JP2008074917A - Polymer light-emitting device, organic transistor and composition useful for them - Google Patents

Abstract

〔式中、Ｒ¹は置換基を表し、Ｒ²は置換基を有していてもよいアルキル基、又は置換基を有していてもよいアルコキシ基を表し、ｎは０〜３の整数を表す。複数存在するＲ²及びｎは、それぞれ、同一であっても異なっていてもよい。Ｒ¹が複数存在する場合には、それらは同一であっても異なっていてもよい。〕
で表される繰り返し単位、電子注入性を有する繰り返し単位、及び正孔注入性を有する繰り返し単位を含む重合体と、燐光発光を示す化合物とを含む組成物。
【選択図】なしA composition that emits light with high luminous efficiency from a light-emitting element when used for manufacturing a light-emitting element.
The following formula (1):

[Wherein, R ¹ represents a substituent, R ² represents an alkyl group which may have a substituent, or an alkoxy group which may have a substituent, and n represents an integer of 0 to 3. To express. A plurality of R ² and n may be the same or different. When a plurality of R ¹ are present, they may be the same or different. ]
A composition comprising: a repeating unit represented by formula: a repeating unit having an electron injecting property; a polymer containing a repeating unit having a hole injecting property; and a compound exhibiting phosphorescence.
[Selection figure] None

Description

  The present invention relates to a polymer light-emitting device (that is, polymer LED), an organic transistor, and a composition useful for them.

  A composition of a polymer and a compound exhibiting phosphorescence emission is usually soluble in a solvent, and various studies have been made since an organic layer in a light-emitting element can be formed by a coating method. As such a composition, for example, a polymer material containing a conjugated polymer and a phosphorescent compound has been proposed. Specifically, a composition (Patent Document 1) of a copolymer containing a fluorenediyl group and a triphenylaminediyl group and a metal complex has been proposed.

International Publication No. 2005/13386 Pamphlet

However, this composition has a problem that the light emitting efficiency is low when a light emitting device is produced using the composition.
Accordingly, an object of the present invention is to provide a composition that emits light with high luminous efficiency from the light emitting device when used for the production of the light emitting device.

〔式中、Ｒ¹は置換基を表し、Ｒ²は置換基を有していてもよいアルキル基又は置換基を有していてもよいアルコキシ基を表し、ｎは０〜３の整数を表す。複数存在するＲ²及びｎは、それぞれ、同一であっても異なっていてもよい。Ｒ¹が複数存在する場合には、それらは同一であっても異なっていてもよい。〕
で表される繰り返し単位、電子注入性を有する繰り返し単位、及び正孔注入性を有する繰り返し単位を含む重合体と、燐光発光を示す化合物とを含有する組成物、を提供する。 The present invention provides the following formula (1):

[Wherein, R ¹ represents a substituent, R ² represents an alkyl group which may have a substituent or an alkoxy group which may have a substituent, and n represents an integer of 0 to 3. . A plurality of R ² and n may be the same or different. When a plurality of R ¹ are present, they may be the same or different. ]
And a polymer containing a repeating unit represented by formula (1), a repeating unit having an electron injecting property, and a repeating unit having a hole injecting property, and a compound exhibiting phosphorescence emission.

When the composition and polymer compound of the present invention are used for production of a light emitting device, a light emitting device in which a phosphorescent material emits light with high luminous efficiency is obtained. In general, the light-emitting element thus obtained has improved maximum brightness and starts to emit light at a low voltage. Thus, the composition and polymer compound of the present invention are useful as a light emitting material.
Therefore, a light emitting device using the composition of the present invention includes a planar light source such as a curved light source or a planar light source (for example, illumination); a segment display device (for example, a segment type display device); a dot matrix. It is useful for display devices such as a display device (for example, a dot matrix flat display) and a liquid crystal display device (for example, a liquid crystal display device, a backlight of a liquid crystal display).
The composition of the present invention is not only suitable as a material used for the production thereof, but also conductive properties such as laser dyes, organic solar cell materials, organic semiconductors for organic transistors, conductive thin films, and organic semiconductor thin films. It is also suitable as a material for a thin film, a light emitting thin film material that emits fluorescence, a material for a polymer field effect transistor, and the like.

  The present invention will be described below. In this specification, the energy level of HOMO (highest occupied level) of a polymer is determined from the oxidation potential of the polymer, and the energy level of LUMO (lowest empty level) of the polymer is the reduction potential of the polymer. Ask from. The oxidation potential was determined by cyclic voltammetry using a silver / silver chloride electrode as a reference electrode, a platinum electrode as a working electrode, and a platinum electrode as a counter electrode in an acetonitrile solvent containing 0.1 wt% tetrabutylammonium-t-fluoroborate. This is a value obtained by measuring after bubbling the solvent with nitrogen for 1 minute. The reduction potential is an acetonitrile solvent containing 0.1 wt% tetrabutylammonium t-fluoroborate in a glove box substituted with nitrogen using a silver / silver ion electrode as a reference electrode, a glassy carbon electrode as a working electrode, and a platinum electrode as a counter electrode. It is a value obtained by measuring in. The potential velocity is measured at 50 mV / s.

<Composition>
The composition of the present invention comprises a polymer containing a repeating unit represented by the formula (1), a repeating unit having an electron injecting property, and a repeating unit having a hole injecting property, and a compound exhibiting phosphorescence. To do.

-Polymer containing repeating units represented by formula (1)-
In the formula (1), examples of the substituent represented by R ¹ include 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, and an aryl group. Alkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group , Substituted carboxyl group, nitro group, cyano group and the like. A hydrogen atom contained in these substituents may be substituted with a fluorine atom. Among these substituents, from the viewpoint of solubility of the polymer in an organic solvent and ease of synthesis of the polymer, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, An arylalkyl group, an arylalkoxy group, and a monovalent heterocyclic group are preferable, and an alkyl group, an alkoxy group, an aryl group, and a monovalent heterocyclic group are more preferable.

In the formula (1), n represents an integer of 0 to 3, and n is preferably 0 or 1 from the viewpoint of easy synthesis of the polymer. When a plurality of R ¹ are present, they may be the same or different.

Description of Substituent Represented by R ^{1 The} alkyl group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, s-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, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl Group, perfluorooctyl group, etc., from the viewpoint of the solubility of the polymer in an organic solvent, device characteristics, ease of synthesis of the polymer and the heat resistance, pentyl group, isoamyl group, A hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, and a 3,7-dimethyloctyl group are preferred.

  The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, s-butoxy group, pentyloxy group, hexyloxy group, Cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy Group, perfluorohexyl group, perfluorooctyl group and the like. From the viewpoint of the heat resistance and the solubility of the polymer in an organic solvent, device characteristics, ease of synthesis of the polymer and the like, pentyl Oxy group, hexyloxy group, octyloxy group, 2-ethylhexyl Alkoxy group, decyloxy group, 3,7-dimethyl octyloxy group are preferable. Moreover, as a substituted alkoxy group, a methoxymethyloxy group, 2-methoxyethyloxy group, etc. are mentioned, for example.

  The alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, i-propylthio group, butylthio group, i-butylthio group, t-butylthio group, s-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, Examples include heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, trifluoromethylthio group, etc., solubility of polymer in organic solvent, element From the viewpoint of characteristics, easiness of polymer synthesis and heat resistance, a pentylthio group, hexylthio group, octylthio group, 2-ethylhexylthio group, decylthio group, and 3,7-dimethyloctylthio group are preferable. .

An 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 aryl group usually has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples of the aryl group, phenyl group, C ₁ -C ₁₂ alkoxyphenyl group ( "C ₁ -C ₁₂ alkoxy" means that the carbon atoms in the alkoxy moiety is 1 to 12. Hereinafter, the same is C ₁ -C ₁₂ alkylphenyl group (“C ₁ -C ₁₂ alkyl” means that the alkyl moiety has 1 to 12 carbon atoms. The same shall apply hereinafter.), 1-naphthyl Group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, pentafluorophenyl group, etc., solubility of polymer in organic solvent, device characteristics, synthesis of polymer from the viewpoint of easiness is, C ₁ -C ₁₂ alkoxyphenyl group, is C ₁ -C ₁₂ alkylphenyl group are preferable. Specific examples C ₁ -C ₁₂ alkoxyphenyl group, methoxyphenyl group, ethoxyphenyl group, propyloxyphenyl group, i- propyl group, a butoxyphenyl group, i- butoxyphenyl, t-butoxyphenyl group, s-butoxyphenyl group, pentyloxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group, 3, Examples thereof include 7-dimethyloctyloxyphenyl group and lauryloxyphenyl group. C ₁ -C ₁₂ alkylphenyl group as specifically methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, i- propylphenyl group, butylphenyl group, i- butyl Examples include phenyl group, t-butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group and the like.

The aryloxy group usually has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples of the aryloxy group include a phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, like 2-naphthyloxy group, pentafluorophenyloxy group and In view of solubility of the polymer in an organic solvent, device characteristics, ease of synthesis of the polymer, and the like, a C _{1 to} C ₁₂ alkoxyphenoxy group and a C _{1 to} C ₁₂ alkylphenoxy group are preferable. Specific examples C ₁ -C ₁₂ alkoxy phenoxy group, methoxyphenoxy group, ethoxyphenoxy group, propyloxy phenoxy group, i- propyloxy phenoxy group, butoxyphenoxy group, i- butoxyphenoxy group, t-butoxyphenoxy group, s-butoxyphenoxy group, pentyloxyphenoxy group, hexyloxyphenoxy group, cyclohexyloxyphenoxy group, heptyloxyphenoxy group, octyloxyphenoxy group, 2-ethylhexyloxyphenoxy group, nonyloxyphenoxy group, decyloxyphenoxy group, 3, Examples thereof include 7-dimethyloctyloxyphenoxy group and lauryloxyphenoxy group. Specific examples C ₁ -C ₁₂ alkylphenoxy group, methylphenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-methylphenoxy group, methylethylphenoxy group, i- propyl phenoxy group Butylphenoxy group, i-butylphenoxy group, t-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group, dodecylphenoxy group, etc. Illustrated.

The arylthio group usually has about 6 to 60 carbon atoms. Specific examples of the arylthio group include a phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group, pentafluorophenylthio group and the like From the viewpoints of solubility of the polymer in an organic solvent, device characteristics, ease of synthesis of the polymer, and the like, a C ₁ -C ₁₂ alkoxyphenylthio group and a C ₁ -C ₁₂ alkylphenylthio group are preferred.

The arylalkyl group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples of the aryl alkyl group, a phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group 1-naphthyl-C ₁ -C ₁₂ alkyl group, 2-naphthyl-C ₁ -C ₁₂ alkyl group, etc., and the solubility of the polymer in an organic solvent, device characteristics, and ease of synthesis of the polymer. in terms of equal, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group.

The arylalkoxy group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples of the arylalkoxy group include phenyl-C _{1 to} C ₁₂ such as phenylmethoxy group, phenylethoxy group, phenylbutoxy group, phenylpentyloxy group, phenylhexyloxy group, phenylheptyloxy group, and phenyloctyloxy group. alkoxy groups, 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, soluble organic solvent, device properties of the polymer, from the viewpoint of easiness of synthesis of a polymer, 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 arylalkylthio group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples of the arylalkylthio group include a 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, etc., and the solubility of the polymer in an organic solvent, device characteristics, and ease of synthesis of the polymer. From the viewpoints such as C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkylthio group is preferred.

The arylalkenyl group usually has about 8 to 60 carbon atoms. Specific examples of the arylalkenyl group include a phenyl -C ₂ -C ₁₂ alkenyl group ( "C ₂ -C ₁₂ alkenyl". Hereinafter, the same which means that the carbon number of the alkenyl portion is 2 to 12 ), C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl-C ₂ -C ₁₂ alkenyl group, 1-naphthyl-C ₂ -C ₁₂ alkenyl group, 2-naphthyl -C ₂ -C ₁₂ alkenyl group and the like. From the viewpoint of solubility of the polymer in an organic solvent, device characteristics, ease of synthesis of the polymer, etc., C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl group, C ₂ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkenyl groups are preferred.

The arylalkynyl group usually has about 8 to 60 carbon atoms. Specific examples of the arylalkynyl group include a phenyl-C ₂ -C ₁₂ alkynyl group (“C ₂ -C ₁₂ alkynyl” means that the alkynyl moiety has 2 to 12 carbon atoms. The same applies hereinafter. C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl-C ₂ -C ₁₂ alkynyl group, 1-naphthyl-C ₂ -C ₁₂ alkynyl group, 2-naphthyl -C ₂ -C ₁₂ alkynyl group and the like. From the viewpoint of solubility of the polymer in an organic solvent, device characteristics, ease of synthesis of the polymer, etc., C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferable.

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. These alkyl group, aryl group, arylalkyl group and monovalent heterocyclic group may have a substituent. The carbon number of the substituted amino group does not include the carbon number of the substituent, and is usually about 1 to 60, preferably 2 to 48. Specific examples of the substituted amino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, i-propylamino group, diisopropylamino group, butylamino group, i-butyl. Amino group, t-butylamino group, s-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7 - dimethyloctyl amino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ ~ ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, Pirajiruamino group, a phenyl -C triazyl amino group ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ Alkyl) amino group, 1-naphthyl-C ₁ -C ₁₂ alkylamino group, 2-naphthyl-C ₁ -C ₁₂ alkylamino group and the like.

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

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

  The acyl group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples of the 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 acyloxy group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples of the 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.

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

（式中、Ｍｅはメチル基を表す。また、波線は、結合手を表し、イミン残基の種類によっては、シス体、トランス体等の幾何異性体を持つ場合があることを意味する。）

(In the formula, Me represents a methyl group. Further, a wavy line represents a bond, and it may have a geometric isomer such as a cis isomer or a trans isomer depending on the type of imine residue.)

  The amide group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, and a dibenzamide group. , Ditrifluoroacetamide group, dipentafluorobenzamide group and the like.

