JP5239129B2 - Polymer light-emitting device, organic transistor and composition useful for them - Google Patents

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, this composition has a problem that, 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.
Accordingly, an object of the present invention is to provide a composition capable of almost selectively obtaining light emission derived from a low-molecular fluorescent material from the light-emitting element when used for production of the light-emitting element.

  The present invention provides the following formula (1):

〔式中、Ａｒは独立に、置換基を有していてもよいアリール基、又は置換基を有していてもよい１価の複素環基を表し、Ｒ¹は独立に、置換基を表し、ｍは独立に０〜３の整数を表す。〕
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。

[In the formula, Ar independently represents an aryl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent, and R ¹ independently represents a substituent. , M independently represents an integer of 0-3. ]
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. Therefore, 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 useful for display devices such as a display device (for example, a dot matrix flat display) and a liquid crystal display device (for example, a liquid crystal display device, a backlight of a liquid crystal display).
The composition of the present invention is not only suitable as a material used for the production thereof, but also conductive properties such as laser dyes, organic solar cell materials, organic semiconductors for organic transistors, conductive thin films, and organic semiconductor thin films. It is also suitable as a material for a thin film, a light emitting thin film material that emits fluorescence, a material for a polymer field effect transistor, and the like.

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

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

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

  The alkoxy group may be linear, branched or cyclic, and usually has 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 and the like. From the viewpoint of the heat resistance and the solubility of the polymer in an organic solvent, device characteristics, ease of synthesis of the polymer, and the like, pentyloxy group, hexyloxy Group, octyloxy group, 2-ethylhexyloxy group, decyl group Alkoxy group, 3,7-dimethyl octyloxy group are preferable. Moreover, as a substituted alkoxy group, a methoxymethyloxy group, 2-methoxyethyloxy group, etc. are mentioned, for example.

  The alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, i-propylthio group, butylthio group, i-butylthio group, t-butylthio group, 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., and the solubility of the polymer in an organic solvent, device characteristics, A pentylthio group, a hexylthio group, an octylthio group, a 2-ethylhexylthio group, a decylthio group, and a 3,7-dimethyloctylthio group are preferable from the viewpoint of the ease of synthesis and the heat resistance.

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., solubility of polymer in organic solvent, device characteristics, synthesis of polymer from the viewpoint of easiness is, C ₁ -C ₁₂ alkoxyphenyl group, is C ₁ -C ₁₂ alkylphenyl group are preferable. Specific examples C ₁ -C ₁₂ alkoxyphenyl group, methoxyphenyl group, ethoxyphenyl group, propyloxyphenyl group, i- propyl group, a butoxyphenyl group, i- butoxyphenyl, t-butoxyphenyl group, 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 of the polymer in an organic solvent, device characteristics, ease of synthesis of the polymer, and the like, a C _{1 to} C ₁₂ alkoxyphenoxy group and a C _{1 to} C ₁₂ alkylphenoxy group are preferable. Specific examples C ₁ -C ₁₂ alkoxy phenoxy group, methoxyphenoxy group, ethoxyphenoxy group, propyloxy phenoxy group, i- propyloxy phenoxy group, butoxyphenoxy group, i- butoxyphenoxy group, t-butoxyphenoxy group, 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 From the viewpoints of solubility of the polymer in an organic solvent, device characteristics, ease of synthesis of the polymer, and the like, a C ₁ -C ₁₂ alkoxyphenylthio group and a C ₁ -C ₁₂ alkylphenylthio group are preferred.

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

The arylalkoxy group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples of the arylalkoxy group include phenyl-C _{1 to} C ₁₂ such as phenylmethoxy group, phenylethoxy group, phenylbutoxy group, phenylpentyloxy group, phenylhexyloxy group, phenylheptyloxy group, and phenyloctyloxy group. alkoxy groups, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl -C ₁ -C ₁₂ alkoxy groups, 2-naphthyl -C ₁ -C ₁₂ alkoxy groups and the like, soluble organic solvent, device properties of the polymer, from the viewpoint of easiness of synthesis of a polymer, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy group are preferable.

The arylalkylthio group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples of the arylalkylthio group include a phenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group 1-naphthyl-C ₁ -C ₁₂ alkylthio group, 2-naphthyl-C ₁ -C ₁₂ alkylthio group, etc., and the solubility of the polymer in an organic solvent, device characteristics, and ease of synthesis of the polymer. From the viewpoints such as C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkylthio group is preferred.

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

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

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. These alkyl group, aryl group, arylalkyl group and monovalent heterocyclic group may have a substituent. The carbon number of the substituted amino group does not include the carbon number of the substituent, and is usually about 1 to 60, preferably 2 to 48. Specific examples of the substituted amino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, i-propylamino group, diisopropylamino group, butylamino group, i-butyl. Amino group, t-butylamino group, 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, thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl, pyridyl, C ₁ -C ₁₂ alkyl pyridyl group, a 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, q2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group , Trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooxy Chill oxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group and the like.

  In the formula (1), Ar is an aryl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. When Ar is an aryl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, and a 9-anthracenyl group from the viewpoint of ease of synthesis of the polymer, device characteristics, and the like. Group is preferably a pentafluorophenyl group. Further, when Ar is a monovalent heterocyclic group, from the viewpoint of ease of synthesis of the polymer, device characteristics, etc., thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidyl group, quinolyl group, isoquinolyl group Etc. are preferred.

