchanged water. After removing the aqueous phase, the organic phase was added dropwise to 70 ml of methanol and stirred at room temperature for 0.5 hour. The obtained precipitate was collected by filtration and dried to obtain 0.47 g of polymer compound 2.
The polymer compound 2 had a polystyrene-equivalent number average molecular weight of 4.2 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 1.9 × 10 ⁵ . In addition, from the charged raw material, it is estimated that the high molecular compound 2 contains the repeating unit represented by a following formula.

で表される化合物α ５．２５ｇ（９．９ｍｍｏｌ）、下記式：

で表される化合物β ４．５５ｇ（９．９ｍｍｏｌ）、メチルトリオクチルアンモニウムクロライド（商品名：Ａｌｉｑｕａｔ３３６、アルドリッチ社製） ０．９１ｇ、及びトルエン６９ｍｌを加えてモノマー溶液を得た。窒素雰囲気下、モノマー溶液を加熱し８０℃で酢酸パラジウム ２ｍｇ、及びトリス（２−メチルフェニル）ホスフィン １５ｍｇを加えた。得られたモノマー溶液に、１７．５重量％炭酸ナトリウム水溶液 ９．８ｇを注加した後、１１０℃で１９時間攪拌した。次に、トルエン１．６ｍｌに溶解したフェニルホウ酸 １２１ｍｇを加え、１０５℃で１時間攪拌した。
有機相を水相と分離した後、有機相にトルエン３００ｍｌを加えた。有機相を３重量％酢酸水溶液 ４０ｍｌ（２回）、イオン交換水 １００ｍｌ（１回）の順番で洗浄し、水相と分離した。有機相にＮ，Ｎ−ジエチルジチオカルバミド酸ナトリウム三水和物 ０．４４ｇ、トルエン １２ｍｌを加え６５℃で４時間攪拌した。
あらかじめトルエンを通液したシリカゲル／アルミナカラムに反応生成物のトルエン溶液を通液し、この溶液をメタノール １４００ｍｌに滴下しポリマーを沈殿させ、沈殿物を濾過後乾燥し固体を得た。この固体をトルエン ４００ｍｌに溶解させ、メタノール １４００ｍｌに滴下しポリマーを沈殿させ、得られた沈殿物を濾過後乾燥し、正孔輸送性高分子化合物を６．３３ｇ得た。正孔輸送性高分子化合物のポリスチレン換算の数平均分子量Ｍｎは８．８×１０⁴であり、重量平均分子量Ｍｗは３．２×１０⁵であった。
なお、正孔輸送性高分子化合物は、仕込み原料から、下記式：

で表される繰り返し単位を、１：１（モル比）で含むものと推定される。 <Synthesis Example 5> (Synthesis of hole transporting polymer material)
In a flask connected to a Dimroth, the following formula:

5.25 g (9.9 mmol) of the compound α represented by the following formula:

A compound solution was obtained by adding 4.55 g (9.9 mmol) of a compound β represented by the following formula: 0.91 g of methyltrioctylammonium chloride (trade name: Aliquat 336, manufactured by Aldrich) and 69 ml of toluene. Under a nitrogen atmosphere, the monomer solution was heated, and 2 mg of palladium acetate and 15 mg of tris (2-methylphenyl) phosphine were added at 80 ° C. To the obtained monomer solution, 9.8 g of a 17.5% by weight sodium carbonate aqueous solution was poured, and the mixture was stirred at 110 ° C. for 19 hours. Next, 121 mg of phenylboric acid dissolved in 1.6 ml of toluene was added and stirred at 105 ° C. for 1 hour.
After separating the organic phase from the aqueous phase, 300 ml of toluene was added to the organic phase. The organic phase was washed in the order of 3% by weight acetic acid aqueous solution (40 ml, twice) and ion-exchanged water (100 ml, once) and separated from the aqueous phase. To the organic phase, 0.44 g of sodium N, N-diethyldithiocarbamate trihydrate and 12 ml of toluene were added and stirred at 65 ° C. for 4 hours.
A toluene solution of the reaction product was passed through a silica gel / alumina column through which toluene was passed in advance, and this solution was dropped into 1400 ml of methanol to precipitate a polymer. The precipitate was filtered and dried to obtain a solid. This solid was dissolved in 400 ml of toluene and dropped into 1400 ml of methanol to precipitate a polymer. The obtained precipitate was filtered and dried to obtain 6.33 g of a hole transporting polymer compound. The number average molecular weight Mn in terms of polystyrene of the hole transporting polymer compound was 8.8 × 10 ⁴ , and the weight average molecular weight Mw was 3.2 × 10 ⁵ .
In addition, the hole transporting polymer compound is represented by the following formula:

