JP2007284580A - Polymer light emitting device, organic transistor and composition useful therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition providing a light-emitting device almost selectively emitting a light derived from a low-molecular fluorescent material and having excellent brightness thereof when used for manufacture of the light-emitting device. <P>SOLUTION: The composition contains a polymer containing a repeating unit represented by formula (1) (wherein, Y' is -O-, -S- or -C(=O)-; Z is a hydrogen atom or a substituent; R<SP>1</SP>is a substituent; n is an integer of 0-3; when a plurality of R<SP>1</SP>s is present, R<SP>1</SP>s may be the same or different), and the low-molecular fluorescent material. <P>COPYRIGHT: (C)2008,JPO&INPIT

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 low-molecular fluorescent material 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. Specifically, for example, a composition containing a polyfluorene derivative and a low-molecular fluorescent material has been proposed (Patent Document 1).

JP 2002-170674 A

However, in this composition, when a light-emitting device is produced using the composition, it is difficult to selectively obtain light emitted from the low-molecular fluorescent material from the light-emitting device. Even when the emitted light is obtained, there is a problem that the luminance is low.
Accordingly, an object of the present invention is to obtain light emission derived from a low-molecular fluorescent material almost selectively from the light-emitting element when used for manufacturing a light-emitting element, and to obtain a light-emitting element with excellent luminance. It is to provide a composition.

  The present invention provides the following formula (1):

〔式中、Ｙ’は、−Ｏ−、−Ｓ−又は−Ｃ（＝Ｏ）−を表し、Ｚは、水素原子又は置換基を表し、Ｒ¹は、置換基を表し、ｎは０〜３の整数を表す。Ｒ¹が複数個存在する場合、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を含む重合体と、低分子蛍光材料とを含有する組成物、を提供する。

[Wherein Y ′ represents —O—, —S— or —C (═O) —, Z represents a hydrogen atom or a substituent, R ¹ represents a substituent, and n represents 0 to 0. An integer of 3 is represented. When a plurality of R ¹ are present, they may be the same or different. ]
A composition comprising a polymer containing a repeating unit represented by the formula (1) and a low-molecular fluorescent material.

When the composition of the present invention is used for production of a light emitting device, light emission derived from a low molecular fluorescent material can be almost selectively obtained from the light emitting device, and a light emitting device having excellent luminance can be obtained. It is. In general, the light emitting device thus obtained is also excellent in luminous efficiency. Thus, the composition of the present invention is 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 suitable 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.

<Composition>
The composition of this invention contains the polymer containing the repeating unit represented by said Formula (1), and a low molecular fluorescent material.

-Polymer containing repeating units represented by formula (1)-
In the formula (1), Y ′ represents —O—, —S— or —C (═O) —, and —O— or —S— is preferable from the viewpoint of device characteristics.

n represents an integer of 0 to 3, and n is preferably 0 or 1 from the viewpoint of ease of synthesis. When a plurality of R ¹ are present, they may be the same or different, and two R ¹ may be bonded to form a ring.

  In the formula (1), Z is preferably a substituent, and examples of the substituent represented by Z 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, a monovalent heterocyclic group and the like can be mentioned. A hydrogen atom contained in these substituents may be substituted with a fluorine atom. Among the substituents represented by Z, from the viewpoint of solubility and ease of synthesis, 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 heterocyclic group is preferable, and an alkyl group, an alkoxy group, an aryl group, and a monovalent heterocyclic group are more preferable. Among the substituents represented by Z, from the viewpoint of device efficiency, an aryl group and a monovalent heterocyclic group are preferable, and an aryl group is more preferable.

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 viewpoints of solubility and ease of synthesis, alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkoxy groups, monovalent groups. The heterocyclic group is preferably an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group.

Description of Substituents Represented by Z and 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, 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 In view of the balance between solubility in organic solvents, device characteristics, easiness of synthesis and heat resistance, pentyl group, isoamyl group, hexyl group, octyl group, 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, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyl. Oxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl Group, perfluorooctyl group, methoxymethyloxy group, 2-methoxyethyloxy group, and the like, and from the balance of solubility in organic solvent, device characteristics, easiness of synthesis and heat resistance, Pentyloxy group, hexyloxy group, octyloxy group 2-ethylhexyl group, decyloxy group, 3,7-dimethyl octyloxy group are preferable.

  The alkylthio group may be linear, branched or cyclic, 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, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group. , 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, trifluoromethylthio group, etc., solubility in organic solvents, device characteristics, ease of synthesis, etc. From the viewpoint of balance between the above and heat resistance, a pentylthio group, a hexylthio group, an octylthio group, a 2-ethylhexylthio group, a decylthio group, and a 3,7-dimethyloctylthio group are preferable.

An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon and having a condensed ring, two or more independent benzene rings or condensed rings bonded directly or via 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., from the viewpoint of solubility in organic solvents, device characteristics, ease of synthesis, etc. 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, Pentyloxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group, 3,7-dimethyloctyloxyphenyl Group, lauryloxyphenyl group and the like. 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 in an organic solvent, device characteristics, easiness of synthesis, etc., 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, Pentyloxyphenoxy group, hexyloxyphenoxy group, cyclohexyloxyphenoxy group, heptyloxyphenoxy group, octyloxyphenoxy group, 2-ethylhexyloxyphenoxy group, nonyloxyphenoxy group, decyloxyphenoxy group, 3,7-dimethyloctyloxyphenoxy Group, lauryloxyphenoxy group and the like are exemplified. 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 solubility in organic solvents, device properties, from the standpoint of easiness of synthesis, C ₁ -C ₁₂ alkoxyphenyl-thio group, a C ₁ -C ₁₂ alkyl phenylthio group are preferable.