  From the viewpoint of device characteristics and the like, Ar is preferably an aryl group which may have a substituent.

  The repeating unit represented by the formula (1) is represented by the following formula (1-1) from the viewpoint of ease of synthesis of the polymer, device characteristics, and the like.

〔式中、Ｒ¹及びｍは独立に、前記と同じ意味を表し、Ｒ²は独立に、置換基を表し、ｎは独立に、０〜５の整数を表す。〕
で表されるものが好ましい。

[Wherein, R ¹ and m independently represent the same meaning as described above, R ² independently represents a substituent, and n independently represents an integer of 0 to 5. ]
The thing represented by these is preferable.

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. The hydrogen atom contained in these substituents may be substituted with a fluorine atom or other group. Among these substituents, from the viewpoint of solubility of the polymer in an organic solvent and ease of synthesis of the polymer, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, An arylalkyl group, an arylalkoxy group, and a monovalent heterocyclic group are preferable, and an alkyl group, an alkoxy group, an aryl group, and a monovalent heterocyclic group are more preferable. Among these substituents, from the viewpoint of device characteristics, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group (the number of carbon atoms is usually 1 to 12, preferably 5 to 8). And substituted carboxyl groups are preferred. The substituent represented by R ² is specifically the same as described and exemplified as R ¹ above.

When R ² is an unsubstituted or substituted alkoxy group, the following formula (a):
* -O- (CH ₂ ) _n1 CH ₃ (a)
[In formula, n1 represents the integer of 0-9. The hydrogen atom in the formula may be substituted with an alkyl group having 1 to 5 carbon atoms. Moreover, it couple | bonds with the benzene ring of said Formula (1-1) in the position of *. ]
Or the following formula (b):
_{* -O- (CH 2) n2 -O-} (CH 2) n3 CH 3 (b)
[Wherein n2 represents an integer of 1 to 10, and n3 represents an integer of 1 to 9. The hydrogen atom in the formula may be substituted with an alkyl group having 1 to 5 carbon atoms. Moreover, it couple | bonds with the benzene ring of said Formula (1-1) in the position of *. ]
The thing represented by these is preferable.

  From the viewpoint of heat resistance of the polymer, n is preferably an integer of 1 to 5.

  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 10 to 99 mol%, more preferably 30 to 98 mol% of all repeating units in the polymer from the viewpoint of luminous efficiency. .

  As the repeating unit represented by the formula (1-1), the following formula (1-2):

（式中、Ｒ²及びｎは独立に、前記と同じである。）
で表されるものが好ましく、下記式（１−３）：

(Wherein R ² and n are independently the same as described above.)
Is preferably represented by the following formula (1-3):

（式中、Ｒ²は独立に、前記と同じである。）
で表されるものがより好ましく、下記式（１−４）：

(Wherein R ² is independently the same as described above.)
More preferably, the following formula (1-4):

（式中、Ｒ^Aは独立に、非置換又は置換のアルキル基を表す。）
で表されるものがさらに好ましい。

(In the formula, R ^A independently represents an unsubstituted or substituted alkyl group.)
Is more preferable.

In the above formula (1-4), the unsubstituted or substituted alkyl group represented by R ^A usually has 1 to 20, preferably 1 to 12, more preferably 5 to 8 carbon atoms. .

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 may have a substituent, an arylene group that is not a group represented by the formula (1), a divalent heterocyclic group that may have a substituent, or a substituent The divalent aromatic amine group which may have a group is represented. ]
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, the following formulas 1 to 3), a naphthalenediyl group (for example, the following formulas 4 to 13), an anthracene-diyl group (for example, the following formulas 14 to 19), Biphenyl-diyl group (for example, the following formulas 20 to 25), terphenyl-diyl group (for example, the following formulas 26 to 28), condensed ring compound groups (for example, the following formulas 29 to 35), fluorene-diyl group (for example, The following formulas 36 to 38), a stilbene-diyl group (the following formulas 39 to 42), a distilben-diyl group (for example, the following formulas 43 and 44), and a benzofluorene-diyl group (for example, the following formulas A-1 to A-3) ), A dibenzofluorene-diyl group (for example, the following formula A-4) and the like.

（式中、Ｒは独立に、水素原子又は置換基を表す。また、Ｒ³は独立に、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、ニトロ基、シアノ基を表す。）

(In the formula, R independently represents a hydrogen atom or a substituent. R ³ independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an amino group, a substituted amino group, a silyl group, or a substituted silyl group. Represents a halogen atom, an acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a nitro group or a cyano group.)