It is estimated that the repeating unit represented by the formula (1) is included at a 1: 1 (molar ratio).

<Example 1> (Preparation of composition A)
2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, which is an acceptor compound, is dissolved in a dichloromethane solvent to give a 0.2% by weight solution, and the acceptor compound is obtained. Solution 1 was prepared.
Moreover, the high molecular compound 1 was dissolved in the dichloromethane solvent so that it might become a 0.3 weight% solution, and the high molecular compound 1 solution was prepared.
These acceptor compound solution 1 and polymer compound 1 solution are mixed so that the weight ratio of polymer compound 1 and acceptor compound in the resulting solution is 80:20, and composition A (mixed solution) Was prepared.

<Example 2> (Preparation of organic electroluminescent element 1)
Composition A was applied on a glass substrate on which an ITO anode was formed by spin coating at a rotation speed of 800 rpm to form a 50 nm thin film. The glass substrate A thus obtained was heat-treated at 200 ° C. for 10 minutes to evaporate the solvent.
Next, a hole transporting polymer material was prepared and dissolved in a xylene solvent so as to be a 0.8 wt% solution, thereby preparing a hole transporting polymer material solution 1. The hole transporting polymer material solution 1 is formed on a glass substrate on which a mixed film of the polymer compound 1 and the acceptor compound is formed so as to have a film thickness of 20 nm by a spin coating method. Layered. The glass substrate B thus obtained was heat-treated at 200 ° C. for 15 minutes to evaporate the solvent.

  Next, a polymer light emitting material (manufactured by Summation Co., Ltd., trade name: BP361) was prepared and dissolved in a xylene solvent so as to be a 1.2 wt% solution to prepare a polymer light emitting material solution 1. The polymer light emitting material solution 1 was formed on the glass substrate A by a spin coat method so as to have a film thickness of 70 nm, thereby forming a light emitting layer. The glass substrate C thus obtained was heat-treated at 130 ° C. for 20 minutes to evaporate the solvent.

  Next, 5 nm of barium and then 80 nm of aluminum were deposited on the glass substrate C by a vacuum evaporation apparatus to form a cathode, thereby obtaining a glass substrate D (cathode formed). Then, the glass substrate D was sealed using an epoxy resin and a glass plate for sealing, and the organic electroluminescent element 1 was produced.

<Example 3> (Preparation of composition B)
In Example 1, a composition prepared in the same manner as in Example 1 except that the polymer compound 2 was used instead of the polymer compound 1 was designated as composition B.

<Example 4> (Preparation of organic electroluminescent element 2)
In Example 2, an organic electroluminescent element produced in the same manner as in Example 2 except that the composition B was used instead of the composition A was designated as an organic electroluminescent element 2.