The arylalkyl group usually has about 7 to 60 carbon atoms, preferably 7 to 48 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., from the viewpoint of solubility in organic solvents, device characteristics, ease of synthesis, etc. C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group are preferable.

The arylalkoxy group usually has about 7 to 60 carbon atoms, preferably 7 to 48 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, solubility in organic solvents, device properties, from the standpoint of easiness of synthesis, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy 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 and the like. From the viewpoint of solubility in organic solvents, device characteristics, easiness of synthesis, etc., C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group are preferable.

The 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 in organic solvents, device characteristics, easiness of synthesis, 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 groups and the like, solubility in organic solvents, device properties, from the standpoint of easiness of synthesis, 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, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, lauryl amino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxy phenylene 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, pentyloxycarbonyl group, hexyloxy Carbonyl 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, perfluorohexyloxycarbonyl group, perfluorooctyl Le oxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group and the like.

  Specific examples of the repeating unit represented by the formula (1) when Z is an aryl group or a monovalent heterocyclic group include the following formulas (1-1) to (1-6):

〔式中、Ｙ’、Ｒ¹、ｎは前記と同じ意味を表す。Ｒ²は置換基を表す。ｐ１は０〜５の整数を表し、ｐ２は０〜７の整数を表し、ｐ３は０〜９の整数を表し、ｐ４は０〜３の整数を表し、ｐ５は０〜４の整数を表す。〕
のいずれかで表される繰り返し単位等が挙げられる。

[Wherein Y ′, R ¹ and n represent the same meaning as described above. R ² represents a substituent. p1 represents an integer of 0 to 5, p2 represents an integer of 0 to 7, p3 represents an integer of 0 to 9, p4 represents an integer of 0 to 3, and p5 represents an integer of 0 to 4. ]
Or a repeating unit represented by any of the above.

Examples of the substituent represented by R ² 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. A hydrogen atom contained in these substituents may be substituted with a fluorine atom. Among these substituents, from the viewpoints of solubility and ease of synthesis, alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkoxy groups, monovalent groups. The heterocyclic group is preferably an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group. Among these substituents, from the viewpoint of device characteristics such as luminance half life, an alkyl group and an alkoxy group are preferable, and an alkyl group is more preferable.

  From the viewpoint of solubility, p1, p2, p3, p4 and p5 are preferably integers of 1 or more.

  Among the formulas (1-1) to (1-6), the structure represented by (1-1) is preferable from the viewpoint of device characteristics such as luminous efficiency and luminance half life, and the following formula (1- The structure represented by 1-1) to (1-1-2) is more preferable.

〔式中、Ｙ’、Ｒ²は前記と同じ意味を表す。〕

[Wherein Y ′ and R ² represent the same meaning as described above. ]

  The polymer may contain a repeating unit other than the repeating unit represented by the formula (1). The repeating unit represented by the formula (1) is preferably 1 mol% or more, more preferably 3 mol% or more of all repeating units in the polymer, from the viewpoint of luminous efficiency.

Examples of the repeating unit other than the repeating unit represented by the formula (1) include the following formula (2):
-Ar _1- (2)
[In the formula, Ar ₁ represents an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or a divalent aromatic which may have a substituent. Represents a group amine group. ]
The repeating unit represented by these is mentioned.

In the formula (2), the arylene group represented by Ar ₁ is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, having a condensed ring, an independent benzene ring or two condensed rings. Those in which the above 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 include a phenylene group (for example, formulas 1 to 3 in the following figure), a naphthalenediyl group (for example, formulas 4 to 13 in the following figure), and an anthracene-diyl group (for example, formulas 14 to 19), a biphenyl-diyl group (for example, formulas 20 to 25 in the following figure), a terphenyl-diyl group (for example, formulas 26 to 28 in the following figure), a condensed ring compound group (for example, formulas 29 to 35 in the following figure), fluorene A diyl group (for example, Formulas 36 to 38 in the following figure), a stilbene-diyl group (Formulas 39 to 42 in the following figure), a distilbene-diyl group (for example, Formulas 43 and 44 in the following figure), a benzofluorene-diyl group (for example, Examples include formulas A-1 to A-3) and dibenzofluorene-diyl groups (for example, formula A-4) shown below.

（式中、Ｒは独立に、水素原子又は置換基を表す。）

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

In the above formulas 1-44 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, and 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, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group and the like. A hydrogen atom contained in these substituents may be substituted with a fluorine atom. These groups, residues, and atoms are the same as those described and exemplified in the section of the substituent represented by Z and R ¹ described above. In the substituent represented by R, at least one R is preferably other than a hydrogen atom from the viewpoints of solubility and device characteristics. 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 refers to the remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound. The divalent heterocyclic group may have a 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, arsenic in the ring. Say. Of the divalent heterocyclic groups, an aromatic heterocyclic group is preferable. Carbon number of the part except the substituent in a bivalent heterocyclic group is about 3-60 normally. Moreover, the total carbon number including the substituent of a bivalent heterocyclic group is about 3-100 normally.