  As an acid imide group, the residue obtained by remove | excluding one hydrogen atom couple | bonded with the nitrogen atom from acid imide is mentioned, and carbon number is about 4-20. Specific examples of the acid imide group include the groups 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 the monovalent heterocyclic group is usually about 4 to 60, preferably 4 to 20. The carbon number of the monovalent heterocyclic group does not include the carbon number of the substituent. The heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, silicon, etc. Say. Specific examples of the monovalent heterocyclic group, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, piperidyl group, quinolyl group, isoquinolyl group etc., and a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

  Examples of the substituted carboxyl group include a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The carbon number of the substituted carboxyl group is usually about 2 to 60, preferably 2 to 48. The carbon number of the substituted carboxyl group does not include the carbon number of the substituent. Specific examples of the substituted carboxyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, i-propoxycarbonyl group, butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, s-butoxycarbonyl group, pentyl. Oxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl Group, dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycal Group, perfluorooctyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group and the like.

In said formula (1), R < ² > is the alkyl group which may have a substituent, or the alkoxy group which may have a substituent. Specific examples of these alkyl groups and alkoxy groups include those exemplified in the section for R ¹ . R ² is preferably an alkyl group which may have a substituent from the viewpoint of device characteristics and the like, and further an alkyl group having 5 to 8 carbon atoms (however, the carbon number of the substituent is not included). It is more preferable that

〔式中、Ｒ¹、Ｒ²及びｎは、それぞれ独立に、前記と同じ意味を表す。複数存在するＲ²及びｎは、それぞれ、同一であっても異なっていてもよい。Ｒ¹が複数存在する場合には、それらは同一であっても異なっていてもよい。〕
で表されるものが好ましい。 The repeating unit represented by the formula (1) is represented by the following formula (1-1) from the viewpoint of ease of synthesis of the polymer, device characteristics, and the like.

[Wherein, R ¹ , R ² and n each independently represent the same meaning as described above. A plurality of R ² and n may be the same or different. When a plurality of R ¹ are present, they may be the same or different. ]
The thing represented by these is preferable.

（式中、Ｒ²は、前記と同じである。複数存在するＲ²は、同一であっても異なっていてもよい。）
で表されるものが好ましい。 The repeating unit represented by the formula (1-1) is represented by the following formula (1-2) from the viewpoint of ease of synthesis of the polymer, device characteristics, and the like:

(In the formula, R ² is the same as described above. A plurality of R ² may be the same or different.)
The thing represented by these is preferable.

等が挙げられる。 As a specific example of the repeating unit represented by the formula (1),

Etc.

-Repeating unit with hole injection property-
In the present invention, the “repeating unit having hole injecting property” means the absolute value of the energy level (eV) of the HOMO (maximum occupied level) of a polymer of 10-mer or more consisting of only the repeating unit. A repeating unit that is smaller than the absolute value of the HOMO energy level (eV) of a polymer of 10-mer or more consisting only of the repeating unit represented by the formula (1), and represented by the formula (1) The absolute value of the energy level (eV) of HOMO is the smallest among all the repeating units constituting the repeating unit, the repeating unit having the electron injecting property, and the polymer including the repeating unit having the hole injecting property. Refers to a repeating unit. Hereinafter, when two or more types of repeating units represented by the formula (1) are contained in the polymer, the formula (1-2) will be described as an example. Two R ² are n-octyl groups. The HOMO and LUMO energy levels of a polymer of 10-mer or higher consisting only of repeating units are the HOMO and LUMO energy levels of a polymer of 10-mer or higher consisting only of the repeating unit represented by the formula (1). It is considered.

  Examples of the repeating unit having a hole injecting property include a divalent aromatic amine group and a divalent heterocyclic group containing only a nitrogen atom as a hetero atom, and a divalent aromatic amine group from the viewpoint of device characteristics. Is preferred.

〔式中、Ａｒ₁、Ａｒ₂、Ａｒ₃及びＡｒ₄は、それぞれ独立に、置換基を有していてもよいアリーレン基又は２価の複素環基を表す。Ａｒ₅、Ａｒ₆及びＡｒ₇は、それぞれ独立に、置換基を有していてもよいアリール基又は１価の複素環基を表す。ｘ及びｙは、それぞれ独立に、０又は正の整数である。〕
で表される基が、発光波長を変化させる観点、発光効率を高める観点、耐熱性を向上させる観点から好ましい。 Examples of the divalent aromatic amine group include an atomic group obtained by removing two hydrogen atoms from the aromatic ring of a compound derived from an aromatic tertiary amine. Among the divalent aromatic amine groups, the following formula (2):

[Wherein, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent an arylene group or a divalent heterocyclic group which may have a substituent. Ar ₅ , Ar ₆ and Ar ₇ each independently represent an aryl group or a monovalent heterocyclic group which may have a substituent. x and y are each independently 0 or a positive integer. ]
Is preferable from the viewpoint of changing the emission wavelength, increasing the luminous efficiency, and improving the heat resistance.

  In the formula (2), x is preferably an integer of 0 to 2, more preferably 0 or 1, from the viewpoint of device characteristics such as luminance half life and ease of synthesis of the polymer. . In the formula (2), y is preferably an integer of 0 to 2, more preferably 0 or 1, from the viewpoint of device characteristics such as lifetime and ease of polymer synthesis. .

In the formula (2), the arylene group represented by Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and having a condensed ring, Those in which two or more independent benzene rings or condensed rings are bonded directly or via a group such as vinylene are also included. The arylene group may have a substituent. Carbon number of the part except the substituent in an arylene group is about 6-60 normally, Preferably it is 6-20. Moreover, the total carbon number including the substituent of an arylene group is about 6-100 normally.

Examples of the arylene group represented by Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ include a phenylene group (for example, the following formulas 1 to 3), a naphthalenediyl group (for example, the following formulas 4 to 13), an anthracene-diyl group ( For example, the following formulas 14 to 19), a biphenyl-diyl group (for example, the following formulas 20 to 25), a terphenyl-diyl group (for example, the following formulas 26 to 28), a condensed ring compound group (for example, the following formulas 29 to 35) ), A fluorene-diyl group (for example, the following formulas 36 to 38), a stilbene-diyl group (the following formulas 39 to 42), a distilben-diyl group (for example, the following formulas 43 and 44), a benzofluorene-diyl group (for example, Examples include the following formulas A-1 to A-3) and a dibenzofluorene-diyl group (for example, the following formula A-4).

（式中、Ｒは、水素原子又は置換基を表す。Ｒ⁴は、水素原子、アルキルチオ基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、ニトロ基又はシアノ基を表す。複数存在するＲ及びＲ⁴は、それぞれ、同一であっても異なっていてもよい。）

(Wherein R represents a hydrogen atom or a substituent. R ⁴ represents a hydrogen atom, an alkylthio group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue) Represents a group, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a nitro group or a cyano group, and a plurality of R and R ⁴ may be the same or different. May be good.)

In the above formulas 1 to 44 and A-1 to A-4, examples of the substituent represented by R include 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, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, Examples thereof include a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, and a cyano group. A hydrogen atom contained in these substituents may be substituted with a fluorine atom. These groups, residues and atoms are the same as those explained and exemplified in the section of the substituent represented by R ¹ . In view of solubility of the polymer in an organic solvent and device characteristics, at least one R is preferably other than a hydrogen atom. The substituent represented by R is preferably an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, or a monovalent heterocyclic group, an alkyl group, An alkoxy group and an aryl group are more preferable.

The divalent heterocyclic group represented by Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ refers to the remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound. The heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, arsenic in the ring. Say. Of the divalent heterocyclic groups, an aromatic heterocyclic group is preferable. Carbon number of a bivalent heterocyclic group is about 3-100 normally.

Examples of the divalent heterocyclic group represented by Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ include a pyridine-diyl group (for example, the following formulas 45 to 50) and a diazaphenylene group (for example, the following formula 51 -54), quinoline diyl group (for example, the following formulas 55 to 69), quinoxaline diyl group (for example, the following formulas 70 to 74), acridine diyl group (for example, the following formulas 75 to 78), bipyridyl diyl group (for example, the following formula 79-81), divalent heterocyclic groups containing a nitrogen atom as a hetero atom, such as a phenanthroline diyl group (for example, the following formulas 82 to 84), a group having a carbazole structure (for example, the following formulas 85 to 87); 5-membered ring heterocyclic group containing atoms such as oxygen, silicon, nitrogen, sulfur, selenium as atoms (for example, the following formulas 88 to 92); 5 containing atoms such as oxygen, silicon, nitrogen, selenium as heteroatoms 5-membered ring heterocyclic group (for example, the following formulas 93 to 103); a 5-membered ring heterocyclic group containing oxygen, silicon, nitrogen, sulfur, selenium, etc. as a hetero atom, and bonded at the α-position of the hetero atom. A dimer or oligomer group (for example, the following formulas 104 to 105); a 5-membered heterocyclic group containing oxygen, silicon, nitrogen, sulfur, selenium or the like as a hetero atom; A group bonded to a phenyl group at the position (for example, the following formulas 106 to 112); a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur, etc. as a hetero atom; Examples include substituted groups (for example, the following formulas 113 to 118).

（式中、Ｒは、前記で定義したとおりである。複数存在するＲは、同一であっても異なっていてもよい。）

(In the formula, R is as defined above. A plurality of R may be the same or different.)

  Specific examples of the group represented by the formula (2) include those represented by the following formulas 119 to 126.

（式中、Ｒは、前記で定義したとおりである。複数存在するＲは、同一であっても異なっていてもよい。）

(In the formula, R is as defined above. A plurality of R may be the same or different.)

〔式中、Ｒ³は、水素原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルコキシ基を表す。複数存在するＲ³は、同一であっても異なっていてもよい。〕
のいずれかで表される基が好ましい。 As the group represented by the formula (2), the following formulas (2-1) to (2-3):

[Wherein R ³ represents a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent. A plurality of R ³ may be the same or different. ]
The group represented by either of these is preferable.

From the viewpoint of luminance half life, R ³ is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms.

  A divalent heterocyclic group containing only a nitrogen atom as a hetero atom means a divalent heterocyclic group containing only a nitrogen atom as a hetero atom. Specific examples thereof include the above formulas 45 to 87, 89, 93, 108, 112 and the like.

等が挙げられる。 As a specific example of the repeating unit having the hole injection property,

Etc.

-Repeating unit with electron injection property-
In the present invention, the “repeating unit having an electron injecting property” means that the absolute value of the LUMO (lowest empty level) energy level (eV) of a polymer of 10-mer or more consisting only of the repeating unit is the above formula. A repeating unit which is larger than the absolute value of the LUMO energy level (eV) of a polymer of 10-mer or more consisting only of the repeating unit represented by (1), and represented by the above-mentioned formula (1) The repeating unit with the largest absolute value of the LUMO energy level (eV) among all the repeating units constituting the repeating unit, the polymer containing the repeating unit having the electron injecting property, and the repeating unit having the hole injecting property Say.

  The repeating unit having an electron injecting property is preferably a divalent heterocyclic group or an optionally substituted benzofluorenediyl group from the viewpoint of device characteristics and the like.

In the benzofluorenediyl group which may have the substituent, the substituent is the same as described and exemplified as the substituent represented by R ¹ .

〔式中、Ｒ¹は前述と同じ意味を表し、ｍ１は０〜３の整数を表し、ｍ２は０〜５の整数を表す。Ｒ¹及びｍ１が複数存在する場合には、それぞれ、それらは同一であっても異なっていてもよい。式（３−１）において、Ｘ’は、−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）−、−Ｓ（＝Ｏ）₂−、−Ｓｉ（Ｒ⁵）₂−Ｓｉ（Ｒ⁵）₂−、−Ｓｉ（Ｒ⁵）₂−、−Ｂ（Ｒ⁵）−、−Ｐ（Ｒ⁵）−、−Ｐ（＝Ｏ）（Ｒ⁵）−、−Ｏ−Ｃ（Ｒ⁵）₂−又は−Ｎ＝Ｃ（Ｒ⁵）−を表し、式（３−２）、（３−３）、（３−４）において、Ｘ’は、−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）−、−Ｓ（＝Ｏ）₂−、−Ｓｉ（Ｒ⁵）₂−Ｓｉ（Ｒ⁵）₂−、−Ｓｉ（Ｒ⁵）₂−、−Ｂ（Ｒ⁵）−、−Ｐ（Ｒ⁵）−、−Ｐ（＝Ｏ）（Ｒ⁵）−、−Ｏ−Ｃ（Ｒ⁵）₂−、−Ｃ（Ｒ⁵）₂−Ｏ−、−Ｃ（Ｒ⁵）＝Ｎ−又は−Ｎ＝Ｃ（Ｒ⁵）−を表し、Ｒ⁵は水素原子又は置換基を表す。Ｒ⁵が複数存在する場合には、それらは同一であっても異なっていてもよい。〕
のいずれかで表される繰り返し単位が、発光効率等の素子特性の観点から好ましい。 Examples of the divalent heterocyclic group include the following formulas (3-1) to (3-4):

[Wherein, R ¹ represents the same meaning as described above, m1 represents an integer of 0 to 3, and m2 represents an integer of 0 to 5. When a plurality of R ¹ and m1 are present, they may be the same or different. In the formula (3-1), X 'is, -O -, - S -, - S (= O) -, - S (= O) 2 -, - Si (R 5) 2 -Si (R 5) _2- , -Si (R ⁵ ) _2- , -B (R ⁵ )-, -P (R ⁵ )-, -P (= O) (R ⁵ )-, -O-C (R ⁵ ) _2- or -N = C (R ⁵⁾ - represents the formula (3-2), in (3-3), (3-4), X 'is, -O -, - S -, - S (= O ) -, - S (= O ) 2 -, - Si (R 5) 2 -Si (R 5) 2 -, - Si (R 5) 2 -, - B (R 5) -, - P (R 5 ) -, - P (= O ) (R 5) -, - O-C (R 5) 2 -, - C (R 5) 2 -O -, - C (R 5) = N- or -N = C (R ⁵ ) — is represented, and R ⁵ represents a hydrogen atom or a substituent. When a plurality of R ⁵ are present, they may be the same or different. ]
Is preferable from the viewpoint of device characteristics such as luminous efficiency.

R ⁵ is preferably a substituent, and examples of the substituent represented by R ⁵ include an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, aryl Alkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic ring Group, carboxyl group, substituted carboxyl group, nitro group, cyano group and the like. A hydrogen atom contained in these groups and residues may be substituted with a fluorine atom. Among R ⁵ , from the viewpoint of device characteristics such as luminance half-life, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, a monovalent complex A cyclic group is preferred, an alkyl group, an alkoxy group, an aryl group, a monovalent heterocyclic group is more preferred, and an alkyl group and an aryl group are particularly preferred. These groups are specifically the same as those described and exemplified as the substituent represented by R ¹ .

  m1 is preferably 1 from the viewpoint of device characteristics. Further, m2 is preferably 1 from the viewpoint of device characteristics.