In the above formulas 1 to 44 and A-1 to A-4, examples of the substituent represented by R include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, Arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, Examples thereof include a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, and a cyano group. A hydrogen atom contained in these substituents may be substituted with a fluorine atom. These groups, residues and atoms are the same as those explained and exemplified in the section of the substituent represented by R ¹ . The substituent represented by R is preferably such that at least one R is other than a hydrogen atom from the viewpoint of solubility of the polymer in an organic solvent 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, the following formulas 45 to 50), a diazaphenylene group (for example, the following formulas 51 to 54), and a quinoline diyl group (for example, The following formulas 55-69), a quinoxaline diyl group (for example, the following formulas 70-74), an acridine diyl group (for example, the following formulas 75-78), a bipyridyldiyl group (for example, the following formulas 79-81), a phenanthroline diyl group ( For example, divalent heterocyclic groups containing nitrogen as a hetero atom, such as the following formulas 82 to 84) and groups having a carbazole structure (for example, the following formulas 85 to 87); oxygen, silicon, nitrogen, sulfur as hetero atoms , Selenium and the like 5-membered ring heterocyclic group (for example, the following formulas 88 to 92); 5-membered condensed heterocyclic group containing oxygen, silicon, nitrogen, selenium and the like as a hetero atom (for example, the following formulas 93 to 10 ); A 5-membered heterocyclic group containing oxygen, silicon, nitrogen, sulfur, selenium, etc. as a heteroatom, bonded at the α-position of the heteroatom to form a dimer or oligomer (for example, the following formula 104 To 105); groups bonded to a phenyl group at the α-position of the hetero atom in a 5-membered heterocyclic group containing oxygen, silicon, nitrogen, sulfur, selenium, etc. as a hetero atom (for example, the following formulas 106 to 112 ); Groups obtained by substituting a phenyl group, a furyl group, or a thienyl group on a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur or the like as a hetero atom (for example, the following formulas 113 to 118).

（式中、Ｒは独立に、前記で定義したとおりである。）

(Wherein R is independently 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 of the polymer. In the formula (4), y 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 of the polymer.

  Specific examples of the group represented by the formula (4) include those represented by the following formulas 119 to 126.

（式中、Ｒは独立に、前記で定義したとおりである。）

(Wherein R is independently as defined above.)

In Ar _1, the following formulas (2-1) to (2-6):

〔式中、Ｒ³は独立に前述と同じ意味を表し、Ｒ⁴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（２−２）において、Ｘ’は、−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）−、−Ｓ（＝Ｏ）₂−、−Ｓｉ（Ｒ^B）₂−Ｓｉ（Ｒ^B）₂−、−Ｓｉ（Ｒ^B）₂−、−Ｂ（Ｒ^B）−、−Ｐ（Ｒ^B）−、−Ｐ（＝Ｏ）（Ｒ^B）−、−Ｏ−Ｃ（Ｒ^B）₂−又は−Ｎ＝Ｃ（Ｒ^B）−を表し、式（２−３）、（２−４）、（２−５）及び（２−６）において、Ｘ’は、−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）−、−Ｓ（＝Ｏ）₂−、−Ｃ（Ｒ^B）₂−、−Ｓｉ（Ｒ^B）₂−Ｓｉ（Ｒ^B）₂−、−Ｓｉ（Ｒ^B）₂−、−Ｂ（Ｒ^B）−、−Ｐ（Ｒ^B）−、−Ｐ（＝Ｏ）（Ｒ^B）−、−Ｏ−Ｃ（Ｒ^B）₂−、−Ｃ（Ｒ^B）₂−Ｏ−、−Ｃ（Ｒ^B）＝Ｎ−又は−Ｎ＝Ｃ（Ｒ^B）−を表し、（２−６）において、Ｘ’は、−Ｏ−、−Ｓ−、−Ｓ（＝Ｏ）−、−Ｓ（＝Ｏ）₂−、−Ｃ（Ｒ^B）₂−、−Ｓｉ（Ｒ^B）₂−Ｓｉ（Ｒ^B）₂−、−Ｓｉ（Ｒ^B）₂−、−Ｂ（Ｒ^B）−、−Ｐ（Ｒ^B）−、−Ｐ（＝Ｏ）（Ｒ^B）−、−Ｏ−Ｃ（Ｒ^B）₂−又は−Ｎ＝Ｃ（Ｒ^B）−を表し、Ｒ^Bは独立に水素原子又は置換基を表す。〕
で表される繰り返し単位、及び前記式１０２、１０３、１１３〜１１６で表される基（該基を繰り返し単位とするもの）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 the same meaning as described above, R ⁴ 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 formula (2-2), X 'is, -O -, - S -, - S (= O) -, - S (= O) 2 -, - Si (R B) 2 -Si (R B) ₂ −, —Si (R ^B ) ₂ —, —B (R ^B ) —, —P (R ^B ) —, —P (═O) (R ^B ) —, —O—C (R ^B ) ₂ — Or -N = C (R ^B )-, and in formulas (2-3), (2-4), (2-5) and (2-6), X ′ represents —O—, —S—. , -S (= O) -, - S (= O) 2 -, - C (R B) 2 -, - Si (R B) 2 -Si (R B) 2 -, - Si (R B) 2 ^{-, - B (R B)} -, - P (R B) -, - P (= O) (R B) -, - O-C (R B) 2 -, - C (R B) 2 -O ^{-, - C (R B)} = N- or -N = C (R ^B) - represents, in (2-6), X 'is, -O -, - S -, - S (= O) - _{, -S (= O) 2 -} , - C (R B ^{_{2 -, - Si (R B}} ) 2 -Si (R B) 2 -, - Si (R B) 2 -, - B (R B) -, - P (R B) -, - P (= O) (R ^B ) —, —O—C (R ^B ) ₂ — or —N═C (R ^B ) — is represented, and R ^B independently represents a hydrogen atom or a substituent. ]
And groups represented by the formulas 102, 103, and 113 to 116 (those having the group as a repeating unit) are preferable from the viewpoint of device characteristics such as luminous efficiency.