Examples of the divalent heterocyclic group represented by Ar ₁ include a pyridine-diyl group (for example, formulas 45 to 50 in the following figure), a diazaphenylene group (for example, formulas 51 to 54 in the following figure), a quinoline diyl group ( For example, formulas 55 to 69 in the following figure, quinoxalinediyl groups (for example, formulas 70 to 74 in the following figure), acridine diyl groups (for example, formulas 75 to 78 in the following figure), bipyridyldiyl groups (for example, formulas 79 to 81 in the following figure) ), A phenanthrolinediyl group (for example, formulas 82 to 84 in the figure below), a group having a carbazole structure (for example, formulas 85 to 87 in the figure below), etc., a divalent heterocyclic group containing nitrogen as a heteroatom; 5-membered heterocyclic groups containing oxygen, silicon, nitrogen, sulfur, selenium, etc. (eg, Formulas 88-92 in the figure below); 5-membered rings containing oxygen, silicon, nitrogen, selenium, etc. as heteroatoms A combined heterocyclic group (for example, formulas 93 to 103 in the figure below); a dimer formed by bonding at the α-position of the heteroatom with a 5-membered heterocyclic group containing oxygen, silicon, nitrogen, sulfur, selenium, etc. as a heteroatom. Or a group that is an oligomer (for example, formulas 104 to 105 in the figure below); a 5-membered heterocyclic group containing oxygen, silicon, nitrogen, sulfur, selenium, etc. as a heteroatom, and a phenyl group at the α-position of the heteroatom A group bonded to (for example, formulas 106 to 112 in the following figure); a group in which a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur or the like as a hetero atom is substituted with a phenyl group, a furyl group, or a thienyl group (for example, And the following formulas 113 to 118).

（式中、Ｒは、前記で定義したとおりである。）

(Wherein R is as defined above.)

Examples of the divalent aromatic amine group represented by Ar ₁ 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 (4):

〔式中、Ａｒ₃、Ａｒ₄、Ａｒ₅及びＡｒ₆は、それぞれ独立に、アリーレン基又は２価の複素環基を表す。Ａｒ₇、Ａｒ₈及びＡｒ₉は、それぞれ独立に、アリール基又は１価の複素環基を表す。Ａｒ₃、Ａｒ₄、Ａｒ₅、Ａｒ₆、Ａｒ₇、Ａｒ₈及びＡｒ₉は置換基を有していてもよい。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。

[Wherein, Ar ₃ , Ar ₄ , Ar ₅ and Ar ₆ each independently represent an arylene group or a divalent heterocyclic group. Ar ₇ , Ar ₈ and Ar ₉ each independently represents an aryl group or a monovalent heterocyclic group. Ar ₃ , Ar ₄ , Ar ₅ , Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ 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 (4), x is preferably an integer of 0 to 2, and more preferably 0 or 1, in view of device characteristics such as lifetime and ease of synthesis. Moreover, in said Formula (4), it is preferable that y is an integer of 0-2 from the element characteristics, such as a lifetime, and the easiness of a synthesis | combination, and it is more preferable that it is 0 or 1.

  Specific examples of the group represented by the formula (4) 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。）

(Wherein R is as defined above.)

In Ar _1, the following formulas (2-1) to (2-5):

〔式中、Ｒ³は独立に置換基を表し、ｍ１は独立に０〜３の整数を表し、ｍ２は独立に０〜５の整数を表す。式（２−１）及び（２−５）において、Ｘ’は、−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）−、−Ｓ（＝Ｏ）₂−、−Ｃ（Ｒ⁴）₂−、−Ｓｉ（Ｒ⁴）₂−Ｓｉ（Ｒ⁴）₂−、−Ｓｉ（Ｒ⁴）₂−、−Ｂ（Ｒ⁴）−、−Ｐ（Ｒ⁴）−、−Ｐ（＝Ｏ）（Ｒ⁴）−、−Ｏ−Ｃ（Ｒ⁴）₂−又は−Ｎ＝Ｃ（Ｒ⁴）−を表し、式（２−２）、（２−３）及び（２−４）において、Ｘ’は、−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）−、−Ｓ（＝Ｏ）₂−、−Ｃ（Ｒ⁴）₂−、−Ｓｉ（Ｒ⁴）₂−Ｓｉ（Ｒ⁴）₂−、−Ｓｉ（Ｒ⁴）₂−、−Ｂ（Ｒ⁴）−、−Ｐ（Ｒ⁴）−、−Ｐ（＝Ｏ）（Ｒ⁴）−、−Ｏ−Ｃ（Ｒ⁴）₂−、−Ｃ（Ｒ⁴）₂−Ｏ−、−Ｃ（Ｒ⁴）＝Ｎ−又は−Ｎ＝Ｃ（Ｒ⁴）−を表し、Ｒ⁴は独立に水素原子又は置換基を表す。〕
で表される基が、発光効率等の素子特性の観点から好ましい。

[Wherein, R ³ independently represents a substituent, m 1 independently represents an integer of 0 to 3, and m 2 independently represents an integer of 0 to 5. In the formulas (2-1) and (2-5), X ′ represents —O—, —S—, —S (═O) —, —S (═O) ₂ —, —C (R ⁴ ) _2. ^{-, - Si (R 4)} 2 -Si (R 4) 2 -, - Si (R 4) 2 -, - B (R 4) -, - P (R 4) -, - P (= O) ( R ⁴ ) —, —O—C (R ⁴ ) ₂ — or —N═C (R ⁴ ) —, and in formulas (2-2), (2-3) and (2-4), X ′ is, -O -, - S -, - S (= O) -, - S (= O) 2 -, - C (R 4) 2 -, - Si (R 4) 2 -Si (R 4) 2 ^{-, - Si (R 4)} 2 -, - B (R 4) -, - P (R 4) -, - P (= O) (R 4) -, - O-C (R 4) 2 -, _{^{-C (R 4) 2 -O -}} , - C (R 4) = N- or -N = C (R ⁴⁾ - represents, R ⁴ represents independently a hydrogen atom or a substituent. ]
Is preferable from the viewpoint of device characteristics such as luminous efficiency.

