JP5217361B2 - Polymer compound and polymer light emitting device using the same - Google Patents

Description

  The present invention relates to a polymer compound and a polymer light emitting device using the polymer compound.

A light-emitting element (polymer light-emitting element) having an organic layer containing a polymer compound is known (Non-Patent Document 1).
Then, it is considered to provide an organic layer in addition to the light emitting layer, and a polymer compound composed of a fluorenediyl group and a phenoxazinediyl group or a phenothiazinediyl group has been proposed as a polymer compound used in the organic layer. (See Patent Document 1).
Advanced Materials Vol. 12 1737-1750 (2000) JP 2004-137456 A

  It was found that providing a polymer compound layer composed of the fluorenediyl group and the phenoxazinediyl group between the light emitting layer and the anode improves the life characteristics compared to the case without the layer. But it was not enough.

  Accordingly, an object of the present invention is to provide a polymer compound capable of providing a polymer light-emitting device having excellent lifetime characteristics when used as a material of the light-emitting device, and a polymer light-emitting device using the polymer compound.

〔ここで、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶はそれぞれ置換基を示し、これらは同一であっても異なっていてもよい。ａおよびｄは、それぞれ独立に０〜３の整数を示し、bおよびcは、それぞれ独立に０〜２の整数を示し、eは０〜５の整数を示す。２個のＲ¹は、同一でも異なっていてもよく、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶がそれぞれ複数個存在する場合それらは同一でも異なっていてもよい。Ｘ¹、Ｘ²およびＸ³はそれぞれ独立に酸素原子または硫黄原子を示す。〕 As a result of diligent studies to solve the above problems, the present inventors have found that a polymer compound containing a thienylene group and a benzothiadiazole diyl group in addition to a fluorenediyl group and a phenoxazinediyl group or a phenothiazinediyl group has life characteristics. As a result, the present invention was completed.
That is, the present invention includes a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), a structural unit represented by the following formula (3), and a structural unit represented by the following formula (4). In addition, the present invention provides a polymer compound having a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ .

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a substituent, and these may be the same or different. a and d each independently represent an integer of 0 to 3, b and c each independently represent an integer of 0 to 2, and e represents an integer of 0 to 5. Two R ^{1 s} may be the same or different, and when there are a plurality of R ² , R ³ , R ⁴ , R ⁵ and R ^6, they may be the same or different. X ¹ , X ² and X ³ each independently represent an oxygen atom or a sulfur atom. ]

The polymer compound of the present invention can provide a polymer light emitting device having excellent lifetime characteristics.
Accordingly, a light emitting element using the polymer compound 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 element); It is useful for display devices such as a matrix 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 polymer compound of the present invention is suitable as a material used for the production of these materials, and is also suitable for conducting laser dyes, organic solar cell materials, organic semiconductors for organic transistors, conductive thin films, organic semiconductor thin films, etc. It is also suitable as a material for a conductive thin film, a light emitting thin film material that emits fluorescence, a material for a polymer field effect transistor, and the like.

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

In the formula (1), a independently represents an integer of 0 to 3, and a is preferably 0 or 1, respectively. When a plurality of R ¹ are present, they may be the same or different.

  Here, the alkyl group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. More preferably, it is 4-8. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, s-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 group and the like. From the viewpoint of the solubility of the polymer compound in an organic solvent, device characteristics, ease of synthesis of the polymer compound and heat resistance, pentyl group, isoamyl Group, n-butyl group, t-butyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, 3,7-dimethyloctyl It is preferred.

  The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. More preferably, it is 4-8. Specific examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, Cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy Group, perfluorohexyloxy group, perfluorooctyloxy group, etc., and balance between the heat resistance of the polymer compound in terms of solubility in organic solvents, device characteristics, ease of synthesis of the polymer compound, etc. From pentyloxy, hexyloxy, octyloxy Group, 2-ethylhexyl group, decyloxy group, 3,7-dimethyl octyloxy group are preferable. Moreover, as a substituted alkoxy group, a methoxymethyloxy group, 2-methoxyethyloxy group, etc. are mentioned, for example.