〔式中、Ｒ¹、ｍ１及びｍ２は、それぞれ独立に、前述と同じ意味を表す。Ｒ¹及びｍ１が複数存在する場合には、それぞれ、それらは同一であっても異なっていてもよい。式（３−５）において、Ｘ’’は、−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）−、−Ｓ（＝Ｏ）₂−、−Ｓｉ（Ｒ⁵）₂−Ｓｉ（Ｒ⁵）₂−、−Ｓｉ（Ｒ⁵）₂−、−Ｂ（Ｒ⁵）−、−Ｐ（Ｒ⁵）−、−Ｐ（＝Ｏ）（Ｒ⁵）−、−Ｏ−Ｃ（Ｒ⁵）₂−又は−Ｎ＝Ｃ（Ｒ⁵）−を表し、式（３−６）において、Ｘ’’は、−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）−、−Ｓ（＝Ｏ）₂−、−Ｓｉ（Ｒ⁵）₂−Ｓｉ（Ｒ⁵）₂−、−Ｓｉ（Ｒ⁵）₂−、−Ｂ（Ｒ⁵）−、−Ｐ（Ｒ⁵）−、−Ｐ（＝Ｏ）（Ｒ⁵）−、−Ｏ−Ｃ（Ｒ⁵）₂−、−Ｃ（Ｒ⁵）₂−Ｏ−、−Ｃ（Ｒ⁵）＝Ｎ−又は−Ｎ＝Ｃ（Ｒ⁵）−を表し、Ｒ⁵は前述と同じ意味を表す。Ｒ⁵が複数存在する場合には、それらは同一であっても異なっていてもよい。〕
が好ましい。 Among the formulas (3-1) to (3-4), the following formulas (3-5) to (3-6):

[Wherein, R ¹ , m 1 and m 2 each independently represent the same meaning as described above. When a plurality of R ¹ and m1 are present, they may be the same or different. In Formula (3-5), X '' is, -O -, - S -, - S (= O) -, - S (= O) 2 -, - Si (R 5) 2 -Si (R 5 ) ₂ −, —Si (R ⁵ ) ₂ —, —B (R ⁵ ) —, —P (R ⁵ ) —, —P (═O) (R ⁵ ) —, —O—C (R ⁵ ) ₂ — Or —N═C (R ⁵ ) —, and in formula (3-6), X ″ represents —O—, —S—, —S (═O) —, —S (═O) _2. ^{-, - Si (R 5)} 2 -Si (R 5) 2 -, - Si (R 5) 2 -, - B (R 5) -, - P (R 5) -, - P (= O) ( R ⁵ ) —, —O—C (R ⁵ ) ₂ —, —C (R ⁵ ) ₂ —O—, —C (R ⁵ ) ═N— or —N═C (R ⁵ ) — ⁵ represents the same meaning as described above. When a plurality of R ⁵ are present, they may be the same or different. ]
Is preferred.

〔式中、Ｒ³は、前述と同じ意味を表し、Ｘ’’’は、−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）−、−Ｓ（＝Ｏ）₂−、−Ｓｉ（Ｒ⁵）₂−Ｓｉ（Ｒ⁵）₂−、−Ｓｉ（Ｒ⁵）₂−、−Ｂ（Ｒ⁵）−、−Ｐ（Ｒ⁵）−、−Ｐ（＝Ｏ）（Ｒ⁵）−、−Ｏ−Ｃ（Ｒ⁵）₂−又は−Ｎ＝Ｃ（Ｒ⁵）−を表し、Ｒ⁵は前述と同じ意味を表す。複数存在するＲ³は、同一であっても異なっていてもよい。Ｒ⁵が複数存在する場合には、それらは同一であっても異なっていてもよい。〕
で表されるものが好ましい。 Among the above formulas (3-1) to (3-4), from the viewpoint of ease of polymer synthesis, device characteristics, etc., the following formula (3):

[Wherein R ³ represents the same meaning as described above, and X ′ ″ represents —O—, —S—, —S (═O) —, —S (═O) ₂ —, —Si (R _{^{5) 2 -Si (R 5)}} 2 -, - Si (R 5) 2 -, - B (R 5) -, - P (R 5) -, - P (= O) (R 5) -, - O—C (R ⁵ ) ₂ — or —N═C (R ⁵ ) — is represented, and R ⁵ represents the same meaning as described above. A plurality of R ³ may be the same or different. When a plurality of R ⁵ are present, they may be the same or different. ]
The thing represented by these is preferable.

From the viewpoint of device characteristics and the like, X ′ ″ in the formula (3) is preferably —O—, —S—, or —Si (R ⁵ ) ₂ —. Further, R ⁵ in the formula (3) is preferably an alkyl group or an alkoxy group.

R ³ in the formula (3) is preferably an alkyl group or an alkoxy group from the viewpoint of device characteristics and the like, and is preferably an alkyl group having 5 to 8 carbon atoms or an alkoxy group having 5 to 8 carbon atoms. preferable.

等が挙げられる。 As a specific example of the repeating unit having the electron injection property,

Etc.

  The polymer may contain two or more types of repeating units represented by the formula (1), may contain two or more types of repeating units having an electron injecting property, and has a hole injecting property. Two or more kinds of repeating units may be included.

Other repeating units The polymer contained in the composition of the present invention is further represented by the following formula (4):
^{-CR 6 = CR 7 - (4} )
(In the formula, R ⁶ and R ⁷ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group.)
And / or the following formula (5):
-C≡C- (5)
The repeating unit represented by these may be included.

In the formula (4), the alkyl group, aryl group, monovalent heterocyclic group, and substituted carboxyl group represented by R ⁶ and R ⁷ are specifically the term of the substituent represented by R ^1. As described and exemplified in FIG.

  The polymer is a range that does not impair the light emission characteristics and charge transport characteristics, and further, the repeating unit represented by the formula (1), the repeating unit having an electron injection property, the repeating unit having a hole injection property, A repeating unit other than the repeating unit represented by (4) and the repeating unit represented by the formula (5) may be included.

  The repeating unit in the polymer may be linked with a non-conjugated structure, or the repeating unit may contain the non-conjugated structure. Examples of this non-conjugated structure include those shown below, and combinations of two or more thereof.

（式中、Ｒは独立に、前記で定義したとおりであり、Ａｒはヘテロ原子を含んでいてもよい炭素数６〜６０の炭化水素基を表す。Ｒが複数存在する場合には、それらは同一であっても異なっていてもよい。）

(In the formula, R is independently as defined above, and Ar represents a hydrocarbon group having 6 to 60 carbon atoms which may contain a hetero atom. When a plurality of R are present, They may be the same or different.)

  In the above formula, examples of the hetero atom include oxygen, sulfur, nitrogen, silicon, boron, phosphorus, selenium, and the like.

  The polymer may be any of a random copolymer, a graft copolymer, and an alternating copolymer. Moreover, the case where there are branches in the main chain and there are 3 or more terminal portions and dendrimers are also included.

  In the polymer, the ratio of the repeating unit represented by the formula (1) in all repeating units is preferably 10 to 95 mol% from the viewpoint of device characteristics such as luminance half life, and 50 to 90 mol. % Is more preferable. Further, the ratio of the repeating unit having electron injecting property in all repeating units is preferably 2 to 50 mol%, more preferably 5 to 30 mol% from the viewpoint of device characteristics such as luminance half life. . In addition, the ratio of the repeating units having hole injection properties in all repeating units is preferably 2 to 50 mol%, more preferably 5 to 30 mol%, from the viewpoint of device characteristics such as luminance half life. preferable.

The number average molecular weight in terms of polystyrene of the polymer is usually about 1 × 10 ³ to 1 × 10 ⁸ , preferably 1 × 10 ⁴ to 1 × 10 ⁶ . In addition, the polystyrene-equivalent weight average molecular weight is usually about 3 × 10 ³ to 1 × 10 ⁸ , and preferably 5 × 10 ⁴ or more from the viewpoint of film formability and light emission efficiency when used as an element. Yes, 1 × 10 ⁵ or more is more preferable, but from the viewpoint of solubility of the polymer in an organic solvent, it is preferably 1 × 10 ^{5 to} 5 × 10 ⁶ . Whether a polymer having a number average molecular weight and a weight average molecular weight in the range of one kind alone is used in the device or when two or more polymers are used in combination in the device, the resulting device has high luminous efficiency. is there. Further, from the viewpoint of improving the film formability of the composition of the present invention, it is preferable that the degree of dispersion defined by the weight average molecular weight / number average molecular weight is 3 or less.

  When a group (usually called a polymerization active group) involved in polymerization remains in a group located at the molecular chain terminal of the polymer (that is, a terminal group), the composition is used for a light emitting device. Since there is a possibility that the light emission characteristics and the lifetime may be reduced, it is preferable that the light-emitting characteristics and the lifetime are protected with a stable group not involved in polymerization. As this terminal group, those having a conjugated bond continuous with the conjugated structure of the molecular chain main chain are preferable, for example, a structure bonded to an aryl group or a heterocyclic group through a carbon-carbon bond is exemplified. Is done. Specifically, substituents described in Chemical formula 10 of JP-A-9-45478 are exemplified.

  In the polymer, at least one end of the molecular chain terminal is selected from a monovalent heterocyclic group, a monovalent aromatic amine group, a monovalent group derived from a heterocyclic coordination metal complex, and an aryl group. It is expected to add various properties by sealing with aromatic end groups. Specifically, the effect of increasing the time required to reduce the luminance of the element, the effect of increasing the charge injection property, the charge transport property, the light emission property, the effect of increasing the compatibility and interaction between polymers, the anchor effect, etc. Is mentioned.

Examples of the method for producing the polymer include a method of polymerizing by a Suzuki reaction (Chemical Review (Chem. Rev.), Vol. 95, page 2457 (1995)), a method of polymerizing by a Grignard reaction (Kyoritsu Shuppan, Molecular Functional Materials Series Volume 2, Polymer Synthesis and Reaction (2), pp. 432-433), Method of Polymerization by Yamamoto Polymerization (Progressive Polymer Science (Prog. Polym. Sci.), Volume 17, 1153- 1205, 1992), a method of polymerizing with an oxidizing agent such as FeCl _3, a method of electrochemically oxidatively polymerizing (Maruzen, Experimental Chemistry Course 4th edition, 28, 339-340) and the like.

  When the composition of the present invention is used for a polymer light-emitting device or the like, the purity of the polymer affects the device performance such as light-emitting properties. Therefore, the monomer before polymerization is distilled, sublimated and purified by a method such as recrystallization. It is preferable to polymerize after purification. Further, after the synthesis, it is preferable to carry out a purification treatment such as reprecipitation purification and fractionation by chromatography.

-Compound exhibiting phosphorescence-
The compound that exhibits phosphorescence usually exhibits phosphorescence at room temperature (ie, 25 ° C.).

Examples of the phosphorescent compound include metal complexes in which a central metal is a transition metal or a lanthanoid. Specifically, for example, Ir (ppy) ₃ , Btp ₂ Ir (acac) having iridium as a central metal, Examples thereof include PtOEP having platinum as a central metal and Eu (TTA) ₃ phen having europium as a central metal.

  In addition, Nature, (1998), 395, 151, Appl. Phys. Lett. (1999), 75 (1), 4, Proc. SPIE-Int. Soc. Opt. Eng. (2001), 4105 (Organic Light-Emitting Materials and Devices IV), 119, J. Am. Chem. Soc., (2001), 123, 4304, Appl. Phys. Lett., (1997), 71 (18), 2596, Syn. Met. , (1998), 94 (1), 103, Syn. Met., (1999), 99 (2), 1361, Adv. Mater., (1999), 11 (10), 852, Jpn.J.Appl. Phys., 34, 1883 (1995), WO0141512, WO03033617, 04-2 Proceedings of Organic EL Study Group (2004), WO2005 / 113704, WO2006 / 014599, etc., represented by the following structural formula And the like are exemplified.

（式中、Ｒは独立に、前記で定義したとおりである。複数存在するＲは、同一であっても異なっていてもよい。）

(In the formula, R is independently as defined above. A plurality of R may be the same or different.)

  In the composition of the present invention, the ratio between the polymer and the phosphorescent compound varies depending on the type of polymer and the property to be optimized, and is not particularly limited. The phosphorescent compound is usually 0.01 to 49 parts by weight, preferably 0.1 to 40 parts by weight.

  In the composition of the present invention, the polymer and the phosphorescent compound may be used singly or in combination of two or more.

-Small molecule fluorescent material-
The low-molecular fluorescent material usually has a photoluminescence emission peak in a wavelength range of 400 to 700 nm. The molecular weight of the low-molecular fluorescent material is usually less than 3000, preferably about 100 to 1000, and more preferably about 100 to 500.

  Examples of the low-molecular fluorescent material include naphthalene derivatives, anthracene, anthracene derivatives, perylene, perylene derivatives, polymethine dyes, xanthene dyes, coumarin dyes, cyanine dyes, and metal complexes of 8-hydroxyquinoline as ligands. Metal complexes having 8-hydroxyquinoline derivatives as ligands, other fluorescent metal complexes, aromatic amines, tetraphenylcyclopentadiene, tetraphenylcyclopentadiene derivatives, tetraphenylcyclobutadiene, tetraphenylcyclobutadiene Of low molecular weight compounds such as derivatives, stilbene, silicon-containing aromatics, oxazoles, furoxanes, thiazoles, tetraarylmethanes, thiadiazoles, pyrazoles, metacyclophanes, acetylenes, etc. Light resistance materials. Specific examples include those described in JP-A-57-51781, JP-A-59-194393, and the like. Hereinafter, in the illustration of the low molecular fluorescent material, R in the formula represents the same meaning as described above, and among them, a hydrogen atom, an alkyl group, a monovalent heterocyclic group, a substituted amino group, a cyano group, or a halogen atom. Is preferred. Moreover, the hydrogen atom contained in these groups may be substituted with a fluorine atom.

  As a naphthalene derivative, the compound represented by a following formula is illustrated.

（式中、Ｒは前述と同じ意味を表す。複数存在するＲは、同一であっても異なっていてもよい。）

(In the formula, R represents the same meaning as described above. A plurality of R may be the same or different.)