  Among the groups represented by the formulas (2-1) to (2-5), the following (2-A) to (2-G):

〔式中、Ｘ’、Ｒ³、ｍ１及びｍ２は前述と同じ意味を表す。〕
で表される基が好ましい。

[Wherein, X ′, R ³ , m1 and m2 represent the same meaning as described above. ]
The group represented by these is preferable.

In the formulas (2-1) to (2-5) and the formulas (2-A) to (2-G), examples of the substituent represented by R ³ include an alkyl group, an alkoxy group, an alkylthio group, and an aryl group. , Aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, 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 viewpoints of solubility and ease of synthesis, alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkoxy groups, monovalent groups. The heterocyclic group is preferably an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group. These groups are specifically the same as those described and exemplified as the substituents represented by Z and R ¹ .

R ⁴ is preferably a substituent, and examples of the substituent represented by R ⁴ include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, and an 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, monovalent Heterocyclic group, carboxyl group, substituted carboxyl group, nitro group, cyano group and the like can be mentioned. A hydrogen atom contained in these groups and residues may be substituted with a fluorine atom. Among R ⁴ , 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 substituents represented by Z and R ¹ .

  Specific examples of the groups represented by the formulas (2-1) to (2-5) include groups represented by the following formulas (2-6) to (2-66).

（式中、Ｒ³及びＲ⁴は、前記で定義したとおりである。）

(Wherein R ³ and R ⁴ are as defined above.)

X ′ represents —O—, —S—, —C (R ⁴ ) ₂ —, —Si (R ⁴ ) ₂ —, —O—C (R) from the viewpoint of device characteristics such as luminous efficiency and luminance half life. ⁴ ) ₂ —, —C (R ⁴ ) ₂ —O— is preferable, —O—, —S—, —C (R ⁴ ) ₂ — is more preferable, and —C (R ⁴ ). _2- is more preferable.

  In the formulas (2-A) to (2-G), the polymer includes a repeating unit represented by formulas (2-A) and (2-C) from the viewpoint of device characteristics and the like. Is preferred.

  The polymer may contain two or more types of repeating units represented by the formula (1), and may contain two or more types of repeating units represented by the formula (2).

The polymer contained in the composition of the present invention is further represented by the following formula (3):
-CR ⁵ = CR ^6- (3)
(Wherein R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group.)
A repeating unit represented by the following formula (4):
-C≡C- (4)
The repeating unit represented by these may be included.

In the formula (3), the alkyl group, aryl group, monovalent heterocyclic group and substituted carboxyl group represented by R ⁵ and R ⁶ are specifically the substituents represented by Z and R ^1. This is as explained and exemplified in the section.

  The polymer may further contain a repeating unit other than the repeating units represented by the formulas (1) to (4) as long as the light emitting characteristics and the charge transport characteristics are not impaired.

  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個の炭化水素基を表す。）

(In the formula, R is as defined above, and Ar represents a hydrocarbon group having 6 to 60 carbon atoms which may contain a hetero atom.)

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

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

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. Moreover, it is preferable that it is 1 * 10 < ⁵ > -5 * 10 < ⁶ > from a soluble viewpoint. 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 heterocyclic group via 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 of molecular chain terminals 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.

-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 3000 or less, 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。）

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

  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。）

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

  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。）

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

  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。）

(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.)

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は独立に、−Ｏ−、−Ｓ−、−ＮＲ−、−ＣＲ₂−、−Ｃ（＝Ｏ）−を表す。）

(Wherein R represents the same meaning as described above, and X _b independently represents —O—, —S—, —NR—, —CR ₂ —, —C (═O) —).

  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は独立にアリール基又は１価の複素環基を表す。）

(Wherein R represents the same meaning as described above, Ar _a represents an arylene group or a divalent heterocyclic group, and Ar _b independently represents an aryl group or a monovalent heterocyclic group.)

  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。）

(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, arrows represent coordination bonds)..

  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。また、※の位置で金属と結合する。）

(In the formula, R represents the same meaning as described above, and binds 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。）

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

  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。）

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

  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。）

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

  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。）

(Wherein, R represents the same as defined above, n _c is an integer of 1-20.)

  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は独立に、−Ｏ−、−Ｓ−、−ＮＲ−又は−ＣＨ＝ＣＨ−を表す。）

(Wherein R represents the same meaning as described above, n _c represents an integer of 1 to 20, and X _e independently represents —O—, —S—, —NR—, or —CH═CH—). )

  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。）

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

  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。）

(In the formula, R represents the same meaning as described above. The arrow from N to O means a coordination bond.)

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

（式中、Ｒ及びＡｒ_aは前述と同じ意味を表す。）

(In the formula, R and Ar _a represent the same meaning as described above.)

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

（式中、Ｒ及びＡｒ_bは前述と同じ意味を表す。）

(In the formula, R and Ar _b represent the same meaning as described above.)

  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。）

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

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

（式中、Ｒ及びＡｒ_bは前述と同じ意味を表す。）

(In the formula, R and Ar _b represent the same meaning as described above.)