<Synthesis Example 5> (Synthesis of Polymer Compound 3)
N, N′-di (p-bromophenyl) -N, N′-di (p-butylphenyl) -1,4-phenylenediamine was synthesized by the method described in Polymer Preprints 2001, 42 (2), 587. did.
Under a nitrogen atmosphere, N, N′-di (p-bromophenyl) -N, N′-di (p-butylphenyl) -1,4-phenylenediamine (2.73 g), 2,7-bis (1,3,3) 2-dioxaborolan-2-yl) -9,9-di-n-octylfluorene 2.11 g, palladium acetate 1.8 mg, tri (o-tolyl) phosphine 11.3 mg, trioctylmethylammonium chloride (manufactured by Aldrich) (Product name: Aliquat 336) 0.52 g and 15 ml of toluene were mixed and heated to 90 ° C. To this reaction solution, 10.9 ml of a 17.5% by weight aqueous sodium carbonate solution was added dropwise and refluxed for 6 hours. After the reaction, 49 mg of phenylboric acid was added, and the mixture was further refluxed for 2 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the mixture was washed twice with 50 ml of water, twice with 50 ml of 3% by weight acetic acid aqueous solution and twice with 50 ml of water, and the resulting solution was dropped into 620 ml of methanol and filtered to obtain a precipitate. . This precipitate was dissolved in 120 ml of toluene and purified by passing through a column in which activated alumina was spread on silica gel. The obtained toluene solution was dropped into 620 ml of methanol and stirred, and then the obtained precipitate was collected by filtration and dried to obtain 3.19 g of the polymer compound 3. The polymer compound 3 had a polystyrene-equivalent number average molecular weight of 4.2 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 1.7 × 10 ⁵ . In addition, it is presumed from the charged raw materials that the polymer compound 3 includes a repeating unit represented by the following formula.

<Synthesis Example 6> (Synthesis of Polymer Compound 4)
Under an inert atmosphere, N, N′-di (p-bromophenyl) -N, N′-di (p-butylphenyl) -1,4-phenylenediamine (10.238 g), 2,2′-bipyridyl ( 6.325 g) was dissolved in 410 mL of dehydrated tetrahydrofuran previously bubbled with argon. After raising the temperature of this solution to 60 ° C., bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (11.140 g) was added, stirred and reacted for 5 hours. The reaction solution was cooled to room temperature, dropped into a mixed solution of 25 wt% ammonia water 54 mL / methanol 410 mL / ion exchanged water 410 mL and stirred for 1 hour, and then the deposited precipitate was filtered and dried under reduced pressure. Dissolved. After dissolution, 1.8 g of radiolite was added and stirred for 30 minutes, and the insoluble material was filtered off. The obtained filtrate was purified through an alumina column. Next, 890 mL of 4 wt% aqueous ammonia was added and stirred for 2 hours, and then the aqueous layer was removed. Further, about 890 mL of ion exchange water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. Thereafter, the organic layer was poured into 1400 ml of methanol and stirred for 0.5 hour, and the deposited precipitate was filtered and dried under reduced pressure to obtain 6.72 g of polymer compound 4. The number average molecular weight Mn in terms of polystyrene of the polymer compound 4 was 8.6 × 10 ³ , and the weight average molecular weight Mw was 9.7 × 10 ⁴ . In addition, from the charged raw material, it is estimated that the high molecular compound 4 contains the repeating unit represented by a following formula.

<Comparative Example 1> (Preparation of Composition C)
A composition C was prepared in the same manner as in Example 1 except that the polymer compound 3 was used instead of the polymer compound 1 in Example 1.

<Comparative example 2> (Preparation of organic electroluminescent element 3)
In Example 2, an organic electroluminescent element produced in the same manner as in Example 2 except that the composition C was used instead of the composition A was designated as an organic electroluminescent element 3.

<Comparative Example 3> (Preparation of Composition D)
In Example 1, composition D was prepared in the same manner as in Example 1 except that polymer compound 4 was used instead of polymer compound 1.
<Comparative example 4> (Preparation of organic electroluminescent element 4)
In Example 2, an organic electroluminescent element produced in the same manner as in Example 2 except that the composition D was used instead of the composition A was designated as an organic electroluminescent element 4.

<Element evaluation>
-Measurement 1-
A constant voltage / current power source was prepared, the ITO anode of the organic electroluminescent elements 1 to 4 was connected to the anode of the power source, the aluminum cathode was connected to the cathode of the power source, voltage was applied, and current injection was performed. Emission luminance 1 cd / m ² o'clock voltages, and luminance half life at the time of continuous driving by the light emitting luminance 1600 cd / m ² was measured. The obtained results are shown in Table 1.