  As the anthracene derivative, a compound represented by the following formula is exemplified.

（式中、Ｒは前述と同じ意味を表す。複数存在するＲは、同一であっても異なっていてもよい。）

(In the formula, R represents the same meaning as described above. A plurality of R may be the same or different.)

  Examples of the perylene derivative include compounds represented by the following formula.

（式中、Ｒは前述と同じ意味を表す。複数存在するＲは、同一であっても異なっていてもよい。）

(In the formula, R represents the same meaning as described above. A plurality of R may be the same or different.)

  Examples of polymethine dyes include compounds represented by the following formula.

（式中、Ｒは前述と同じ意味を表し、ｎ_aは２〜２０の整数を表し、Ｘ_a ^-はハロゲンを含有するアニオンを表し、Ｍａ⁺は金属イオンを表す。Ｒが複数存在する場合には、それらは同一であっても異なっていてもよい。）

(In the formula, R represents the same meaning as described above, n _a represents an integer of 2 to 20, X _a ⁻ represents an anion containing halogen, and Ma ⁺ represents a metal ion. They may be the same or different.)

X _a ^- Specific examples of the anion containing a halogen represented by ^{the, I -, Br -, Cl} -, ClO 4 - , and the like.

  Examples of xanthene dyes include compounds represented by the following formula.

（式中、Ｒは前述と同じ意味を表し、Ｘ_bは、−Ｏ−、−Ｓ−、−ＮＲ⁷−、−ＣＲ⁷ ₂−又は−Ｃ（＝Ｏ）−を表す。ここで、Ｒ⁷は置換基を表す。複数存在するＲ及びＸ_bは、それぞれ、同一であっても異なっていてもよい。Ｒ⁷が複数存在する場合には、それらは同一であっても異なっていてもよい。）

(Wherein R represents the same meaning as described above, and X _b represents —O—, —S—, —NR ⁷ —, —CR ⁷ ₂ — or —C (═O) —, where R ⁷ represents a substituent, and a plurality of R and X _b may be the same or different, and when a plurality of R ⁷ are present, they may be the same or different. Good.)

Examples of the substituent represented by R ⁷ include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, Amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, nitro group And a cyano group. The hydrogen atom contained in these substituents may be substituted with a fluorine atom or other group. Among these substituents, from the viewpoint of solubility of the polymer in an organic solvent and ease of synthesis of the polymer, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, An arylalkyl group, an arylalkoxy group, and a monovalent heterocyclic group are preferable, and an alkyl group, an alkoxy group, an aryl group, and a monovalent heterocyclic group are more preferable. Among these substituents, from the viewpoint of device characteristics, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group (the number of carbon atoms is usually 1 to 12, preferably 5 to 8). And substituted carboxyl groups are preferred. The substituent represented by R ⁷ is specifically the same as described and exemplified as R ¹ above.

  Examples of the coumarin dye include compounds represented by the following formula.

（式中、Ｒは前述と同じ意味を表し、Ａｒ_aはアリーレン基又は２価の複素環基を表し、Ａｒ_bはアリール基又は１価の複素環基を表す。複数存在するＲ及びＡｒ_bは、それぞれ、同一であっても異なっていてもよい。）

(Wherein R represents the same meaning as described above, Ar _a represents an arylene group or a divalent heterocyclic group, and Ar _b represents an aryl group or a monovalent heterocyclic group. A plurality of R and Ar _b exist. Each may be the same or different.)

Examples of the arylene group represented by Ar _a and the divalent heterocyclic group include the same groups as those described above for Ar _1. Examples of the aryl group represented by Ar _b and the monovalent heterocyclic group include those described above. Examples are the same as those for R ¹ .

  Examples of cyanine dyes include compounds represented by the following formula.

（式中、Ｒは前述と同じ意味を表し、ｎ_bは、０〜３の整数を表し、Ｘ_cは独立に、−Ｏ−、−Ｓ−、−ＮＲ−、−Ｓｅ−又は−ＣＨ＝ＣＨ−を表し、Ｘ_d ^-は、ハロゲン化物イオンを表し、Ｍ_bは金属原子を表す。また、矢印は配位結合を表す。複数存在するＲ及びＸ_cは、それぞれ、同一であっても異なっていてもよい。）

(Wherein R represents the same meaning as described above, n _b represents an integer of 0 to 3, and X _c independently represents —O—, —S—, —NR—, —Se— or —CH═. represents CH-, X _d ^-.. represents a halide ion, M _b represents a metal atom or, R and X _c arrow presence of a plurality represents a coordinate bond, respectively, be the same May be different.)

Examples of X _d ⁻ include fluoride ions, chloride ions, and bromide ions. Examples of M _b include magnesium, chromium, iron, nickel, copper, zinc, gallium, and lead.

  As the 8-hydroxyquinoline derivative, a compound represented by the following formula is exemplified.

（式中、Ｒは前述と同じ意味を表す。複数存在するＲは、同一であっても異なっていてもよい。また、※の位置で金属と結合する。）

(In the formula, R represents the same meaning as described above. A plurality of R may be the same or different. In addition, R is bonded to a metal at the position of *).

  The other fluorescent metal complex means a metal complex that emits fluorescence at room temperature (that is, 25 ° C.), and usually does not include a metal complex that exhibits phosphorescence. Specific examples of other fluorescent metal complexes include beryllium, magnesium, aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, ruthenium, palladium, silver, cadmium, Examples of the complex include indium and tin. Examples of the ligand constituting these complexes include, but are not limited to, phenylpyridine, bipyridine, chenylpyridine, biquinoline, phenanthroline, biimidazole, phenylpyrazole, chlorophenylpyrazole, nitrophenylpyrazole, and the like. .

  Examples of the aromatic amine include compounds represented by the following formula.

（式中、Ｒは前述と同じ意味を表す。複数存在するＲは、同一であっても異なっていてもよい。）

(In the formula, R represents the same meaning as described above. A plurality of R may be the same or different.)

  Examples of the tetraphenylcyclopentadiene derivative include compounds represented by the following formula.

（式中、Ｒは前述と同じ意味を表す。複数存在するＲは、同一であっても異なっていてもよい。）

(In the formula, R represents the same meaning as described above. A plurality of R may be the same or different.)

  Examples of the tetraphenylcyclobutadiene derivative include compounds represented by the following formula.

（式中、Ｒは前述と同じ意味を表す。複数存在するＲは、同一であっても異なっていてもよい。）

(In the formula, R represents the same meaning as described above. A plurality of R may be the same or different.)

  Examples of the stilbene-based low molecular weight compounds include compounds having a structure represented by the following formula.

（式中、Ｒは前述と同じ意味を表し、ｎ_cは１〜２０の整数を表す。複数存在するＲは、同一であっても異なっていてもよい。）

(Wherein, R represents the same as defined above, n _c is. Plurality of represents an integer of 1 to 20 R may be be the same or different.)

  Examples of the silicon-containing aromatic low-molecular compound include compounds having a structure represented by the following formula.

（式中、Ｒは前述と同じ意味を表し、ｎ_cは１〜２０の整数を表し、Ｘ_eは、−Ｏ−、−Ｓ−、−ＮＲ−又は−ＣＨ＝ＣＨ−を表す。複数存在するＲ及びＸ_eは、それぞれ、同一であっても異なっていてもよい。）

(In the formula, R represents the same meaning as described above, n _c represents an integer of 1 to 20, and X _e represents —O—, —S—, —NR—, or —CH═CH—. And R and X _e may be the same or different.)

  Examples of the oxazole-based low molecular weight compound include compounds represented by the following formula.

（式中、Ｒは前述と同じ意味を表す。複数存在するＲは、同一であっても異なっていてもよい。）

(In the formula, R represents the same meaning as described above. A plurality of R may be the same or different.)

  Examples of the furoxan low molecular weight compounds include compounds represented by the following formulae.

（式中、Ｒは前述と同じ意味を表す。ＮからＯへの矢印は、配位結合を意味する。複数存在するＲは、同一であっても異なっていてもよい。）

(In the formula, R represents the same meaning as described above. An arrow from N to O means a coordination bond. A plurality of R may be the same or different.)

  Examples of thiazole-based low molecular weight compounds include compounds represented by the following formula.

（式中、Ｒ及びＡｒ_aは独立に前述と同じ意味を表す。複数存在するＲは、同一であっても異なっていてもよい。）

(In the formula, R and Ar _a independently represent the same meaning as described above. A plurality of R may be the same or different.)

  Examples of the tetraarylmethane-based low molecular weight compound include compounds represented by the following formulae.

（式中、Ａｒ_bは前述と同じ意味を表す。複数存在するＡｒ_bは、同一であっても異なっていてもよい。）

(In the formula, Ar _b represents the same meaning as described above. A plurality of Ar _b may be the same or different.)

  Examples of the thiadiazole-based low molecular weight compound include compounds represented by the following formula.

（式中、Ｒは前述と同じ意味を表す。複数存在するＲは、同一であっても異なっていてもよい。）

(In the formula, R represents the same meaning as described above. A plurality of R may be the same or different.)

  Examples of the pyrazole-based low molecular weight compound include compounds represented by the following formula.

（式中、Ｒ及びＡｒ_bは独立に前述と同じ意味を表す。Ｒが複数存在する場合には、それらは同一であっても異なっていてもよい。複数存在するＡｒ_bは、同一であっても異なっていてもよい。）

(In the formula, R and Ar _b independently represent the same meaning as described above. When a plurality of R are present, they may be the same or different. A plurality of Ar _b are the same. Or different.)

  Examples of metacyclophane-based low molecular weight compounds include compounds represented by the following formulae.

（式中、Ｒは前述と同じ意味を表す。複数存在するＲは、同一であっても異なっていてもよい。）

(In the formula, R represents the same meaning as described above. A plurality of R may be the same or different.)

  Examples of the acetylene-based low molecular weight compound include compounds represented by the following formulae.

（式中、Ｒは前述と同じ意味を表す。複数存在するＲは、同一であっても異なっていてもよい。）

(In the formula, R represents the same meaning as described above. A plurality of R may be the same or different.)

  In the composition of the present invention, the ratio of the polymer and the low-molecular fluorescent material is not particularly limited because it varies depending on the type of polymer and the property to be optimized, but with respect to 100 parts by weight of the polymer, The low-molecular fluorescent material is usually 0.01 to 49 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and still more preferably 1.0 to 5.0 parts by weight. When such a range is satisfied, the light emission efficiency and luminance are increased.

  In the composition of the present invention, each of the polymer and the low molecular fluorescent material may be used alone or in combination of two or more.

-Other ingredients-
The composition of the present invention comprises components other than the repeating unit represented by the formula (1), a repeating unit having an electron injecting property, a polymer having a repeating unit having a hole injecting property, and a compound exhibiting phosphorescence. You may contain. Specifically, for example, a polymer having no repeating unit represented by the formula (1), a low molecular compound other than a compound exhibiting phosphorescence, and the like may be included. Their content ratio may be determined according to the application.

  In addition, the composition of the present invention may contain a solvent, a hole transport material, an electron transport material, a stabilizer, an additive for adjusting viscosity and / or surface tension, an antioxidant, and the like. Each of these optional components may be used alone or in combination of two or more.

  Examples of the hole transport material that the composition of the present invention may contain include, for example, polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, aryl Amine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof Etc.

  Examples of the electron transport material that may be contained in the composition of the present invention include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthra. Quinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, and the like It is done.

  Examples of the stabilizer that may be contained in the composition of the present invention include phenolic antioxidants and phosphorus antioxidants.

  Examples of the additive for adjusting the viscosity and / or surface tension that may be contained in the composition of the present invention include a high molecular weight compound (thickener) for increasing the viscosity, a poor solvent, and a decrease in viscosity. A low molecular weight compound for reducing the surface tension and a surfactant for reducing the surface tension may be used in appropriate combination.

  The high molecular weight compound is not particularly limited as long as it does not inhibit light emission or charge transport. When the composition contains a solvent, it is usually soluble in the solvent. As the high molecular weight compound, for example, high molecular weight polystyrene, high molecular weight polymethyl methacrylate, or the like can be used. The high molecular weight compound preferably has a polystyrene equivalent weight average molecular weight of 500,000 or more, more preferably 1,000,000 or more. A poor solvent can also be used as a thickener. That is, when the composition of the present invention contains a solvent (that is, a liquid composition described later), the viscosity of the composition can be increased by adding a small amount of a poor solvent to the solid content in the composition. Can be increased. When a poor solvent is added for this purpose, the type and amount of the poor solvent may be selected as long as the solid content in the composition does not precipitate. Considering the stability during storage, the amount of the poor solvent is preferably 50% by weight or less, more preferably 30% by weight or less based on the entire composition.

  The antioxidant that may be contained in the composition of the present invention is not limited as long as it does not inhibit light emission and charge transport. When the composition contains a solvent, it is usually soluble in the solvent. . Examples of the antioxidant include phenolic antioxidants and phosphorus antioxidants. By using an antioxidant, the storage stability of the composition and solvent of the present invention can be improved.

  When the composition of the present invention contains a hole transport material, the ratio of the hole transport material in the composition is usually 1% by weight to 80% by weight, preferably 5% by weight to 60% by weight. %. When the composition of the present invention contains an electron transport material, the proportion of the electron transport material in the composition is usually 1% by weight to 80% by weight, preferably 5% by weight to 60% by weight. is there. The composition of the present invention may contain a fluorescent polymer in addition to the low-molecular fluorescent material.

<Polymer compound>
The polymer compound of the present invention includes a repeating unit represented by the formula (1), a repeating unit having an electron injecting property, a repeating unit having a hole injecting property, and a residue of a compound exhibiting phosphorescence. (That is, those contained within the same molecule). Here, the residue of the compound exhibiting phosphorescence means the remaining group excluding part or all of the hydrogen atoms in the compound exhibiting phosphorescence. Further, in the following description of the polymer compound of the present invention, matters not specifically mentioned are as explained and exemplified in the section of the composition of the present invention.

  The repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (1-1) from the viewpoint of characteristics such as efficiency of a light emitting element, and the formula (1-1) The repeating unit represented by the formula (1-2) is more preferably a repeating unit represented by the formula (1-2).