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

  The polymer contained in the composition of the present invention is preferably a repeating unit represented by the above formula (1-3), and the following formula, from the viewpoint that light emission derived from a low molecular fluorescent material can be almost selectively obtained. (2-A):

（式中、Ｒ^Cは独立に、置換基を有していてもよいアルキル基を表す。）
で表される繰り返し単位とを含むもの、又は前記式（１−３）で表される繰り返し単位と、下記式（２−Ｂ）：

(In the formula, R ^C independently represents an alkyl group which may have a substituent.)
Or a repeating unit represented by the above formula (1-3) and the following formula (2-B):

（式中、Ｒ^Dは、置換基を有していてもよいアルキル基を表す。）
で表される繰り返し単位とを含むものであり、より好ましくは、前記式（１−４）で表される繰り返し単位と前記式（２−Ａ）で表される繰り返し単位、又は前記式（１−４）で表される繰り返し単位と前記式（２−Ｂ）で表される繰り返し単位とを含むものである。また、素子の発光効率の観点から、好ましくは、前記式（１−３）で表される繰り返し単位と、前記式（２−Ａ）で表される繰り返し単位とを含むもの、より好ましくは、前記式（１−４）で表される繰り返し単位と、前記式（２−Ａ）で表される繰り返し単位とを含むものが好ましい。

(In the formula, R ^D represents an alkyl group which may have a substituent.)
More preferably, the repeating unit represented by the formula (1-4) and the repeating unit represented by the formula (2-A), or the formula (1) -4) and the repeating unit represented by the formula (2-B). In addition, from the viewpoint of the luminous efficiency of the device, preferably, it includes a repeating unit represented by the formula (1-3) and a repeating unit represented by the formula (2-A), more preferably What contains the repeating unit represented by said Formula (1-4) and the repeating unit represented by said Formula (2-A) is preferable.

The alkyl group optionally having a substituent represented by R ^C in the formula (2-A) and R ^D in the formula (2-B) independently has a carbon number, 1 to 20, preferably 1 to 12, and more preferably 5 to 8 from the viewpoint of device characteristics and the like. Specific examples of the alkyl group which may have this substituent include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a pentyl group, Isoamyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, 1-undecanyl group, 1-dodecanyl group, 1-tridecanyl group, 1 -A tetradecanyl group, 1-pentadecanyl group, 1-hexadecanyl group and the like can be mentioned, and from the viewpoint of device characteristics, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, and an octyl group are preferable.

  [Formula (1-3): Formula (2-A)], [Formula (1-3): Formula (2-B)], [Formula (1-4): Formula (2-A)] and The ratio of the repeating units of [Formula (1-4): Formula (2-B)] is usually 10:90 to 99: 1 in terms of molar ratio, and is preferably 30 from the viewpoint of device characteristics. : 70 to 98: 2.

  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.)
And / or 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 term of the substituent represented by R ^1. As described and exemplified in FIG.

  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は独立に、前記で定義したとおりであり、Ａｒはヘテロ原子を含んでいてもよい炭素数６〜６０の炭化水素基を表す。）

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

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

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

  As a polymer contained in the composition of the present invention, the following formula (5-1):

（式中、ｘ及びｙは独立に整数であり、Ｒ^A及びＲ^Cは独立に前記と同じである。）
で表されるもの、及び下記式（５−２）：

(Wherein x and y are independently integers, and R ^A and R ^C are independently the same as described above.)
And the following formula (5-2):

（式中、ｐ及びｑは独立に整数であり、Ｒ^A及びＲ^Dは独立に前記と同じである。）
で表されるものが好ましく、下記式（５−３）：

(In the formula, p and q are independently integers, and R ^A and R ^D are independently the same as described above.)
Is preferably represented by the following formula (5-3):

（式中、ｘ及びｙは前記と同じである。）
で表されるもの、及び下記式（５−４）：

(Wherein x and y are the same as above)
And the following formula (5-4):

（式中、ｐ及びｑは前記と同じである。）
で表されるものがより好ましい。また、素子の発光効率の観点から、好ましくは、前記式（５−１）で表されるものであり、より好ましくは、前記式（５−３）で表されるものである。

(Wherein p and q are the same as above)
Is more preferable. Moreover, from a viewpoint of the luminous efficiency of an element, Preferably, it is represented by said Formula (5-1), More preferably, it is represented by said Formula (5-3).

  In the formulas (5-1) and (5-3), x and y are integers in which x: y (molar ratio) usually satisfies 1:99 to 90:10. From the viewpoint of device characteristics, Preferably, it is an integer satisfying 2:98 to 70:30, more preferably an integer satisfying 50:50 to 70:30.

  In the formulas (5-2) and (5-4), p and q are integers in which p: q (molar ratio) usually satisfies 10:90 to 99: 1, and are derived from a low-molecular fluorescent material. From the viewpoint of almost selectively obtaining the light emission, it is preferably an integer satisfying 30:70 to 98: 2, and more preferably an integer satisfying 50:50 to 95: 5.