-Evaluation 1
As can be seen from Table 1, the organic electroluminescent devices 1 and 2 using the composition of the present invention have an emission luminance of 1 cd / m ² compared to the organic electroluminescent devices 3 and 4 using other compositions. It is recognized that the voltage (light emission starting voltage) decreases and the luminance half-life increases. Therefore, it is recognized that the composition of the present invention is excellent in hole injection property and device lifetime.

Claims (10)

Following formula (1):

(In the formula, A ring, B ring and C ring each independently represent a monocyclic aromatic ring or a condensed aromatic ring, R ¹ and R ⁴ each independently represent a monovalent group, R ² , R ³ , R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an alkenyl group or an alkynyl group, A ring, B ring, C ring, R ¹ and R ⁴ are (The aryl group, arylalkyl group, alkenyl group and alkynyl group represented by R ² , R ³ , R ⁵ and R ⁶ may have a substituent.)
Or a compound having a residue thereof, or the following formula (2):

(In the formula, A ring, B ring, C ring, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as described above, provided that A ring and C ring are bonded to each other. Have a hand.)
The composition containing the compound containing the repeating unit represented by these, and an acceptor compound.   The composition according to claim 1, wherein the A ring, B ring and C ring are monocyclic aromatic rings which may have a substituent. The composition according to claim 1 or 2, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are an aryl group which may have a substituent. Furthermore, the following formula (3):

(In the formula, Ar ¹ represents an arylene group or a divalent heterocyclic group. R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. n represents 0 or 1. Ar ¹ , R ⁷ and R ⁸ may have a substituent.
The composition as described in any one of Claims 1-3 containing the repeating unit represented by these. The repeating unit represented by the formula (3) is represented by the following formula (4-1):

(In the formula, each of C ⁴ ring and C ⁵ ring independently represents an aromatic hydrocarbon ring which may have a substituent, and two bonds are present on C ⁴ ring or C ⁵ ring, respectively. , Rw and Rx are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, alkenyl group, alkynyl group, 2 Rw represents a substituted amino group, a trisubstituted silyl group, an acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a substituted carboxyl group, a heteroaryloxy group, or a heteroarylthio group. And Rx may have a substituent.)
The composition of Claim 4 which is represented by these. The compound containing the repeating unit represented by the formula (2) is further selected from the group consisting of repeating units represented by the following formulas (5-1), (5-2) and (5-3). The composition according to any one of claims 1 to 5, which is a compound containing one type of repeating unit.

(In the formula, Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ each independently represent an arylene group or a divalent heterocyclic group. Ar ⁶ , Ar ⁷ and Ar ⁸ each independently represent an aryl group or a monovalent group. And B and b each independently represent 0 or a positive integer, Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ and Ar ⁸ have a substituent. May be.)

(In the formula, D ring and E ring each independently represent an aromatic ring. Y ¹ represents —O—, —S— or —C (═O) —. R ²⁰ represents a monovalent group. D ring and E ring each have a bond. D ring, E ring, Y ¹ and R ²⁰ may have a substituent.)

(In the formula, Y ² represents —O— or —S—.)   The acceptor compound is a quinone compound, a transition metal complex compound, an organic closed-shell anionic compound, a fluorene compound having a cyano group and a nitro group, tetracyanoethylene, tetracyanobutadiene, lithium hexafluoroarsenate, phosphoric acid trichloride The composition according to claim 1, which is selected from the group consisting of fluoranyl, chloranil, and bromanyl.   The acceptor compound is 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, tetracyanoethylene, tetra Cyanobutadiene, 2,3-dichloro-5,6-dicyano-p-benzoquinone, 9-dicyanomethylene-2,4,5,7-tetranitrofluorenone, lithium hexafluoroarsenate, phosphoric acid trichloride, fluoranyl, chloranil and bromanyl The composition according to claim 7, which is selected from the group consisting of:   The ratio of the acceptor compound is 0.001 part by weight with respect to 100 parts by weight of the compound represented by the formula (1), the compound having a residue thereof, or the compound containing the repeating unit represented by the formula (2). It is 1-100 weight part, The composition as described in any one of Claims 1-8.   The organic electroluminescent element which has a layer which uses the composition as described in any one of Claims 1-9.