  In the polymer compound of the present invention, the repeating unit having hole injecting property is preferably a repeating unit represented by the formula (2) from the viewpoint of device characteristics and the like, and is represented by the formula (2). The repeating unit is more preferably a repeating unit represented by any one of the formulas (2-1) to (2-3).

  In the polymer compound of the present invention, from the viewpoint of device characteristics and the like, the repeating unit having an electron injecting property is preferably a divalent heterocyclic group or a benzofluorenediyl group which may have a substituent. More preferably, it is a divalent heterocyclic group. The divalent heterocyclic group is preferably a repeating unit represented by any one of the formulas (3-1) to (3-4) from the viewpoint of device characteristics and the like, and is represented by the formula (3). More preferred is a repeating unit.

The polymer compound of the present invention has a polystyrene-equivalent number average molecular weight of usually 1 × 10 ³ to 1 × 10 ⁸ , and a polystyrene-equivalent weight average molecular weight of usually 3 × 10 ³ to 1 × 10 ⁸ . .

  The polymer compound of the present invention includes a total of the repeating unit represented by the formula (1), the repeating unit having an electron injecting property, and the repeating unit having a hole injecting property, and a residue of the compound exhibiting phosphorescence. Is usually 99.99: 0.01 to 51:49, preferably 99.9: 0.1 to 60:40.

  Examples of the polymer compound of the present invention include, for example, a main chain and a side of a polymer containing the repeating unit represented by the formula (1), the repeating unit having an electron injecting property, and the repeating unit having a hole injecting property. Examples thereof include those having a residue of a compound exhibiting phosphorescence at the chain or terminal, or at two or more positions thereof.

  A polymer compound having a residue of a compound exhibiting phosphorescence in a side chain of a polymer containing the repeating unit represented by the formula (1), a repeating unit having an electron injecting property, and a repeating unit having a hole injecting property Has a structure represented by the following formula, for example.

〔式中、Ａｒ¹⁸は、２価の芳香族基、又は酸素原子、ケイ素原子、ゲルマニウム原子、スズ原子、リン原子、ホウ素原子、硫黄原子、セレン原子及びテルル原子からなる群から選ばれる原子を一個以上有する２価の複素環基を表す。但し、Ａｒ¹⁸は、−Ｌ−Ｘで表される基を１〜４個有する。ここで、Ｘは独立に、燐光発光を示す化合物の１価の残基を表し、Ｌは独立に、単結合、−Ｏ−、−Ｓ−、―ＣＯ−、−ＣＯ₂−、−ＳＯ−、−ＳＯ₂−、−ＳｉＲ⁶⁸Ｒ⁶⁹−、ＮＲ⁷⁰−、−ＢＲ⁷¹−、−ＰＲ⁷²−、−Ｐ（＝Ｏ）（Ｒ⁷³）−、置換されていてもよいアルキレン基、置換されていてもよいアルケニレン基、置換されていてもよいアルキニレン基、置換されていてもよいアリーレン基、又は置換されていてもよい２価の複素環基を表す。但し、該アルキレン基、該アルケニレン基、該アルキニレン基が−ＣＨ₂−基を含む場合、該アルキレン基に含まれる−ＣＨ₂−基の一個以上、該アルケニレン基に含まれる−ＣＨ₂−基の一個以上、該アルキニレン基に含まれる−ＣＨ₂−基の一個以上が、各々、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ₂−、−ＳＯ−、−ＳＯ₂−、−ＳｉＲ⁷⁴Ｒ⁷⁵−、ＮＲ⁷⁶−、−ＢＲ⁷⁷−、−ＰＲ⁷⁸−及び−Ｐ（＝Ｏ）（Ｒ⁷⁹）−からなる群から選ばれる基で置換されていてもよい。ここで、Ｒ⁶⁸〜Ｒ⁷⁹は独立に、水素原子、アルキル基、アリール基、１価の複素環基及びシアノ基からなる群より選ばれる基を表す。Ａｒ¹⁸は、−Ｌ−Ｘで表される基以外に、さらに、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基及びシアノ基からなる群から選ばれる置換基を有していてもよい。Ａｒ¹⁸が複数の置換基を有する場合、それらは同一であってもよいし、それぞれ異なっていてもよい。〕

[In the formula, Ar ¹⁸ represents a divalent aromatic group or an atom selected from the group consisting of oxygen atom, silicon atom, germanium atom, tin atom, phosphorus atom, boron atom, sulfur atom, selenium atom and tellurium atom. It represents a divalent heterocyclic group having one or more. However, Ar ¹⁸ has 1 to 4 groups represented by -L-X. Here, X independently represents a monovalent residue of a phosphorescent compound, and L independently represents a single bond, —O—, —S—, —CO—, —CO ₂ —, —SO—. , —SO ₂ —, —SiR ⁶⁸ R ⁶⁹ —, NR ⁷⁰ —, —BR ⁷¹ —, —PR ⁷² —, —P (═O) (R ⁷³ ) —, an optionally substituted alkylene group, substituted An alkenylene group which may be substituted, an alkynylene group which may be substituted, an arylene group which may be substituted, or a divalent heterocyclic group which may be substituted. However, the alkylene group, the alkenylene group, the alkynylene group is -CH ₂ - when containing group, -CH ₂ contained in the alkylene group - group one or more, -CH ₂ contained in the alkenylene group - the group one or more, -CH ₂ contained in the alkynylene group - one or more groups, each, -O -, - S -, - CO -, - CO 2 -, - SO -, - SO 2 -, - SiR 74 ^{R 75 -, NR 76 -,} - BR 77 -, - PR 78 - and ^{-P (= O) (R 79} ) - group may be substituted selected from the group consisting of. Here, R ^{68 to} R ⁷⁹ independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, and a cyano group. In addition to the group represented by -LX, Ar ¹⁸ is further 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 aryl Alkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group And may have a substituent selected from the group consisting of a substituted carboxyl group and a cyano group. When Ar ¹⁸ has a plurality of substituents, they may be the same or different. ]

Examples of the divalent aromatic group represented by Ar ¹⁸ include phenylene, pyridinylene, pyrimidylene, naphthylene, and the like.

  A polymer compound having a residue of a compound exhibiting phosphorescence emission in a main chain of a polymer containing the repeating unit represented by the formula (1), a repeating unit having an electron injecting property, and a repeating unit having a hole injecting property Has a structure represented by the following formula, for example.

〔式中、Ｌ₁及びＬ₂は、それぞれ独立に、燐光発光を示す化合物から水素原子及び／又は置換基を２個若しくは３個取り除いた構造を表し、式中のＬ₁及びＬ₂が有する結合手は、重合体が有する繰り返し単位と結合している。〕

[Wherein, L ₁ and L ₂ each independently represents a structure in which two or three hydrogen atoms and / or substituents are removed from a phosphorescent compound, and L ₁ and L ₂ in the formula have The bond is bonded to the repeating unit of the polymer. ]

  The high molecular compound which has the residue of the compound which shows a phosphorescence emission in the terminal of the polymer containing the repeating unit represented by said Formula (1) is represented by a following formula, for example.

〔式中、Ｌ₃は燐光発光を示す化合物の１価の残基を表し、その結合手はＹを介して重合体が有する繰り返し単位と結合している。Ｙは単結合、置換されていてもよいアルケニレン基、置換されていてもよいアルキニレン基、置換されていてもよいアリーレン基、又は置換されていてもよい２価の複素環基を表す。〕

[In the formula, L ₃ represents a monovalent residue of a phosphorescent compound, and the bond is bonded to the repeating unit of the polymer via Y. Y represents a single bond, an optionally substituted alkenylene group, an optionally substituted alkynylene group, an optionally substituted arylene group, or an optionally substituted divalent heterocyclic group. ]

A polymer having a monovalent residue of a phosphorescent compound at a side chain, main chain or terminal is, for example, a method of polymerizing by a Suzuki reaction using a monomer having the residue, by a Grignard reaction. It can be produced by a polymerization method, a polymerization method by Yamamoto polymerization method, a polymerization method by an oxidizing agent such as FeCl ₃ , an electrochemical oxidation polymerization method and the like.

  The polymer compound of the present invention is composed by mixing with the low molecular fluorescent material, hole transport material, electron transport material, stabilizer, additive for adjusting viscosity and / or surface tension, antioxidant and the like. A product may be prepared. Further, a liquid composition containing the polymer compound and the solvent may be prepared by mixing the polymer compound and a solvent. Details of the liquid composition will be described later. Each of these optional components may be used alone or in combination of two or more.

<Liquid composition>
The composition of the present invention is particularly useful as a liquid composition for the production of light emitting devices such as polymer light emitting devices and organic transistors. The liquid composition is one in which the composition of the present invention contains a solvent as necessary. In the present specification, the “liquid composition” means a liquid that is liquid at the time of device fabrication, and typically means a liquid at normal pressure (ie, 1 atm) and 25 ° C. The liquid composition is generally called an ink, an ink composition, a solution or the like.

When forming a film using this liquid composition (for example, a composition in a solution state) at the time of producing a polymer light emitting device, it is only necessary to remove the solvent by drying after applying the liquid composition, In addition, when a charge transport material or a light emitting material is mixed, the same method can be applied, which is very advantageous in manufacturing. In addition, in the case of drying, you may dry in the state heated at about 50-150 degreeC, and may be dried under reduced pressure to about 10 ^<-3 > Pa.

  The film formation method using the liquid composition includes 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.

  The ratio of the solvent in the liquid composition is usually 1% by weight to 99.9% by weight, preferably 60% by weight to 99.9% by weight, and more preferably 90% by weight with respect to the total weight of the liquid composition. % By weight to 99.8% by weight. The viscosity of the liquid composition varies depending on the printing method, but it is preferably in the range of 0.5 to 500 mPa · s at 25 ° C. If the liquid composition such as the ink jet printing method passes through a discharge device, clogging or flight during discharge In order to prevent bending, the viscosity is preferably in the range of 0.5 to 20 mPa · s at 25 ° C. Further, the sum of the weight of the polymer containing the repeating unit represented by the formula (1) and the low molecular weight fluorescent material is usually 20% by weight to the total weight of all components excluding the solvent from the liquid composition. 100% by weight, preferably 40% by weight to 100% by weight.

  As the solvent contained in the liquid composition, those capable of dissolving or dispersing components other than the solvent in the composition are preferable. Examples of the solvent include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorinated solvents such as chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, toluene, xylene, and trimethyl. Aromatic hydrocarbon solvents such as benzene and mesitylene, aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, methyl benzoate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether Polyethylene alcohol and its derivatives such as ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerol, 1,2-hexanediol, methanol, ethanol, propanol, isopropanol, cyclohexanol, etc. Examples thereof include alcohol-based solvents, sulfoxide-based solvents such as dimethyl sulfoxide, and amide-based solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These solvents may be used alone or in combination. Among the solvents, it is preferable to include one or more organic solvents having a structure containing at least one benzene ring and having a melting point of 0 ° C. or lower and a boiling point of 100 ° C. or higher in view of viscosity, film formability, and the like. To preferred.

  Solvents include aromatic hydrocarbon solvents and aliphatic hydrocarbon solvents from the viewpoints of solubility in organic solvents other than the solvent in the liquid composition, uniformity during film formation, viscosity characteristics, etc. Ester solvents and ketone solvents are preferred, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, mesitylene, n-propylbenzene, i-propylbenzene, n-butylbenzene, i-butylbenzene, s-butylbenzene, anisole , Ethoxybenzene, 1-methylnaphthalene, cyclohexane, cyclohexanone, cyclohexylbenzene, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, methylbenzoate, 2-propylcyclohexanone, 2-heptanone, - heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2-decanone, dicyclohexyl ketone are preferred, xylene, anisole, mesitylene, cyclohexylbenzene, and it is more preferable to contain at least one of bicyclohexyl methyl benzoate.

  The type of solvent contained in the liquid composition is preferably two or more, more preferably two to three, and more preferably two from the viewpoints of film forming properties and device characteristics. Further preferred.

  When two kinds of solvents are contained in the liquid composition, one of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, it is preferable that one type of solvent has a boiling point of 180 ° C. or higher, and the other one type of solvent preferably has a boiling point of less than 180 ° C. One type of solvent has a boiling point of 200 ° C. More preferably, the solvent has a boiling point of less than 180 ° C. Further, from the viewpoint of viscosity, at 60 ° C., it is preferable that 0.2% by weight or more of the component excluding the solvent from the liquid composition is dissolved in the solvent, and one of the two solvents has 25 ° C. In this case, it is preferable that 0.2% by weight or more of the component excluding the solvent from the liquid composition is dissolved.

  When the liquid composition contains three kinds of solvents, one or two kinds of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, at least one of the three solvents is preferably a solvent having a boiling point of 180 ° C. or higher, and at least one solvent is preferably a solvent having a boiling point of less than 180 ° C. At least one of the types of solvents is a solvent having a boiling point of 200 ° C. or more and 300 ° C. or less, and at least one of the solvents is more preferably a solvent having a boiling point of less than 180 ° C. Further, from the viewpoint of viscosity, it is preferable that two of the three types of solvents have 0.2% by weight or more of the component obtained by removing the solvent from the liquid composition dissolved at 60 ° C. in the solvent. Of these solvents, it is preferable that 0.2% by weight or more of the component obtained by removing the solvent from the liquid composition is dissolved in the solvent at 25 ° C.

  When two or more kinds of solvents are contained in the liquid composition, the solvent having the highest boiling point is 40 to 90% by weight of the total solvent contained in the liquid composition from the viewpoint of viscosity and film formability. Preferably, it is 50 to 90% by weight, more preferably 65 to 85% by weight.

  As the solvent contained in the liquid composition, from the viewpoint of viscosity and film formability, a combination of anisole and bicyclohexyl, a combination of anisole and cyclohexylbenzene, a combination of xylene and bicyclohexyl, a combination of xylene and cyclohexylbenzene, mesitylene and methyl A combination of benzoates is preferred.

  From the viewpoint of solubility of the components other than the solvent contained in the liquid composition in the solvent, the difference between the solubility parameter of the solvent and the solubility parameter of the polymer contained in the composition of the present invention is preferably 10 or less. , 7 or less is more preferable. These solubility parameters can be determined by the method described in “Solvent Handbook (Kodansha, 1976)”.

<Thin film>
Next, the thin film of the present invention will be described. This thin film is formed by using the composition, the polymer compound or the liquid composition. Examples of the thin film include a light-emitting thin film, a conductive thin film, and an organic semiconductor thin film.