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

  When a group (usually called a polymerization active group) involved in polymerization remains in a group located at the molecular chain terminal of the polymer (that is, a terminal group), the composition is used for a light emitting device. Since there is a possibility that the light emission characteristics and the lifetime may be reduced, it is preferable that the light-emitting characteristics and the lifetime are protected with a stable group not involved in polymerization. As this terminal group, those having a conjugated bond continuous with the conjugated structure of the molecular chain main chain are preferable, for example, a structure bonded to an aryl group or 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 less than 3000, preferably about 100 to 1000, and more preferably about 100 to 500.

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

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

（式中、Ｒは独立に前述と同じ意味を表す。）

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

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

（式中、Ｒは独立に前述と同じ意味を表す。）

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

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

（式中、Ｒは独立に前述と同じ意味を表す。）

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

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

（式中、Ｒは独立に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 independently 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は独立に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。）

(In the formula, R independently 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は独立に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。）

(In the formula, R independently 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は独立に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。）

(In the formula, R independently 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 — represents CH = 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は独立に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 independently represents the same meaning as described above, and is bonded to a metal at the position of *.)

  The other fluorescent metal complex means a metal complex that emits fluorescence at room temperature (that is, 25 ° C.), and usually does not include a metal complex that exhibits phosphorescence. Specific examples of other fluorescent metal complexes include beryllium, magnesium, aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, ruthenium, palladium, silver, cadmium, Examples of the complex include indium and tin. Examples of the ligands 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は独立に前述と同じ意味を表す。）

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

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

（式中、Ｒは独立に前述と同じ意味を表す。）

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

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

（式中、Ｒは独立に前述と同じ意味を表す。）

(In the formula, R independently 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は独立に前述と同じ意味を表し、ｎ_cは１〜２０の整数を表す。）

(Wherein, R is independently the same meanings 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は独立に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 is independently the same meanings as defined above, n _c represents an integer of 1 to 20, X _e is independently, -O -, - S -, - NR- or -CH = CH- Represents.)

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

（式中、Ｒは独立に前述と同じ意味を表す。）

(In the formula, R independently 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は独立に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 independently 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は独立に前述と同じ意味を表す。）

(In the formula, R and Ar _a independently 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は独立に前述と同じ意味を表す。）

(In the formula, R and Ar _b independently 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は独立に前述と同じ意味を表す。）

(In the formula, R independently 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は独立に前述と同じ意味を表す。）

(In the formula, R and Ar _b independently 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は独立に前述と同じ意味を表す。）

(In the formula, R independently 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は独立に前述と同じ意味を表す。）

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

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

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

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

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

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

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

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

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

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

  The film formation method using the liquid composition includes spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen. Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

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

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

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

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

  When two kinds of solvents are contained in the liquid composition, one of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, it is preferable that one type of solvent has a boiling point of 180 ° C. or higher, and the other one type of solvent preferably has a boiling point of 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 determined by the method described in “Solvent Handbook (Kodansha, 1976)”.

<Thin film>
Next, the thin film of the present invention will be described. This thin film is formed 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 further preferably 70% or more from the viewpoint of the brightness of the device, the light emission voltage, and the like. .

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

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

<Use of composition>
Next, the use of the composition 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 backlight of a liquid crystal display). 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. The thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm.

  Examples of the method for forming the light emitting layer include a method of forming a film from a liquid composition. 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.

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

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

Specific examples of the polymer light-emitting device of the present invention include the following structures a) to d).
a) Anode / light emitting layer / cathode b) Anode / hole transport layer / light emitting layer / cathode c) Anode / light emitting layer / electron transport layer / cathode d) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (Here, / indicates that each layer is laminated adjacently. The same shall apply hereinafter.)

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

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

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

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

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

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

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

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

  Examples of the polysilane and derivatives thereof include compounds described in Chemical Review, Vol. 89, page 1359 (1989), GB 2300196 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 and derivatives thereof have almost no hole transporting property in the siloxane skeleton structure, those having the structure of the low molecular weight hole transporting material in the side chain or main chain are preferably used. Particularly, those having a hole transporting aromatic amine in the side chain or main chain are exemplified.

  Although there is no restriction | limiting in the film-forming method of a positive hole transport layer, The method by the film-forming from a mixed solution with a polymer binder is illustrated in the low molecular hole transport material. Examples of the polymer hole transport material include a method of forming a film from a solution (that is, a mixture of a hole transport material and a solvent).

  As 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 and derivatives thereof, anthraquinone and derivatives thereof, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and 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, and more preferably 5 nm to 200 nm.

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

  Further, in order to improve adhesion with the electrode and charge injection from the electrode, the charge injection layer or the insulating layer may be provided adjacent to the electrode, and the adhesion at the interface is improved or mixing is prevented. For this purpose, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.

  The order and number of layers to be laminated, and the thickness of each layer can be appropriately 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 the leakage current between the light emitting pixels for the smaller is more preferably less 10 ^-5 S / cm or more and 10 ² S / cm, more preferably not more than 10 ^-5 S / cm or more and 10 ¹ S / cm. Usually, in order to make the electric conductivity of the conductive polymer 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, the conductive polymer is doped with an appropriate amount of ions.

  The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and the like. Examples of the cation include lithium ion, sodium ion, potassium ion, tetrabutylammonium ion and the like.

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

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

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

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

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

  The polymer light-emitting device of the present invention is usually formed on a substrate. This substrate may be any substrate that does not change when an electrode is formed and an organic layer is formed. Examples of the material 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. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an anode.