  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。）

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

  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。）

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

-Relationship between polymers and low-molecular fluorescent materials-
From the viewpoint of luminous efficiency, the absolute value of the LUMO energy level of the polymer is preferably smaller than the absolute value of the LUMO energy level of the low-molecular fluorescent material. The difference (absolute value) in LUMO energy level between the polymer and the low-molecular fluorescent material is preferably 0.2 eV or less, more preferably 0.15 eV or less, from the viewpoint of luminous efficiency. More preferably, it is 1 eV or less. The lower limit is usually 0 eV.

  The absolute value of the HOMO (highest occupied level) energy level of the polymer is preferably larger than the absolute value of the HOMO energy level of the low-molecular fluorescent material from the viewpoint of luminous efficiency. The difference in HOMO energy level (absolute value) between the polymer and the low-molecular fluorescent material is preferably 0.2 eV or less, more preferably 0.15 eV or less, and more preferably 0.1 eV from the viewpoint of luminous efficiency. More preferably, it is as follows. The lower limit is usually 0 eV.

  The HOMO energy level and LUMO energy level of the above-described polymer and low-molecular fluorescent material can be measured using a cyclic voltammetry apparatus. If the polymer or low-molecular fluorescent material to be measured is insoluble in the solvent used for measurement, a thin film of the polymer or low-molecular fluorescent material is prepared on the electrode surface, and the electrode, counter electrode, and reference electrode are added to the solvent to which the electrolyte is added. Insert. A potential at which a flowing current starts to flow by applying a positive potential is defined as an oxidation potential, and a potential at which a flowing current starts to flow by applying a negative potential is defined as a reduction potential. Since the standard electrode potential differs depending on the combination of electrode type, solvent, electrolyte, etc., in order to compare the oxidation potential or reduction potential, measurement must be performed using the same combination of electrode, solvent, and electrolyte. When the polymer or low-molecular fluorescent material to be measured is dissolved in the solvent used for measurement, the polymer or low-molecular fluorescent material is dissolved in the solvent to which the electrolyte is added, and the electrode, counter electrode, and reference electrode are placed in the solvent. . A potential at which a flowing current starts to flow by applying a positive potential is defined as an oxidation potential, and a potential at which a flowing current starts to flow by applying a negative potential is defined as a reduction potential.

  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 to be combined 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.

  The composition of the present invention may contain components other than the polymer containing the repeating unit represented by the formula (1) and the low molecular fluorescent material. Specifically, for example, a polymer having no repeating unit represented by the formula (1), a low molecular compound other than the low molecular fluorescent material, 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. However, the composition of the present invention usually does not contain a compound that exhibits phosphorescence.

  Examples of the hole transport material that may be contained in the composition of the present invention include, for example, polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in a side chain or a main chain, a pyrazoline derivative, an aryl Amine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, poly (2,5-thienylene vinylene) or derivatives thereof Etc.

  Examples of the electron transport material that may be contained in the composition of the present invention include oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthra. Quinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof, etc. Can be mentioned.

  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 has a polystyrene-equivalent weight average molecular weight of preferably 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 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.

<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 by reducing 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 proportion 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, based on the total weight of the liquid composition. Preferably it is 90 weight%-99.8 weight%. Although the viscosity of the liquid composition varies depending on the printing method, it is preferably in the range of 0.5 to 500 mPa · s at 25 ° C. If the liquid composition such as an ink jet printing method passes through a discharge device, clogging during discharge And the viscosity is preferably in the range of 0.5 to 20 mPa · s at 25 ° C. in order to prevent flight bending. Further, the sum of the weights of the polymer containing the repeating unit represented by the formula (1) and the low-molecular 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 180 ° C. or lower. More preferably, the solvent has a boiling point of 180 ° C. or lower. 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 180 ° C. or lower. 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 180 ° C. or less. 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 viewpoints 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 obtained by the method described in “Solvent Handbook (published by Kodansha, 1976)”.

<Thin film>
Next, the thin film of the present invention will be described. This thin film is formed using the 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 still more preferably 70% or more, from the viewpoint of device brightness, 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 of the present invention (including a liquid composition) 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 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 liquid crystal display backlight). Further, the composition of the present invention can be used as a laser dye, an organic solar cell material, an organic semiconductor for an organic transistor, a conductive thin film, a conductive thin film material such as an organic semiconductor thin film, 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 has 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. 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. It is 1 nm-1 micrometer, Preferably it is 2 nm-500 nm, More preferably, it is 5 nm-200 nm.

  Examples of the method for forming the light emitting layer include a method of forming a film from a liquid composition. Film formation methods from liquid compositions include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and 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. 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.

  The polymer light-emitting device of the present invention preferably has a maximum external quantum yield of 1% or more when a voltage of 3.5 V or more is applied between the anode and the cathode from the viewpoint of device brightness and the like. More preferably, it is 5% or more.

  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 or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, a polyaniline or a derivative thereof , Polythiophene or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, and a polymer hole transport material such as poly (2,5-thienylene vinylene) or a derivative thereof is preferable, polyvinylcarbazole or a derivative thereof, polysilane or 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. Polymer binders include poly (N-vinylcarbazole), polyaniline or derivatives thereof, polythiophene or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, poly (2,5-thienylene vinylene) or derivatives thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

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

  Examples of polysilane or derivatives thereof include compounds described in Chemical Review, Vol. 89, page 1359 (1989), GB GB2300196 published specification, and the like. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.