  The light-emitting thin film preferably has a quantum yield of light emission of 50% or more, more preferably 60% or more, and further preferably 70% or more from the viewpoint of the brightness of the device, the light emission voltage, and the like. .

  The conductive thin film preferably has a surface resistance of 1 KΩ / □ or less. The electrical conductivity can be increased by doping the thin film with a Lewis acid, an ionic compound or the like. The surface resistance is more preferably 100Ω / □ or less, and further preferably 10Ω / □ or less.

The organic semiconductor thin film has a higher electron mobility or hole mobility, preferably 10 ⁻⁵ cm ² / V / second or more, more preferably 10 ⁻³ cm ² / V / second or more, More preferably, it is 10 ^-1 cm ² / V / second or more. In addition, an organic transistor can be manufactured using an organic semiconductor thin film. Specifically, an organic transistor can be formed by forming an organic semiconductor thin film on a Si substrate on which an insulating film such as SiO ₂ and a gate electrode are formed, and forming a source electrode and a drain electrode with Au or the like. .

<Use of composition>
Next, the use of the composition (including the liquid composition) of the present invention will be described.
The composition of the present invention usually emits fluorescence in a solid state and can be used as a polymer light emitter (that is, a high molecular weight light emitting material). In addition, the composition of the present invention has an excellent charge transport ability, and can be suitably used as a material for a polymer light emitting device or a charge transport material. A polymer light emitting device using the polymer light emitter is a high performance polymer light emitting device that can be driven at a low voltage and a high luminous efficiency. Therefore, the composition of the present invention comprises a surface light source such as a curved light source or a planar light source (for example, illumination); a segment display device (for example, a segment type display element); a dot matrix display device (for example, a dot light source). It is useful as a material for display devices such as a matrix flat display) and a liquid crystal display device (for example, a liquid crystal display device, a backlight of a liquid crystal display). In addition, the composition of the present invention includes a laser dye, an organic solar cell material, an organic semiconductor material for an organic transistor, a conductive thin film, a conductive thin film material such as an organic semiconductor thin film, and a luminescent thin film material that emits fluorescence. Etc. can also be used. The organic transistor can be used as a bipolar transistor or a field effect transistor such as a polymer field effect transistor.

<Polymer light emitting device>
Next, the polymer light emitting device of the present invention will be described.
The polymer light-emitting device of the present invention comprises an electrode composed of an anode and a cathode, and an organic layer (that is, a layer containing an organic substance) provided between the electrodes and containing the composition and / or the polymer compound. is there. The organic layer may be any of a light emitting layer, a hole transport layer, an electron transport layer, and the like, but the organic layer is preferably a light emitting layer. The polymer light-emitting device of the present invention includes those in which the composition of the present invention is contained in a hole transport layer and / or an electron transport layer.

  The light emitting layer refers to a layer having a function of emitting light. The hole transport layer refers to a layer having a function of transporting holes. The electron transport layer refers to a layer having a function of transporting electrons. The hole transport layer and the electron 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 present independently.

  When the polymer light-emitting device of the present invention has a light-emitting layer, the thickness of the light-emitting layer varies depending on the material used and may be selected so that the drive voltage and the light emission efficiency are appropriate values. The thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm.

  Examples of the method for forming the light emitting layer include a method of forming a film from a liquid composition. For film formation from a liquid composition, spin coating method, 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 printing method Application methods such as flexographic printing, offset printing, and inkjet printing can be used. Printing methods such as a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method are preferable in that pattern formation and multicolor coating are easy.

  In the polymer light-emitting device of the present invention, the maximum external quantum yield when a voltage is applied between the anode and the cathode is preferably 1% or more, and 1.5% or more from the viewpoint of the luminance of the device. Is more preferable.

  Examples of the polymer light emitting device of the present invention include a polymer light emitting device in which an electron transport layer is provided between a cathode and a light emitting layer, and a polymer light emitting device in which a hole transport layer is provided between an anode and a light emitting layer. And a polymer light emitting device 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.

Specific examples of the polymer light-emitting device of the present invention include the following structures a) to d).
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.)

  When the composition of the present invention is used for a hole transport layer, the composition of the present invention contains a polymer compound having a hole transporting group (for example, an aromatic amino group, a thienyl group, etc.), or It is preferable that the polymer containing the repeating unit represented by the formula (1) has the hole transporting group. Specific examples of the polymer compound containing a hole transporting group include a polymer containing an aromatic amine and a polymer containing stilbene.

  When the composition of the present invention is used for an electron transporting layer, does the composition of the present invention include a polymer compound having an electron transporting group (for example, an oxadiazole group, an oxathiadiazole group, a pyridyl group, etc.)? Or the polymer containing the repeating unit represented by the formula (1) preferably has the electron transporting group. Specific examples of the polymer compound containing an electron transporting group include a polymer containing oxadiazole, a polymer containing triazole, a polymer containing quinoline, a polymer containing quinoxaline, and a polymer containing benzothiadiazole. It is done.

  When the polymer light-emitting device of the present invention has a hole transporting layer, a hole transporting material (including low molecular weight and high molecular weight materials) is usually used for the hole transporting layer. Examples of the hole transport material include those exemplified for the hole transport material that may be contained in the composition of the present invention.

  Specific examples of the hole transport material include JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, and JP-A-2. Examples are those described in JP-A-209988, JP-A-3-7992 and JP-A-3-152184.

  Among these, as the hole transport material used for the hole transport layer, polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine compound group in the side chain or main chain, polyaniline and derivatives thereof , Polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, and polymer hole transport materials such as poly (2,5-thienylene vinylene) and derivatives thereof are preferable, polyvinyl carbazole and derivatives thereof, polysilane and A polysiloxane derivative having an aromatic amine in its derivative, side chain or main chain is more preferred.

  Examples of the low molecular hole transport material include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, and triphenyldiamine derivatives. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.

  As the polymer binder, those that do not extremely inhibit charge transport are preferable, and those that do not strongly absorb visible light are preferably used. As the polymer binder, poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

  Polyvinylcarbazole and derivatives thereof are obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.

  Examples of the polysilane and derivatives thereof include compounds described in Chemical Review (Chem. Rev.), 89, 1359 (1989), and British Patent No. 2300196. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.

  Since polysiloxane and derivatives thereof have almost no hole transporting property in the siloxane skeleton structure, those having the structure of the low molecular weight 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, The method by the film-forming from a mixed solution with a polymer binder is illustrated in the low molecular hole transport material. Examples of the polymer hole transport material include a method of forming a film from a solution (that is, a mixture of a hole transport material and a solvent).

  As the solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing the hole transport material is preferable. Examples of the solvent include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorinated solvents such as chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, toluene, xylene and the like. Aromatic hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, cyclohexanone Such as ketone solvents, ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxy ether , Propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, polyhydric alcohols such as 1,2-hexanediol and derivatives thereof, alcohol solvents such as methanol, ethanol, propanol, isopropanol, cyclohexanol, dimethyl Examples include sulfoxide solvents such as sulfoxide and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents may be used alone or in combination of two or more.

  For film formation from solution, spin coating method 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 printing A coating method such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  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, but at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element may increase, which is not preferable. Therefore, the thickness of the hole transport layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  When the polymer light-emitting device of the present invention has an electron transport layer, usually, an electron transport material (including low molecular weight and high molecular weight materials) is used for the electron transport layer. Examples of the electron transport material include those exemplified for the electron transport material that may be contained in the composition of the present invention.

  Specific examples of the electron transport material include JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, and JP-A-2-135. Examples are those described in 209988, JP-A-3-7992 and JP-A-3-152184.

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

  There are no particular restrictions on the method of forming the electron transport layer, but examples of low molecular electron transport materials include vacuum evaporation from powder and film formation from a solution or a molten state. Then, a method by film formation from a solution or a molten state is exemplified. When forming a film from a solution or a molten state, the polymer binder may be used in combination.

  As a solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing an electron transport material and / or a polymer binder is preferable. Specifically, what was illustrated as a solvent used for the film-forming from the solution of a positive hole transport layer in the term of the said positive hole transport layer is mentioned. These solvents may be used alone or in combination of two or more.

  Examples of the film formation method from a solution or a molten state include those exemplified as the film formation method from the solution of the hole transport layer in the section of the hole transport layer.

  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 film thickness of the electron transport layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  Among the hole transport layer and electron transport layer provided adjacent to the electrode, those having the function of improving the charge injection efficiency from the electrode and having the effect of lowering the driving voltage of the element are particularly positive. Generally referred to as a hole injection layer or an electron injection layer (hereinafter, these generic names may be referred to as “charge injection layers”).

  Further, in order to improve adhesion with the electrode and charge injection from the electrode, the charge injection layer or the insulating layer may be provided adjacent to the electrode, and the adhesion at the interface is improved or mixing is prevented. For this purpose, 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 adjusted in consideration of light emission efficiency and element lifetime.

In the present invention, the polymer light emitting device provided with the charge injection layer includes, for example, a polymer light emitting device provided with a charge injection layer adjacent to the cathode, and a polymer light emitting device provided with a charge injection layer adjacent to the anode. Is mentioned. Specifically, the following structures e) to p) are mentioned.
e) Anode / hole injection layer / light emitting layer / cathode f) Anode / light emitting layer / electron injection layer / cathode g) Anode / hole injection layer / light emitting layer / electron injection layer / cathode h) Anode / hole injection layer / Hole transport layer / light emitting layer / cathode i) anode / hole transport layer / light emitting layer / electron injection layer / cathode j) anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode k ) Anode / hole injection layer / light emitting layer / electron transport layer / cathode l) Anode / light emitting layer / electron transport layer / electron injection layer / cathode m) Anode / hole injection layer / light emitting layer / electron transport layer / electron injection Layer / cathode n) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode o) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode p) anode / Hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

  As described above, the polymer light-emitting device of the present invention includes those in which the composition of the present invention is contained in a hole transport layer and / or an electron transport layer. The polymer light-emitting device of the present invention includes those in which the composition of the present invention is contained in a hole injection layer and / or an electron injection layer.

  When the composition of the present invention is used for a hole injection layer, it is preferably used simultaneously with an electron accepting compound. When the composition of the present invention is used for an electron transport layer, it is preferably used simultaneously with an electron donating compound. Here, for simultaneous use, there are methods such as mixing, copolymerization and introduction as a side chain.

  Specific examples of the charge injection layer include a layer containing a conductive polymer, an anode and a hole transport layer, and an intermediate value between the anode material and the hole transport material contained in the hole transport layer. Examples include a layer including a material having an ionization potential, a layer including a material provided between the cathode and the electron transport layer, and having a material having an electron affinity intermediate between the cathode material and the electron transport material included in the electron transport layer. It is done.

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, and the leakage current between the light emitting pixels for the smaller is more preferably less 10 ^-5 S / cm or more and 10 ² S / cm, more preferably not more than 10 ^-5 S / cm or more and 10 ¹ S / cm. Usually, in order to make the electric conductivity of the conductive polymer 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 the like. Examples of the cation include lithium ion, sodium ion, potassium ion, tetrabutylammonium ion and the like.

  The thickness of the charge injection layer is usually 1 nm to 100 nm, preferably 2 nm to 50 nm.

  The material used for the charge injection layer may be appropriately selected in relation to the material of the electrode and the adjacent layer. Polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, 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 phthalocyanine (copper phthalocyanine, etc.), carbon, etc. .

  The insulating layer usually has a thickness of 0.5 to 4.0 nm and has a function of facilitating charge injection. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials.

Examples of the polymer light emitting device provided with the insulating layer include a polymer light emitting device provided with an insulating layer adjacent to the cathode and a polymer light emitting device provided with an insulating layer adjacent to the anode. Specific examples include the following structures q) to ab).
q) anode / insulating layer / light emitting layer / cathode r) anode / light emitting layer / insulating layer / cathode s) anode / insulating layer / light emitting layer / insulating layer / cathode t) anode / insulating layer / hole transport layer / light emitting layer / Cathode u) anode / hole transport layer / light emitting layer / insulating layer / cathode v) anode / insulating layer / hole transport layer / light emitting layer / insulating layer / cathode w) anode / insulating layer / light emitting layer / electron transport layer / Cathode x) anode / light emitting layer / electron transport layer / insulating layer / cathode y) anode / insulating layer / light emitting layer / electron transport layer / insulating layer / cathode z) anode / insulating layer / hole transport layer / light emitting layer / Electron transport layer / cathode aa) anode / hole transport layer / light emitting layer / electron transport layer / insulating layer / cathode ab) anode / insulating layer / hole transport layer / light emitting layer / electron transport layer / insulating layer / cathode

  The polymer light-emitting device of the present invention is the device structure exemplified in the above-mentioned a) to ab), in any one of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer. Contains the composition of the invention.

  The polymer light-emitting device of the present invention is usually formed on a substrate. This substrate may be any substrate that does not change when an electrode is formed and an organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. In the case of an opaque substrate, the opposite electrode (that is, the electrode far from the substrate) is preferably transparent or translucent. Usually, at least one of the anode and the cathode of the polymer light-emitting device of the present invention is transparent or translucent. The anode side is preferably transparent or translucent.

  As the material for the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film made of conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of a method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an anode.

  The film thickness of the anode can be appropriately adjusted in consideration of light transmittance and electrical conductivity, but is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. .

  In order to facilitate charge injection, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided on the anode.

  As a material for the cathode, a material having a small work function is preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like Two or more of these alloys, or an alloy of one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite intercalation compound, etc. Is used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy and the like. The cathode may have a laminated structure of two or more layers.

  The film thickness of the cathode can be appropriately adjusted in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

  As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used. In addition, 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 may be provided between the cathode and the organic layer. You may provide the protective layer which protects. In order to use the polymer light emitting device stably for a long period of time, it is preferable to provide a protective layer and / or a protective cover in order to protect the device from the outside.

  As the protective layer, a polymer compound, metal oxide, metal fluoride, metal boride, metal nitride, organic-inorganic hybrid material, or 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 of sealing and sealing the cover with an element substrate with a thermosetting resin or a photocurable resin is preferably used. It is done. If a space is maintained using a spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, the cathode can be prevented from being oxidized, and moisture adsorbed in the manufacturing process by installing a desiccant such as barium oxide in the space. It becomes easy to suppress giving an image to an element. Among these, it is preferable to take any one or more measures.