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

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

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

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

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

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

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

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

  The planar light emitting element is self-luminous thin and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can also be used as a curved light source or display device.

<Organic transistor (polymer field effect transistor)>
Next, a polymer field effect transistor which is an embodiment of the organic transistor will be described.
The 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 forming method from a liquid composition comprising a solvent containing a polymer soluble in an organic solvent, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method 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.

<Synthesis Example 1>
-Synthesis of Polymer 1-
In a 300 mL four-necked flask connected to a Dimroth, the following formula:

で表される化合物Ａ 2.63ｇ(5.0mmol)、下記式：

2.63 g (5.0 mmol) of the compound A represented by the formula:

で表される化合物Ｂ 3.38g(5.0mmol)、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）0.65g、及びトルエン50mlを加えた。窒素雰囲気下、酢酸パラジウム 1.8mg、及びトリス（２−メトキシフェニル）ホスフィン 13.1mgを加え、85℃に加熱した。このモノマー溶液に、17.5重量％炭酸ナトリウム水溶液 9.8gを滴下しながら105℃に加熱した後、1.5時間攪拌した。次に、トルエン2.5mLに溶解したｔ−ブチルフェニルホウ酸 89mgを加え、105℃で２時間攪拌した。更に、Ｎ，Ｎ−ジエチルチオカルバミド酸ナトリウム三水和物 3.0g、及びイオン交換水 30mLを加え65℃で２時間攪拌した。有機層を水層と分離した後、イオン交換水 約65mLで洗浄した。テトラヒドロフラン 400mLに追加し、メタノールに滴下しポリマーを沈殿させ、沈殿物を濾過後乾燥し、重合体１を4.47g得た。

3.38 g (5.0 mmol) of the compound B represented by the formula, 0.65 g of methyltrioctylammonium chloride (trade name: aliquot 336, manufactured by Aldrich) and 50 ml of toluene were added. Under a nitrogen atmosphere, 1.8 mg of palladium acetate and 13.1 mg of tris (2-methoxyphenyl) phosphine were added and heated to 85 ° C. To this monomer solution, 9.8 g of a 17.5 wt% sodium carbonate aqueous solution was added dropwise and heated to 105 ° C., followed by stirring for 1.5 hours. Next, 89 mg of t-butylphenylboric acid dissolved in 2.5 mL of toluene was added and stirred at 105 ° C. for 2 hours. Further, 3.0 g of sodium N, N-diethylthiocarbamate trihydrate and 30 mL of ion-exchanged water were added and stirred at 65 ° C. for 2 hours. The organic layer was separated from the aqueous layer and then washed with about 65 mL of ion exchange water. The solution was added to 400 mL of tetrahydrofuran and added dropwise to methanol to precipitate a polymer. The precipitate was filtered and dried to obtain 4.47 g of polymer 1.

The polystyrene equivalent number average molecular weight Mn of the polymer 1 was 1.1 × 10 ⁵ , and the polystyrene equivalent weight average molecular weight Mw was 3.1 × 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.

<Example 1>
-Preparation of Composition 1-
Polymer 1 (photoluminescence emission peak: 465 nm) 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”).

<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 a sputtering method. The film was formed to a thickness and dried on a hot plate at 200 ° C. for 10 minutes. Next, composition 1 was dissolved in toluene at a concentration of 1.5% by weight, and the resulting toluene solution was used to form a film having a thickness of about 80 nm by spin coating. Then, after drying for 1 hour at 90 ° C. in a nitrogen atmosphere where the oxygen concentration and water concentration are both 10 ppm or less (weight basis), lithium fluoride is about 4 nm, then calcium is about 5 nm, and finally aluminum is used as the cathode. A polymer light emitting device was fabricated by vapor deposition of about 100 nm. The element configuration is
ITO / Baytron P (about 80 nm) / Composition 1 (about 80 nm) / LiF / Ca / Al
Met. Note that after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.

  When a voltage of 9.0 V was applied to the obtained polymer light emitting device, fluorescence was emitted with a peak top of the fluorescence wavelength of 560 nm. Fluorescence with a fluorescence wavelength peak top of 465 nm was also observed, but when the fluorescence intensity at 560 nm was 1.00, the fluorescence intensity at 465 nm was 0.06. When the voltage was changed, the luminous efficiency was 12.3 V and the maximum value (2.28 cd / A).

<Synthesis Example 2>
-Synthesis of polymer 2-
In a 200 mL three-necked flask connected to a Dimroth, the following formula:

で表される化合物Ｃ 2.30g(3.0mmol)、前記化合物Ｂ 0.81g(1.2mmol)、下記式：

Compound C 2.30 g (3.0 mmol), Compound B 0.81 g (1.2 mmol) represented by the following formula:

で表される化合物Ｄ 0.83g(1.8mmol)、及びトルエン23mlを加えた。窒素雰囲気下、モノマー溶液を加熱し70℃で酢酸パラジウム 1.3mg、トリス（２−メトキシフェニル）ホスフィン 8.5mg、及び20重量％テトラエチルアンモニウムヒドロキシド水溶液 10.2gを注加した。105℃に加熱した後、0.8時間攪拌した。次に、トルエン1.5mLに溶解したｔ−ブチルフェニルホウ酸 267mgを加え、105℃で２時間攪拌した。更に、Ｎ，Ｎ−ジエチルチオカルバミド酸ナトリウム三水和物 0.6g、及びイオン交換水 ９ｍＬを加え65℃で２時間攪拌した。そして、有機層を水層と分離した後、有機層を２Ｍ塩酸 約70mL（１回）、10重量％酢酸ナトリウム水溶液 約70mL（１回）、イオン交換水 約70mL（３回）の順番で洗浄した。有機層をメタノール 約1100mLに滴下し、ポリマーを沈殿させ、沈殿物を濾過後乾燥し、固体を得た。この固体をトルエン 約90mLに溶解させ、あらかじめトルエンを通液したシリカゲルカラム及びアルミナカラムに溶液を通液し、この溶液をメタノール 約1100mLに滴下しポリマーを沈殿させ、沈殿物を濾過後乾燥し、重合体２を2.45g得た。

0.83 g (1.8 mmol) of the compound D represented by the formula (2) and 23 ml of toluene were added. Under a nitrogen atmosphere, the monomer solution was heated, and 1.3 mg of palladium acetate, 8.5 mg of tris (2-methoxyphenyl) phosphine, and 10.2 g of a 20 wt% tetraethylammonium hydroxide aqueous solution were added at 70 ° C. After heating to 105 ° C., the mixture was stirred for 0.8 hours. Next, 267 mg of t-butylphenylboric acid dissolved in 1.5 mL of toluene was added, and the mixture was stirred at 105 ° C. for 2 hours. Further, 0.6 g of sodium N, N-diethylthiocarbamate trihydrate and 9 mL of ion-exchanged water were added and stirred at 65 ° C. for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed in the order of about 70 mL of 2M hydrochloric acid (once), about 70 mL of 10% aqueous sodium acetate solution (once), and about 70 mL of ion-exchanged water (once). did. The organic layer was dropped into about 1100 mL of methanol to precipitate a polymer, and the precipitate was filtered and dried to obtain a solid. This solid is dissolved in about 90 mL of toluene, and the solution is passed through a silica gel column and an alumina column through which toluene has been passed in advance, and this solution is dropped into about 1100 mL of methanol to precipitate a polymer, and the precipitate is filtered and dried. 2.45 g of polymer 2 was obtained.

The polystyrene equivalent number average molecular weight Mn of the polymer 2 was 6.0 × 10 ⁴ , and the polystyrene equivalent weight average molecular weight Mw was 1.4 × 10 ⁵ .

  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.

<Example 3>
-Preparation of composition 2-
Polymer 2 (photoluminescence emission peak: 445 nm) 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 2”).

<Example 4>
-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 a sputtering method. The film was formed to a thickness and dried on a hot plate at 200 ° C. for 10 minutes. Next, the composition 2 was dissolved in toluene at a concentration of 1.8% by weight, and the resulting toluene solution was used to form a film with a thickness of about 80 nm by spin coating. Then, after drying for 1 hour at 90 ° C. in a nitrogen atmosphere where the oxygen concentration and water concentration are both 10 ppm or less (weight basis), lithium fluoride is about 4 nm, then calcium is about 5 nm, and finally aluminum is about about 10 nm. A polymer light emitting device was fabricated by vapor deposition of 100 nm. The element configuration is
ITO / Baytron P (80nm) / Composition 2 (80nm) / LiF / Ca / Al
Met. Note that after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.

  When a voltage of 9.0 V was applied to the obtained device, fluorescence was emitted with a peak top of the fluorescence wavelength of 560 nm. Fluorescence with a fluorescence wavelength peak top of 445 nm was also observed, but when the fluorescence intensity at 560 nm was 1.00, the fluorescence intensity at 445 nm was 0.04. When the voltage was changed, the luminous efficiency was 14.4 V, which was the maximum value (0.95 cd / A).

<Synthesis Example 3>
-Synthesis of Polymer 3-
After 9,63-dioctyl-2,7-dibromofluorene (8.63 g), compound D (3.0 g) and 2,2′-bipyridyl (8.25 g) were charged into a reaction vessel, the reaction system was replaced with nitrogen gas. To this, 750 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, 15.0 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and the mixture was stirred at room temperature for 10 minutes and then reacted at 60 ° C. for 3 hours. The reaction was performed in a nitrogen gas atmosphere.

  After the reaction, this reaction solution was cooled, and a mixed solution of 25% by weight ammonia water 70 ml / methanol 700 ml / ion exchanged water 700 ml was poured into this solution and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution was filtered to remove insoluble matters, and the resulting toluene solution was purified by passing through a column filled with alumina. The toluene solution thus obtained was washed with about 3 wt% aqueous ammonia, allowed to stand and liquid-separated, and then the toluene solution was recovered. Next, this toluene solution was washed with ion-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 3”). The polystyrene equivalent weight average molecular weight Mw of the polymer 3 was 1.4 × 10 ⁵ , and the polystyrene equivalent number average molecular weight Mn was 4.1 × 10 ⁴ .

  From the charge ratio of the starting materials, the polymer 3 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.