  Since polysiloxane or a derivative thereof has almost no hole transporting property in the siloxane skeleton structure, those having the structure of the low molecular 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 a 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.

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

  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 or derivatives thereof, anthraquinones or derivatives thereof, metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof are preferred. 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, 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 an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode, and the adhesion at the interface may be improved. In order to prevent mixing, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.

  The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

In the present invention, 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.

  A specific example of the charge injection layer is a layer containing a conductive polymer, provided between the anode and the hole transport layer, and having 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 a 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, the conductive polymer is doped with an appropriate amount of ions in order to set the electric conductivity of the conductive polymer to 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less.

  The 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 having a thickness of 2 nm or less has a function of facilitating charge injection. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials.

The polymer light emitting device provided with an insulating layer having a thickness of 2 nm or less includes a polymer light emitting device provided with an insulating layer having a thickness of 2 nm or less adjacent to the cathode, and an insulating layer having a thickness of 2 nm or less adjacent to the anode. The provided polymer light emitting element is mentioned. Specific examples include the following structures q) to ab).
q) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / cathode r) Anode / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode s) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / film thickness 2 nm Insulating layer / cathode t) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / cathode u) Anode / hole transporting layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode v) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode w) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / cathode x) anode / Light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode y) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode z) anode / film Insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / cathode aa) anode / hole transport layer / light emitting layer / electron transport Layer / thickness 2nm or less of the insulating layer / cathode ab) anode / thickness 2nm or less of the insulating layer / hole transport layer / light emitting layer / electron transporting layer / thickness 2nm or less of the insulating layer / cathode

  The 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 of the substrate include glass, plastic, polymer film, silicon substrate, and the like. 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. Further, as the anode, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used.

  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 on the anode, 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 having an average film thickness of 2 nm or less It may be provided.

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

  As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used. Further, a layer made of a conductive polymer or a layer made of a metal oxide, a metal fluoride, an organic insulating material or the like having an average film thickness of 2 nm or less may be provided between the cathode and the organic layer. A protective layer for protecting the polymer light emitting device may be provided. 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 (eg, illumination), a segment display device (eg, a segment type display device), a dot matrix display device (eg, , 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 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. As a film formation method from a liquid composition in which a composition containing an organic solvent-soluble polymer contains a 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 Application 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 Examples, the polystyrene-equivalent number average molecular weight and 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 as the mobile phase of GPC, and flowed at a flow rate of 0.6 mL / min. As for the column, two TSKgel SuperHM-H (manufactured by Tosoh) 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 energy level and LUMO energy level-
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. The HOMO energy level of the low molecular fluorescent material was determined from the oxidation potential of the low molecular fluorescent material, and the LUMO energy level of the low molecular fluorescent material was determined from the reduction potential of the low molecular fluorescent material. For the measurement of the oxidation potential and the reduction potential, cyclic voltammetry (manufactured by BAS, trade name: ALS600) was used, and 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.

<Synthesis Example 1>
-Synthesis of Polymer 1-
768 mg of 9,9-dioctyl-2,7-dibromofluorene and the following structural formula:

で表される化合物 ２８４ｍｇと、２，２’−ビピリジル ８４３ｍｇ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（ＴＨＦ）（脱水溶媒）１０８ｍｌ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）｛Ｎｉ（ＣＯＤ）₂｝を１４８５ｍｇ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。

In a reaction vessel, 284 mg of the compound represented by the following formula and 843 mg of 2,2′-bipyridyl were charged, and the inside of the reaction system was replaced with nitrogen gas. To this, 108 ml of tetrahydrofuran (THF) (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, 1485 mg of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added to this mixed solution, stirred at room temperature for 10 minutes, and reacted at 60 ° C. for 3 hours. The reaction was performed in a nitrogen gas atmosphere.

  After the reaction, this solution was cooled, then poured into a mixed solution of 25% by weight aqueous ammonia 7.2 ml / methanol 108 ml / ion exchanged water 108 ml, and stirred for about 1 hour. Next, the produced precipitate was recovered by filtration. This precipitate was dried under reduced pressure and then dissolved in 60 ml of toluene. The solution was filtered to remove insoluble matters, and then the solution was purified by passing through a column filled with alumina. Next, this solution was washed with 5.2 wt% aqueous hydrochloric acid. After separation, the toluene layer was washed with 4% by weight aqueous ammonia. After separation, the toluene layer was washed with ion exchange water. After separation, the toluene solution was recovered. Next, this toluene solution was poured into methanol with stirring and purified by reprecipitation. After the produced precipitate was recovered, this precipitate was washed with methanol. This precipitate was dried under reduced pressure to obtain 500 mg of a polymer (hereinafter referred to as “polymer 1”).

The polystyrene equivalent number average molecular weight of the polymer 1 was 2.1 × 10 ⁴ , and the polystyrene equivalent weight average molecular weight was 1.9 × 10 ⁵ .

  From the charge ratio of the starting materials, the polymer 1 has the following formula:

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。

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

-Measurement of HOMO energy level and LUMO energy level-
According to the measurement method described above, the HOMO energy level and LUMO energy level of the polymer 1 and rubrene were measured. Polymer 1 had a HOMO energy level of 5.3 eV and a LUMO energy level of 2.4 eV. The energy level of rubrene HOMO was 5.2 eV, and the energy level of LUMO was 3.2 eV.

<Example 1>
-Preparation of Composition 1-
Polymer 1 and rubrene (photoluminescence emission peak: 560 nm) were mixed at a weight ratio of 95: 5 to prepare a composition (hereinafter referred to as “composition 1”).