  The polymer light-emitting device of the present invention includes, for example, a curved light source, a planar light source such as a planar light source (for example, illumination), a segment display device (for example, a segment type display device), a dot matrix display device (for example, , A dot matrix flat display, etc.), a liquid crystal display device (for example, a liquid crystal display device, a backlight of a liquid crystal display, etc.).

  In order to obtain planar light emission using the polymer light emitting device of the present invention, the planar anode and cathode may be arranged so as to overlap each other. In order to obtain pattern-like light emission, a method in which a mask having a pattern-like window is provided on the surface of a planar light-emitting element, an organic layer of a non-light-emitting portion is formed to be extremely thick and substantially non-light-emitting. There is a method of forming either one of the anode or the cathode or both electrodes in a pattern. By forming a pattern by any of these methods and arranging some electrodes so that they can be turned on / off independently, a segment type display element capable of displaying numbers, letters, simple symbols and the like can be obtained. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multi-color display are possible by a method of separately coating a plurality of types of polymer phosphors 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 actively driven in combination with a TFT or the like. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

  The planar light emitting element is self-luminous thin 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 also be used as a curved light source or display device.

<Organic transistor (polymer field effect transistor)>
Next, a polymer field effect transistor which is an embodiment of the organic transistor will be described.
The organic transistor of the present invention has the thin film. The composition of the present invention can be suitably used as a polymer field effect transistor material, particularly as an active layer. As a structure of a polymer field effect transistor, a source electrode and a drain electrode are usually provided in contact with an active layer made of a polymer, and a gate electrode is provided with an insulating layer in contact with the active layer interposed therebetween. Just do it.

  The polymer field effect transistor is usually formed on a supporting substrate. The material of the support substrate is not particularly limited as long as the characteristics as a field effect transistor are not hindered, but a glass substrate, a flexible film substrate, or a plastic substrate can also be used.

  The polymer field effect transistor can be produced by a known method, for example, a method described in JP-A-5-110069.

  In forming the active layer, it is very advantageous and preferable to use a composition containing an organic solvent-soluble polymer. For film formation from a liquid composition comprising a solvent containing a polymer that is soluble in an organic solvent, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, Coating methods such as wire bar coating, dip coating, spray coating, screen printing, flexographic printing, offset printing, and inkjet printing can be used.

  A sealed polymer field effect transistor obtained by sealing after producing a polymer field effect transistor is preferred. Thereby, the polymer field effect transistor is shielded from the atmosphere, and deterioration of the characteristics of the polymer field effect transistor can be suppressed.

  Examples of the sealing method include a method of covering with an ultraviolet (UV) curable resin, a thermosetting resin, an inorganic SiONx film, or the like, and a method of bonding a glass plate or film with a UV curable resin, a thermosetting resin, or the like. In order to effectively cut off from the atmosphere, it is preferable to carry out the steps from the preparation of the polymer field effect transistor to the sealing without exposure to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

-Method for measuring number average molecular weight and weight average molecular weight-
In the examples, the polystyrene-equivalent number average molecular weight and the polystyrene-equivalent weight average molecular weight were determined by gel permeation chromatography (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 for 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) and one TSKgel SuperH2000 (manufactured by Tosoh) were connected in series. A differential refractive index detector (manufactured by Shimadzu Corporation, trade name: RID-10A) was used as the detector.

-Measurement of HOMO and LUMO energy levels-
The HOMO energy level of the polymer was determined from the oxidation potential of the polymer, and the LUMO energy level of the polymer was determined from the reduction potential of the polymer. For the measurement of the oxidation potential and the reduction potential, cyclic voltammetry (manufactured by BAS, trade name: ALS600) was used, and the measurement was performed in an acetonitrile solvent containing 0.1 wt% tetrabutylammonium t-fluoroborate. went. The oxidation potential was measured using a silver / silver chloride electrode as a reference electrode, a platinum electrode as a working electrode, and a platinum electrode as a counter electrode, and bubbling the solvent with nitrogen for 1 minute. On the other hand, the reduction potential was measured in a glove box substituted with nitrogen using a silver / silver ion electrode as a reference electrode, a glassy carbon electrode as a working electrode, and a platinum electrode as a counter electrode. The potential velocity was measured at 50 mV / s.

Ａ−１
で表される化合物Ａ−１（茶色の固体）を４．４３ｇ得た。ＬＣ−ＭＳ測定結果から、二量体等の副生成物も生成しており、化合物Ａ−１の純度は７７％であった（ＬＣ面積百分率）。 <Synthesis Example 1> (Synthesis of Compound A)
(1) Synthesis of Compound A-1 Into a 1 l four-necked flask under an inert atmosphere, 7 g of 2,8-dibromodibenzothiophene and 280 ml of THF were added, stirred at room temperature, dissolved, and then cooled to −78 ° C. did. 29 ml of n-butyllithium (1.6 molar hexane solution) was added dropwise. After completion of the dropping, the mixture was stirred for 2 hours while maintaining the temperature, and 13 g of trimethoxyboronic acid was added dropwise. After completion of dropping, the temperature was slowly returned to room temperature. After stirring at room temperature for 3 hours, disappearance of the raw material was confirmed by TLC. The reaction was terminated by adding 100 ml of 5% by weight sulfuric acid and stirred at room temperature for 12 hours. Water was added for washing, and the organic layer was extracted. After replacing the solvent with ethyl acetate, 5 ml of 30 wt% aqueous hydrogen peroxide was added and stirred at 40 ° C for 5 hours. Thereafter, the organic layer was extracted, washed with a 10% by weight aqueous ammonium iron (II) sulfate solution, dried, and the solvent was removed to obtain the following formula:

A-1
4.43 g of compound A-1 (brown solid) represented by From the LC-MS measurement results, by-products such as dimers were also produced, and the purity of Compound A-1 was 77% (LC area percentage).

Ａ−２
で表される化合物Ａ−２を８．４９ｇ（ＬＣ面積百分率９７％、収率９４％）得た。 (2) Synthesis of Compound A-2 4.43 g of Compound A-1, 25.1 g of n-octyl bromide, and 12.5 g (23.5 mmol) of potassium carbonate were added to a 200 ml three-necked flask under an inert atmosphere. Then, 50 ml of methyl isobutyl ketone was added as a solvent, and the mixture was heated to reflux at 125 ° C. for 6 hours. After completion of the reaction, the solvent was distilled off, and the organic layer was extracted by separating with chloroform and water, and further washed twice with water. After drying over anhydrous sodium sulfate, purification with a silica gel column (developing solvent: toluene / cyclohexane = 1/10 (volume ratio)) yields the following formula:

A-2
8.49 g (LC area percentage 97%, yield 94%) was obtained.

Ａ−３
で表される化合物Ａ−３を６．９６ｇ（ＬＣ面積百分率９０％、収率９７％）得た。 (3) Synthesis of Compound A-3 6.67 g of Compound A-2 and 40 ml of acetic acid were placed in a 100 ml three-necked flask, and the temperature was raised to 140 ° C. with an oil bath. Next, 13 ml of 30% by weight hydrogen peroxide solution was added from the condenser, and stirred vigorously for 1 hour, and then poured into 180 ml of cold water to complete the reaction. After extraction with chloroform and drying, the following formula is obtained by removing the solvent:

A-3
6.96 g (LC area percentage 90%, yield 97%) was obtained.

Ａ−４
で表される化合物Ａ−４を４．４６ｇ（ＬＣ面積百分率９８％、収率８４％）得た。 (4) Synthesis of Compound A-4 In a 200 ml four-necked flask under an inert atmosphere, 3.96 g of Compound A-3 and 15 ml of a mixture of acetic acid / chloroform = 1: 1 (volume ratio) were added and stirred at 70 ° C. Dissolved. Next, 6.02 g of bromine was dissolved in 3 ml of the above solvent and stirred for 3 hours. A sodium thiosulfate aqueous solution was added to remove unreacted bromine, followed by separation with chloroform and water, and the organic layer was extracted and dried. Next, the solvent was removed, and purification was performed using a silica gel column (developing solvent: chloroform / hexane = 1/4 (volume ratio)) to obtain the following formula:

A-4
4.46 g of the compound A-4 represented by formula (LC area percentage 98%, yield 84%) was obtained.

化合物Ａ
で表される化合物Ａを１．８ｇ（ＬＣ面積百分率９９％、収率４９％）得た。 (5) Synthesis of Compound A Compound A-4 (3.9 g) and diethyl ether (50 ml) were placed in a 200 ml three-necked flask under an inert atmosphere, and the mixture was heated to 40 ° C. and stirred. 1.17 g of lithium aluminum hydride was added in small portions and reacted for 5 hours. Excess lithium aluminum hydride was decomposed by adding water little by little and washed with 5.7 ml of 36 wt% hydrochloric acid. After separating with chloroform and water, the organic layer was extracted and dried. By purifying with a silica gel column (developing solvent: chloroform / hexane = 1/5 (volume ratio)), the following formula:

Compound A
1.8 g (LC area percentage 99%, yield 49%) was obtained.

で表される４−ｔ−ブチル−２，６−ジメチルブロモベンゼン３４．２ｇを白色の固体として得た。 <Synthesis Example 2> (Synthesis of N, N′-bis (4-bromophenyl) -N, N′-bis (4-tert-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine)
(1) Synthesis of 4-t-butyl-2,6-dimethylbromobenzene In an inert atmosphere, 225 g of acetic acid was placed in a 500 ml three-necked flask, and 24.3 g of 5-t-butyl-m-xylene was added. It was. Subsequently, after adding 31.2 g of bromine, it was made to react at 15-20 degreeC for 3 hours. The reaction solution was added to 500 ml of water, and the deposited precipitate was filtered. Wash twice with 250 ml of water and use the following formula:

In this manner, 34.2 g of 4-t-butyl-2,6-dimethylbromobenzene represented by the formula (1) was obtained as a white solid.

で表されるＮ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（４−ｔ−ブチル−２，６−ジメチルフェニル）−１，４−フェニレンジアミン ９．９ｇを白色の固体として得た。 (2) Synthesis of N, N′-diphenyl-N, N′-bis (4-tert-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine, 100 ml of three necks in an inert atmosphere 36 ml of degassed dehydrated toluene was put into the flask, and 0.63 g of tri (t-butyl) phosphine was added. Subsequently, 0.41 g of tris (dibenzylideneacetone) dipalladium, 9.6 g of the above-mentioned 4-t-butyl-2,6-dimethylbromobenzene, 5.2 g of sodium t-butoxy, N, N′-diphenyl-1, After adding 4.7 g of 4-phenylenediamine, the mixture was reacted at 100 ° C. for 3 hours. The reaction solution was added to 300 ml of saturated brine and extracted with 300 ml of chloroform warmed to about 50 ° C. After distilling off the solvent, 100 ml of toluene was added, and the mixture was heated and allowed to cool until the solid was dissolved. Then, the precipitate was filtered, and the following formula:

9.9 g of N, N′-diphenyl-N, N′-bis (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine represented by the following formula was obtained as a white solid.

で表されるＮ，Ｎ’−ビス（４−ブロモフェニル）−Ｎ，Ｎ’−ビス（４−ｔ−ブチル−２，６−ジメチルフェニル）−１，４−フェニレンジアミン ４．４ｇを白色の固体として得た。 (3) Synthesis of N, N′-bis (4-bromophenyl) -N, N′-bis (4-tert-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine under an inert atmosphere In a 1000 ml three-necked flask, 350 ml of dehydrated N, N-dimethylformamide was placed, and the above N, N′-diphenyl-N, N′-bis (4-t-butyl-2,6-dimethylphenyl) -1 After dissolving 5.2 g of 1,4-phenylenediamine, 3.5 g of N-bromosuccinimide / N, N-dimethylformamide solution was added dropwise in an ice bath and allowed to react overnight. 150 ml of water was added to the reaction solution, and the deposited precipitate was filtered and washed twice with 50 ml of methanol.

4.4 g of N, N′-bis (4-bromophenyl) -N, N′-bis (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine represented by the formula Obtained as a solid.

<Synthesis Example 3> (Synthesis of Polymer 1)
9,9-Dioctyl-2,7-dibromofluorene 461 mg, 2,7-dibromo-9,9-diisopentylfluorene 97 mg, Compound A 126 mg, N, N′-bis (4-bromophenyl) -N, N After dissolving 103 mg of '-bis (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine and 550 mg of 2,2'-bipyridyl in 39 mL of dehydrated tetrahydrofuran, this solution was added under a nitrogen atmosphere. , 960 mg of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added, and the temperature was raised to 60 ° C. and reacted for 3 hours. After the reaction, the resulting reaction solution was cooled to room temperature, dropped into a mixed solution of 25% by weight ammonia water 20 ml / methanol 240 ml / ion exchange water 100 ml and stirred for 30 minutes, and then the deposited precipitate was filtered for 2 hours. It was dried under reduced pressure and dissolved in 60 ml of toluene. After adding 60 mL of 1N hydrochloric acid and stirring for 3 hours, the aqueous layer was removed, and 60 mL of 4 wt% aqueous ammonia was added to the organic layer and stirred for 3 hours, and then the aqueous layer was removed. The organic layer was dropped into 300 mL of methanol and stirred for 30 minutes, the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 60 mL of toluene. Then, it refine | purified through the alumina column (alumina amount 20g), and the collect | recovered toluene solution was dripped at methanol 400mL, and was stirred for 30 minutes. The deposited precipitate was filtered and dried under reduced pressure for 2 hours to obtain 410 mg of a polymer (hereinafter, this polymer is referred to as “polymer 1”).

The polystyrene equivalent number average molecular weight Mn of the polymer 1 was 1.3 × 10 ⁵ , and the polystyrene equivalent weight average molecular weight Mw was 5.7 × 10 ⁵ .

で表される割合で上記単位を有するものであると推測される。 From the charge ratio of the starting materials, the polymer 1 has the following formula:

It is estimated that it has the said unit in the ratio represented by these.

  In the polymer 1, the 26.3-mer polymer consisting only of the repeating unit A has a HOMO energy level of 5.9 eV, a LUMO energy level of 2.4 eV, and a 44.8 amount consisting only of the repeating unit B. The HOMO energy level of the polymer is 5.7 eV, the LUMO energy level is 2.5 eV, and the HOMO energy level of the 11.0-mer polymer consisting only of the repeating unit C is 5.0 eV, LUMO. The energy level of is 2.0 eV. That is, in the polymer 1, the repeating unit having hole injecting property is the repeating unit C, and the repeating unit having electron injecting property is the repeating unit B. These values were determined as described later.