<Comparative Example 1>
-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 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 a sputtering method. The film was formed to a thickness and dried on a hot plate at 200 ° C. for 10 minutes. Next, composition 3 was dissolved in toluene at a concentration of 2.0% by weight, and the resulting toluene solution was used to form a film having a thickness of about 80 nm by spin coating. Then, after drying for 1 hour at 90 ° C. in a nitrogen atmosphere where the oxygen concentration and water concentration are both 10 ppm or less (weight basis), lithium fluoride is about 4 nm, then calcium is 5 nm, and finally aluminum is about 10 nm. A polymer light emitting device was fabricated by vapor deposition of 100 nm. The element configuration is
ITO / Baytron P (80nm) / Composition 3 (80nm) / LiF / Ca / Al
Met. Note that after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.

  When a voltage of 9.0 V was applied to the obtained device, fluorescence was emitted with a peak top of the fluorescence wavelength of 560 nm. Fluorescence with a fluorescence wavelength peak top of 455 nm was also observed, but when the fluorescence intensity at 560 nm was 1.00, the fluorescence intensity at 455 nm was 0.48. When the voltage was changed, the luminous efficiency was 11.6 V and the maximum value (0.92 cd / A).

<Synthesis Example 4>
-Synthesis of polymer 4-
Under a nitrogen atmosphere, 1.65 g of 9,9-dioctyl-2,7-dibromofluorene, 1.80 g of the compound A, and 1.21 g of methyltrioctylammonium chloride (trade name: Aliquot 336, manufactured by Aldrich) were used as a reaction vessel. Then, an aqueous potassium carbonate solution prepared by dissolving 1.31 g of potassium carbonate in 56 g of water was added thereto. Further, 6.9 mg of tetrakis (triphenylphosphine) palladium was added and heated to reflux for 10 hours. Thereafter, 61 mg of bromobenzene was added and the mixture was further heated to reflux for 2 hours. After cooling to room temperature, the organic layer was added dropwise to methanol, and the deposited precipitate was filtered off and dried to obtain a polymer (hereinafter, this polymer is referred to as “polymer (4-1)”).
Separately, the same synthesis operation was performed twice to obtain a polymer (4-2) and a polymer (4-3). The polymer (4-1), polymer (4-2) and polymer (4-3) thus obtained are mixed, dissolved in 150 mL of toluene, and this solution is passed through a column packed with silica and alumina. And purified. Thereafter, the obtained purified product (solution) was dropped into 500 mL of methanol, and the deposited precipitate was filtered and dried to obtain 3.82 g of a polymer (hereinafter, this polymer is referred to as “polymer 4”).

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

  From the starting material, the polymer 4 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.

<Comparative Example 3>
-Preparation of composition 4-
Polymer 4 and rubrene were mixed at a weight ratio of 95: 5 to prepare a composition (hereinafter referred to as “Composition 4”).

<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 4 was used instead of the composition 1.

  When a voltage of 6.0 V was applied to the obtained device, the device emitted fluorescence having a peak wavelength of 440 nm.

<Evaluation>
In the devices prepared in Examples 2 and 4, light emission when a voltage was applied was substantially derived from a low molecular fluorescent material. In other words, it is recognized that light was almost selectively obtained from the low-molecular fluorescent material.
On the other hand, the element produced in Comparative Example 2 was a mixture of light emission when a voltage was applied derived from a low molecular phosphor and a polymer. Further, in the device produced in Comparative Example 4, light emission when a voltage was applied was substantially derived from the polymer. In other words, it is not recognized that light is almost selectively obtained from the low-molecular fluorescent material.

Claims (10)

The following formula (1 -3):

[ Wherein , R ² independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituted carboxyl group . ]
A repeating unit represented in,
The following formula (2-A):

(In the formula, R ^C independently represents an alkyl group which may have a substituent.)
Or a repeating unit represented by the following formula (2-B):

(In the formula, R ^D represents an alkyl group which may have a substituent.)
A composition containing a polymer containing a repeating unit represented by : and a low-molecular fluorescent material ,
The molar ratio of the repeating units contained in the polymer is formula (1-3): formula (2-A) = 30: 70 to 98: 2, or formula (1-3): formula (2- B) = 30:70 to 98: 2 composition .   The polymer includes a repeating unit represented by the formula (1-3) and a repeating unit represented by the formula (2-A),
  The composition of Claim 1 whose molar ratio of the repeating unit contained in a polymer is Formula (1-3): Formula (2-A) = 30: 70-98: 2.   The composition of Claim 1 or 2 whose content of the said low molecular fluorescent material is 0.5-10 weight part with respect to 100 weight part of said polymers. The repeating unit represented by the formula (1-3) is represented by the following formula (1-4):

(In the formula, R ^A represents an alkyl group.)
The composition according to any one of claims 1 to 3 , which is a repeating unit represented by: Formula (1 -3) The composition according to any one of claims 1-4 represented further comprising a no polymer repeating unit in. The composition according to any one of claims 1 to 5 , wherein the polymer having a repeating unit represented by the formula (1-3) has a polystyrene-equivalent weight average molecular weight of 3 x 10 ³ to 1 x 10 ^8. object. Furthermore, the liquid composition which consists of a composition as described in any one of Claims 1-6 containing a solvent. A thin film using the composition according to any one of claims 1 to 6 or the liquid composition according to claim 7 . An organic transistor having the thin film according to claim 8 . Electrodes consisting of an anode and a cathode, a polymer light emitting device having an organic layer containing the composition according to any one of claims 1 to 6 disposed between the electrodes.