<Synthesis Example 2>
-Synthesis of polymer 2-
9.63 g of 9,9-dioctyl-2,7-dibromofluorene and the following structural formula:

で表される化合物 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）を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。

After charging 3.0 g of the compound represented by the formula (2) and 8.25 g of 2,2′-bipyridyl into the reaction vessel, the inside of 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 then a mixed solution of 25 wt% ammonia water 70 ml / methanol 700 ml / ion exchanged water 700 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 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-exchanged 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 2”). The polystyrene equivalent weight average molecular weight of the polymer 2 was 1.4 × 10 ⁵ , and the polystyrene equivalent number average molecular weight was 4.1 × 10 ⁴ .

  From the charge ratio of the starting materials, the polymer 2 has the following formula:

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。

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

-Measurement of HOMO energy level and LUMO energy level-
According to the measurement method described above, the HOMO energy level and LUMO energy level of the polymer 2 were measured. Polymer 2 had a HOMO energy level of 5.5 eV and a LUMO energy level of 2.3 eV.

<Comparative Example 1>
-Preparation of composition 2-
Polymer 2 and rubrene were mixed at a weight ratio of 95: 5 to prepare a composition (hereinafter referred to as “Composition 2”).

<Example 2>
-Fabrication of light-emitting elements-
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (from Bayer, Bytron P AI4083) was applied to a glass substrate with an ITO film having a thickness of 150 nm by sputtering, and a thickness of 80 nm by spin coating. Then, the film was formed on a hot plate and dried at 200 ° C. for 10 minutes. Next, the composition 1 was dissolved in toluene at a concentration of 1.5% by weight, and a film was formed to a thickness of about 80 nm by spin coating using the toluene solution. Then, after drying for 1 hour at 90 ° C. in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less, lithium fluoride was deposited as a cathode at about 4 nm, then calcium was deposited at 5 nm, and finally aluminum was deposited at about 100 nm. A molecular light emitting device was produced. The device configuration was ITO / Baytron P (80 nm) / Composition 1 (80 nm) / LiF / Ca / Al. Note that, after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.

When a voltage of 6.0 V was applied to the obtained device, fluorescence was emitted with a luminance of 1000 cd / m ² and a peak top of the fluorescence wavelength of 550 nm, and the light emission efficiency was 0.87 cd / A.

<Comparative example 2>
-Fabrication of light-emitting elements-
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (from Bayer, Bytron P AI4083) was applied to a glass substrate with an ITO film having a thickness of 150 nm by sputtering, and a thickness of 80 nm by spin coating. Then, the film was formed on a hot plate and dried at 200 ° C. for 10 minutes. Next, the composition 2 was dissolved in toluene at a concentration of 2.0% by weight, and a film having a thickness of about 80 nm was formed by spin coating using the toluene solution. Then, after drying for 1 hour at 90 ° C. in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less, lithium fluoride was deposited as a cathode at about 4 nm, then calcium was deposited at 5 nm, and finally aluminum was deposited at about 100 nm. A molecular light emitting device was produced. The device configuration was ITO / Baytron P (80 nm) / Composition 2 (80 nm) / LiF / Ca / Al. Note that, after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.

When a voltage of 6.3 V was applied to the obtained device, fluorescence was emitted with a luminance of 1000 cd / m ² and a peak top of the fluorescence wavelength of 550 nm, and the light emission efficiency was 0.53 cd / A. The luminance at 6.0 V was 724 cd / m ² .

<Synthesis Example 3>
-Synthesis of Polymer 3-
Under a nitrogen atmosphere, 9.65 g of 9,9-dioctyl-2,7-dibromofluorene and the following structural formula:

で表される化合物１．８０ｇ、メチルトリオクチルアンモニウムクロライド（商品名：アリコート３３６、アルドリッチ社製）１．２１ｇ とを反応容器に仕込んだ後、トルエン５２ｇに溶解させ、これに炭酸カリウム１．３１ｇを水５６ｇに溶解させた炭酸カリウム水溶液を加えた。さらにテトラキス(トリフェニルホスフィン)パラジウム ６．９ｍｇを加え、１０時間加熱還流した。その後、ブロモベンゼン６１ｍｇを加え更に２時間加熱還流した。室温まで冷却後、有機層をメタノールに滴下し、析出した沈殿を濾別し乾燥して重合体（以下、この重合体を「重合体（３−１）」という。）を得た。
別途、同様の合成操作を２回行い、重合体（３−２）及び重合体（３−３）を得た。こうして得られた重合体（３−１）、重合体（３−２）及び重合体（３−３）を混合し、トルエン１５０ｍＬに溶解させ、この溶液をシリカとアルミナを充填したカラムを通すことで精製した。その後、得られた精製物（溶液）をメタノール５００ｍＬに滴下し、析出した沈殿を濾別、乾燥し、重合体３．８２ｇを得た（以下、この重合体を「重合体３」という）。

And 1.21 g of methyltrioctylammonium chloride (trade name: aliquot 336, manufactured by Aldrich) were charged into a reaction vessel and dissolved in 52 g of toluene, and 1.31 g of potassium carbonate was added thereto. A potassium carbonate solution in which 56 g of water was dissolved was added. 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 and dried to obtain a polymer (hereinafter, this polymer is referred to as “polymer (3-1)”).
Separately, the same synthesis operation was performed twice to obtain a polymer (3-2) and a polymer (3-3). The polymer (3-1), polymer (3-2) and polymer (3-3) thus obtained are mixed, dissolved in 150 mL of toluene, and this solution is passed through a column filled with silica and alumina. Purified with. Thereafter, the purified product (solution) obtained 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 3”).