<Synthesis Example 4> (Synthesis of Polymer 2)
Under a nitrogen atmosphere, 1.65 g of 9,9-dioctyl-2,7-dibromofluorene, 1.80 g of 9,9-n-dioctylfluorene-2,7-diethyleneboronate and methyltrioctylammonium chloride (trade name: Aliquot 336 (manufactured by Aldrich Co.) was charged into a reaction vessel, dissolved in 52 g of toluene, and an aqueous potassium carbonate solution prepared by dissolving 1.31 g of potassium carbonate in 56 g of water was added thereto. Further, 6.9 mg of tetrakis (triphenylphosphine) palladium was added and heated to reflux for 10 hours. Thereafter, 61 mg of bromobenzene was added, and the mixture was further heated to reflux for 2 hours. After cooling to room temperature, the organic layer was added dropwise to methanol, and the deposited precipitate was filtered off and dried to obtain a polymer (hereinafter, this polymer is referred to as “polymer (2-1)”).

  Separately, the same synthesis operation was performed twice to obtain a polymer (2-2) and a polymer (2-3). The polymer (2-1), polymer (2-2) and polymer (2-3) thus obtained were mixed, dissolved in 150 mL of toluene, and this solution was passed through a column packed with silica and alumina. And purified. Thereafter, the obtained purified product (solution) was dropped into 500 mL of methanol, and the deposited precipitate was filtered and dried to obtain 3.82 g of a polymer (hereinafter, this polymer is referred to as “polymer 2”).

The polystyrene equivalent number average molecular weight Mn of the polymer 2 was 1.1 × 10 ⁴ , and the polystyrene equivalent weight average molecular weight Mw was 2.3 × 10 ⁴ .

で表される繰り返し単位を有するものと推測される。 From the starting material, the polymer 2 has the following formula:

It is estimated that it has the repeating unit represented by these.

-Measurement of HOMO and LUMO energy levels-
According to the measurement method described above, the HOMO energy level and LUMO energy level of polymer 2 (26.3-mer) were measured. Polymer 2 had a HOMO energy level of 5.9 eV and a LUMO energy level of 2.4 eV. These values were regarded as those of the polymer 1 consisting of only the repeating unit A in the polymer 1.

<Synthesis Example 5> (Synthesis of Polymer 3)
After 352 mg of Compound A and 274 mg of 2,2′-bipyridyl were dissolved in 20 mL of dehydrated tetrahydrofuran, the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, 500 mg of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added to this solution, and the temperature was raised to 60 ° C. and reacted for 3 hours. After the reaction, the resulting reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25 wt% ammonia water 10 ml / methanol 120 ml / ion-exchanged water 50 ml and stirred for 1 hour, and then the deposited precipitate was removed. The solution was filtered, dried under reduced pressure for 2 hours, and dissolved in 30 ml of toluene. Thereafter, 30 ml of 1N hydrochloric acid was added and stirred for 1 hour, the aqueous layer was removed, and 30 ml of 4 wt% aqueous ammonia was added to the organic layer, and the mixture was stirred for 1 hour, and then the aqueous layer was removed. The organic layer was dropped into 200 ml of methanol and stirred for 1 hour, the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 30 ml of toluene. Then, it refine | purifies by passing through an alumina column (alumina amount 5g), The collect | recovered toluene solution is dripped at methanol 250ml, it stirs for 1 hour, The depositing precipitate is filtered and dried under reduced pressure for 2 hours. This polymer was referred to as “Polymer 3”).

The polystyrene equivalent number average molecular weight Mn of the polymer 3 was 2.1 × 10 ⁴ , and the polystyrene equivalent weight average molecular weight Mw was 8.1 × 10 ⁴ .

で表される繰り返し単位を有するものと推測される。 From the starting material, the polymer 3 has the following formula:

It is estimated that it has the repeating unit represented by these.

-Measurement of HOMO and LUMO energy levels-
According to the measurement method described above, the HOMO energy level and LUMO energy level of Polymer 3 (44.8 mer) were measured. Polymer 3 had a HOMO energy level of 5.7 eV and a LUMO energy level of 2.5 eV.

<Synthesis Example 6> (Synthesis of Polymer 4)
11.1 g of N, N′-bis (4-bromophenyl) -N, N′-bis (4-tert-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine and 2,2′-bipyridyl After charging 5.6 g into the reaction vessel, the inside of the reaction system was replaced with nitrogen gas. To this, 400 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, 10.0 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and the mixture was stirred at room temperature for 10 minutes, and then reacted at 60 ° C. for 3 hours. The reaction was performed in a nitrogen gas atmosphere.

  After the reaction, this reaction solution was cooled, and then a mixed solution of 25 wt% ammonia water 50 ml / methanol 200 ml / ion exchanged water 200 ml was poured into the solution and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution was filtered to remove insoluble matters, and the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was washed with about 1N hydrochloric acid, allowed to stand and separated, and then the toluene solution was recovered. The toluene solution thus obtained was washed with about 3% by weight aqueous ammonia, allowed to stand and separated, and then the toluene solution was recovered. Next, the toluene solution thus obtained was washed with ion-exchanged water, allowed to stand and separated, and then the toluene solution was recovered. Next, the toluene solution thus obtained was poured into methanol and reprecipitated. Next, the produced precipitate was recovered, and this precipitate was dried under reduced pressure to obtain 4.7 g of a polymer (hereinafter, this polymer is referred to as “polymer 4”).

The polystyrene equivalent number average molecular weight Mn of the polymer 4 was 6.7 × 10 ³ , and the polystyrene equivalent weight average molecular weight Mw was 4.5 × 10 ⁴ .

で表される繰り返し単位を有するものと推測される。 From the starting material, the polymer 4 has the following formula:

It is estimated that it has the repeating unit represented by these.

-Measurement of HOMO and LUMO energy levels-
According to the measurement method described above, the HOMO energy level and LUMO energy level of Polymer 4 (11.0 mer) were measured. Polymer 4 had a HOMO energy level of 5.0 eV and a LUMO energy level of 2.0 eV.

化合物Ｄ
で表される化合物Ｄ 3.0gと、２，２’−ビピリジル 8.25gとを、反応容器に仕込んだ後、反応系内を窒素ガスで置換した。これに、予めアルゴンガスでバブリングして脱気したテトラヒドロフラン（脱水溶媒）750gを加えた。次に、この混合溶液に、ビス（１，５−シクロオクタジエン）ニッケル（０） 15.0gを加え、室温で10分間攪拌した後、60℃で３時間反応した。なお、反応は、窒素ガス雰囲気中で行った。 <Synthesis Example 7>
-Synthesis of Polymer 5-
9.63 g of 9,9-dioctyl-2,7-dibromofluorene and the following formula:

Compound D
Compound D (3.0 g) and 2,2′-bipyridyl (8.25 g) were charged into a reaction vessel, and the reaction system was replaced with nitrogen gas. To this, 750 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, 15.0 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and the mixture was stirred at room temperature for 10 minutes and then reacted at 60 ° C. for 3 hours. The reaction was performed in a nitrogen gas atmosphere.

  After the reaction, this reaction solution was cooled, and a mixed solution of 25% by weight ammonia water 70 ml / methanol 700 ml / ion exchanged water 700 ml was poured into this solution and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution was filtered to remove insoluble matters, and the resulting toluene solution was purified by passing through a column filled with alumina. The toluene solution thus obtained was washed with about 3 wt% aqueous ammonia, allowed to stand and liquid-separated, and then the toluene solution was recovered. Next, this toluene solution was washed with ion exchange water, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was poured into methanol and purified by reprecipitation.

Next, the produced precipitate was recovered, and this precipitate was dried under reduced pressure to obtain 4.5 g of a polymer (hereinafter referred to as “polymer 5”). The polystyrene equivalent weight average molecular weight Mw of the polymer 5 was 1.4 × 10 ⁵ , and the polystyrene equivalent number average molecular weight Mn was 4.1 × 10 ⁴ .

で表される割合で上記単位を有するものであると推測される。 From the charge ratio of the starting materials, the polymer 5 has the following formula:

It is estimated that it has the said unit in the ratio represented by these.

<Example 1>
-Preparation of Composition 1-
A mixture obtained by mixing the polymer 1 and the following iridium complex A (manufactured by American Dye Sauce Co., Ltd.) at a weight ratio of 98: 2 was dissolved in chloroform, whereby a 0.4 wt% chloroform solution (hereinafter, referred to as “the mixture”) was dissolved. "Composition 1") was prepared.

イリジウム錯体Ａ

Iridium complex A

<Example 2>
-Fabrication of light-emitting elements-
A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is used to form a film with a thickness of 50 nm by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Bayer, BaytronP). Dried on plate for 10 minutes at 200 ° C. Next, the composition 1 was formed into a film by spin coating at a rotational speed of 2500 rpm. The film thickness was about 120 nm. Further, this was dried at 130 ° C. for 1 hour in a nitrogen atmosphere, and then, as a cathode, barium was vapor-deposited at about 5 nm, and then aluminum was vapor-deposited at about 80 nm to produce an EL device. In addition, after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.

By applying voltage to the obtained polymer light emitting device, EL light emission having a peak at 620 nm was obtained. The device started to emit light at about 4.9 V, the maximum luminous efficiency was 1.50 cd / A, the luminance was maximum at 18.2 V, and the maximum luminance was 3180 cd / m ² .

<Comparative Example 1>
-Preparation of composition 2-
A mixture obtained by mixing the polymer 5 and the iridium complex A at a weight ratio of 98: 2 is dissolved in chloroform, whereby a 0.4 wt% chloroform solution of the mixture (hereinafter referred to as “composition C1”). Was prepared.

<Comparative example 2>
-Fabrication of light-emitting elements-
A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is used to form a film with a thickness of 50 nm by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Bayer, BaytronP). Dried on plate for 10 minutes at 200 ° C. Next, the composition C1 was formed by spin coating at a rotational speed of 2500 rpm. The film thickness was about 100 nm. Further, this was dried at 130 ° C. for 1 hour in a nitrogen atmosphere, and then, as a cathode, barium was vapor-deposited at about 5 nm, and then aluminum was vapor-deposited at about 80 nm to produce an EL device. In addition, after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.

By applying voltage to the obtained polymer light emitting device, EL light emission having a peak at 620 nm was obtained. The device started to emit light at about 5.1 V, the maximum luminous efficiency was 0.07 cd / A, the luminance was maximum at 10.4 V, and the maximum luminance was 229 cd / m ² .

Claims (18)

Following formula (1):

[Wherein, R ¹ represents a substituent, R ² represents an alkyl group which may have a substituent, or an alkoxy group which may have a substituent, and n represents an integer of 0 to 3. To express. A plurality of R ² and n may be the same or different. When a plurality of R ¹ are present, they may be the same or different. ]
A composition comprising: a repeating unit represented by formula: a repeating unit having an electron injecting property; a polymer containing a repeating unit having a hole injecting property; and a compound exhibiting phosphorescence.   The composition according to claim 1, wherein the repeating unit having a hole injecting property is a divalent aromatic amine group. The divalent aromatic amine group has the following formula (2):

[Wherein, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent an arylene group or a divalent heterocyclic group which may have a substituent. Ar ₅ , Ar ₆ and Ar ₇ each independently represent an aryl group or a monovalent heterocyclic group which may have a substituent. x and y are each independently 0 or a positive integer. ]
The composition of Claim 2 which is represented by these. The divalent aromatic amine group represented by the formula (2) is represented by the following formulas (2-1) to (2-3):

[Wherein, R ³ represents a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent. A plurality of R ³ may be the same or different. ]
The composition according to claim 3, which is represented by any one of the following:   The composition according to any one of claims 1 to 4, wherein the electron-injecting repeating unit is a divalent heterocyclic group or a benzofluorenediyl group optionally having a substituent. The divalent heterocyclic group has the following formula (3):

[Wherein R ³ represents the same meaning as described above, and X ′ ″ represents —O—, —S—, —S (═O) —, —S (═O) ₂ —, —Si (R _{^{5) 2 -Si (R 5)}} 2 -, - Si (R 5) 2 -, - B (R 5) -, - P (R 5) -, - P (= O) (R 5) -, - O—C (R ⁵ ) ₂ — or —N═C (R ⁵ ) — is represented, and R ⁵ represents a hydrogen atom or a substituent. A plurality of R ³ may be the same or different. When a plurality of R ⁵ are present, they may be the same or different. ]
The composition of Claim 5 which is represented by these.   The composition as described in any one of Claims 1-6 which further contains the polymer which does not have a repeating unit represented by the said Formula (1). The composition according to any one of claims 1 to 7, wherein the polymer has a polystyrene-equivalent weight average molecular weight of 3 x 10 ³ to 1 x 10 ⁸ .   The composition according to any one of claims 1 to 8, wherein a content of the phosphorescent compound is 0.01 to 49 parts by weight with respect to 100 parts by weight of the polymer.   A polymer compound having a repeating unit represented by the formula (1), a repeating unit having an electron injecting property, a repeating unit having a hole injecting property, and a residue of a compound exhibiting phosphorescence.   The polymer compound according to claim 10, wherein the repeating unit having hole injecting property is a repeating unit represented by the formula (2).   The polymer compound according to claim 10 or 11, wherein the repeating unit having an electron injecting property is a repeating unit represented by the formula (3). The polymer compound according to any one of claims 10 to 12, which has a polystyrene-reduced weight average molecular weight of 3 x 10 ³ to 1 x 10 ⁸ .   Furthermore, the liquid composition which consists of a composition as described in any one of Claims 1-9 containing a solvent.   A liquid composition comprising the polymer compound according to any one of claims 10 to 13 and a solvent.   A thin film comprising the composition according to any one of claims 1 to 9, the polymer compound according to any one of claims 10 to 13, or the liquid composition according to claim 14 or 15. .   An organic transistor having the thin film according to claim 16.   An electrode comprising an anode and a cathode, and the composition according to any one of claims 1 to 9 and / or the polymer compound according to any one of claims 10 to 13 provided between the electrodes. A polymer light emitting device having an organic layer.