The polystyrene equivalent number average molecular weight of the polymer 3 was 1.1 × 10 ⁴ , and the polystyrene equivalent weight average molecular weight was 2.3 × 10 ⁴ .

  From the starting material, the polymer 3 has the following formula:

で表される繰り返し単位を有するものと推測される。

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

-Measurement of HOMO energy level and LUMO energy level-
According to the measurement method described above, the HOMO energy level and LUMO energy level of the polymer 3 were measured. Polymer 3 had a HOMO energy level of 5.89 eV and a LUMO energy level of 2.37 eV.

<Comparative Example 3>
-Preparation of Composition 3-
Polymer 3 and rubrene were mixed at a weight ratio of 95: 5 to prepare a composition (hereinafter referred to as “Composition 3”).

<Comparative example 4>
-Fabrication of light-emitting elements-
In Example 2, a polymer light emitting device was produced in the same manner as in Example 2 except that the composition 3 was used instead of the composition 1.

  When a voltage of 6.0 V was applied to the resulting device, fluorescence was emitted with a peak wavelength of 440 nm. This luminescence was substantially luminescence from the polymer 3.

<Evaluation>
In the device manufactured in Example 2 and the device manufactured in Comparative Example 2, the light emission when a voltage was applied was substantially derived from a low molecular fluorescent material. Compared with the element produced in Comparative Example 2, the element produced in Example 2 was remarkably superior.
Further, in the device produced in Comparative Example 4, light emission when a voltage was applied was substantially derived from the polymer. That is, almost no light emission derived from the low molecular fluorescent material was observed.

Claims (15)

Following formula (1):

[Wherein Y ′ represents —O—, —S— or —C (═O) —, Z represents a hydrogen atom or a substituent, R ¹ represents a substituent, and n represents 0 to 0. An integer of 3 is represented. When a plurality of R ¹ are present, they may be the same or different. ]
The composition containing the polymer containing the repeating unit represented by these, and a low molecular fluorescent material.   Z may have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a substituent. The composition according to claim 1, which is a monovalent heterocyclic group. The repeating unit represented by the formula (1) is represented by the following formula (1-1):

[Wherein, Y ′, R ¹ and n represent the same meaning as described above, R ² represents a substituent, and p1 represents an integer of 0 to 5. ]
The composition according to claim 1 or 2, which is represented by: The polymer is further represented by the following formula (2):
-Ar _1- (2)
[In the formula, Ar ₁ represents an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or a divalent aromatic which may have a substituent. Represents a group amine group. ]
The composition as described in any one of Claims 1-3 containing the repeating unit represented by these. The repeating unit represented by the formula (2) is represented by the following formulas (2-1) to (2-5):

[Wherein, R ³ independently represents a substituent, m1 represents an integer of 0 to 3, and m2 represents an integer of 0 to 5. In the formulas (2-1) and (2-5), X ′ represents —O—, —S—, —S (═O) —, —S (═O) ₂ —, —C (R ⁴ ) _2. ^{-, - Si (R 4)} 2 -Si (R 4) 2 -, - Si (R 4) 2 -, - B (R 4) -, - P (R 4) -, - P (= O) ( R ⁴ ) —, —O—C (R ⁴ ) ₂ — or —N═C (R ⁴ ) —, and in formulas (2-2), (2-3) and (2-4), X ′ is, -O -, - S -, - S (= O) -, - S (= O) 2 -, - C (R 4) 2 -, - Si (R 4) 2 -Si (R 4) 2 ^{-, - Si (R 4)} 2 -, - B (R 4) -, - P (R 4) -, - P (= O) (R 4) -, - O-C (R 4) 2 -, _{^{-C (R 4) 2 -O -}} , - C (R 4) = N- or -N = C (R ⁴⁾ - represents, R ⁴ represents independently a hydrogen atom or a substituent. ]
The composition according to claim 4, which is a repeating unit represented by any one of: The composition according to claim 5, wherein X ′ is —C (R ⁴ ) ₂ —. The composition according to any one of claims 1 to 6, wherein the polymer has a weight average molecular weight in terms of polystyrene of 3 x 10 ³ to 1 x 10 ⁸ .   The absolute value of the LUMO energy level of the polymer is smaller than the absolute value of the LUMO energy level of the low-molecular fluorescent material, and the difference between them is 0.2 eV or less. The composition as described.   The absolute value of the HOMO energy level of the polymer is larger than the absolute value of the HOMO energy level of the low-molecular fluorescent material, and the difference between them is 0.2 eV or less. The composition as described.   The composition according to any one of claims 1 to 9, further comprising a polymer having no repeating unit represented by the formula (1).   The composition according to any one of claims 1 to 10, wherein the content of the low-molecular fluorescent material is 0.01 to 49 parts by weight with respect to 100 parts by weight of the polymer.   Furthermore, the liquid composition which consists of a composition as described in any one of Claims 1-11 containing a solvent.   A thin film using the composition according to any one of claims 1 to 11 and / or the liquid composition according to claim 12.   An organic transistor having the thin film according to claim 13. The polymer light emitting element which has an electrode which consists of an anode and a cathode, and the organic layer which is provided between this electrode and contains the composition as described in any one of Claims 1-11.