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

  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 through a group such as vinylene. Also included. The aryl group usually has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, pentafluorophenyl group, and the like. And may have a substituent such as an alkyloxycarbonyl group. From the viewpoint of solubility in these organic solvents, device characteristics, easiness of synthesis, etc., an alkyl group having 1 to 12 carbon atoms and / or an alkoxy group having 1 to 12 carbon atoms and / or an alkyloxycarbonyl group is used. A phenyl group having one or more substituents is preferred, and specific examples thereof include 3-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 4-propylphenyl group, mesityl group, 4-i -Propylphenyl group, 4-butylphenyl group, 4-i-butylphenyl group, 4-t-butylphenyl group, 4-pentylphenyl group, 4-isoamylphenyl group, 4-hexylphenyl group, 2,6-dimethyl -4-t-butylphenyl group, 4-heptylphenyl group, 4-octylphenyl group, 4-nonylphenyl group, 4-decylphenyl group, -Dodecylphenyl group, 3-methyloxyphenyl group, 4-methyloxyphenyl group, 3,5-dimethyloxyphenyl group, 4-propyloxyphenyl group, 4-i-propyloxyphenyl group, 4-butyloxyphenyl group 4-i-butyloxyphenyl group, 4-t-butyloxyphenyl group, 4-hexyloxyphenyl group, 3,5-dihexyloxyphenyl group, 4-heptyloxyphenyl group, 4-octyloxyphenyl group, 4 -Nonyloxyphenyl group, 4- (methoxymethoxy) phenyl group, 3- (methoxymethoxy) phenyl group, 4- (2-ethoxy-ethoxy) phenyl group, 3- (2-ethoxy-ethoxy) phenyl group, 3, 5-bis (2-ethoxy-ethoxy) phenyl group, 3-methoxycarbonylphenyl group, 4- Toxicarbonylphenyl group, 3,5-dimethoxycarbonylphenyl group, 3-ethoxycarbonylphenyl group, 4-ethoxycarbonylphenyl group, 3-ethyloxycarbonyl-4-methoxyphenyl group, 3-ethyloxycarbonyl-4-ethoxyphenyl Group, 3-ethyloxycarbonyl-4-hexyloxyphenyl 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 (“C ₁ -C ₁₂ alkoxy” means that the alkoxy moiety has 1 to 12 carbon atoms), a phenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, and a pentafluorophenyl group and the like, solubility, device properties of a polymer compound in an organic solvent, the synthesis of the polymer compound From the standpoint of easiness to perform, C ₁ -C ₁₂ alkoxyphenoxy group, C ₁ -C ₁₂ alkyl (“C ₁ -C ₁₂ alkyl” means that the alkyl moiety has 1 to 12 carbon atoms. Means) Phenoxy groups are preferred. Specific examples of the C ₁ -C ₁₂ alkoxyphenoxy group include a methoxyphenoxy group, an ethoxyphenoxy group, a propyloxyphenoxy group, an i-propyloxyphenoxy group, a butoxyphenoxy group, an i-butoxyphenoxy group, and an s-butoxyphonoxy 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. Specific examples C ₁ -C ₁₂ alkylphenoxy group, methylphenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-methylphenoxy group, methylethylphenoxy group, i- propyl phenoxy group Butylphenoxy group, i-butylphenoxy group, t-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group, dodecylphenoxy group, etc. Illustrated.

The arylthio group usually has about 6 to 60 carbon atoms. Specific examples of the arylthio group include a phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group, pentafluorophenylthio group and the like solubility of a polymer compound in an organic solvent, device properties, from the standpoint of easiness of synthesis of a polymer compound, C ₁ -C ₁₂ alkoxyphenyl-thio group, a C ₁ -C ₁₂ alkyl phenylthio group preferable.

The arylalkyl group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples of the aryl alkyl group, a phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group , 1-naphthyl-C ₁ -C ₁₂ alkyl group, 2-naphthyl-C ₁ -C ₁₂ alkyl group, etc., and the solubility of polymer compounds in organic solvents, device characteristics, and synthesis of polymer compounds from the viewpoint of easiness is, 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 group and the like. From the viewpoint of solubility of the polymer compound in an organic solvent, device characteristics, ease of synthesis of the polymer compound, etc., C ₁ -C ₁₂ alkoxyphenyl- C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy group are preferable.

The arylalkylthio group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples of the arylalkylthio group include a phenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group , 1-naphthyl-C ₁ -C ₁₂ alkylthio group, 2-naphthyl-C ₁ -C ₁₂ alkylthio group, and the like. Solubility of polymer compounds in organic solvents, device characteristics, synthesis of polymer compounds from the viewpoint of easiness is, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, a C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group are 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 compound in an organic solvent, device characteristics, ease of synthesis of the polymer compound, 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 compound in an organic solvent, device characteristics, easiness of synthesis of the polymer compound, 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, s-butylamino group, t-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7 - dimethyloctyl amino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ ~ ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, Pirajiruamino group, a phenyl -C triazyl amino group ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ Alkyl) amino group, 1-naphthyl-C ₁ -C ₁₂ alkylamino group, 2-naphthyl-C ₁ -C ₁₂ alkylamino group and the like.

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

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

  The acyl group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

  The acyloxy group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

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

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

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

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

  As an acid imide group, the residue obtained by remove | excluding one hydrogen atom couple | bonded with the nitrogen atom from acid imide is mentioned, and carbon number is about 4-20. Specific examples of the acid imide group include the groups shown below.

The monovalent heterocyclic group refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound. The carbon number of the monovalent heterocyclic group is usually about 4 to 60, preferably 4 to 20. The carbon number of the monovalent heterocyclic group does not include the carbon number of the substituent. The heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, silicon, etc. Say. Specific examples of the monovalent heterocyclic group, 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, s-butoxycarbonyl group, t-butoxycarbonyl group, pentyl. Oxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group , 2 -ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl Group, dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycar Examples include a bonyl group, a perfluorooctyloxycarbonyl group, a phenoxycarbonyl group, a naphthoxycarbonyl group, and a pyridyloxycarbonyl group.

In the formula (2), examples of the substituent represented by R ³ 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, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group are considered from the viewpoints of solubility of the polymer compound in an organic solvent and ease of synthesis of the polymer compound. Group, arylalkyl group, arylalkoxy group, and monovalent heterocyclic group are preferable, and alkyl group, alkoxy group, aryl group, and monovalent heterocyclic group are more preferable. These groups are specifically the same as those described and exemplified as the substituent represented by R ¹ .

In the formula (2), b represents an integer of 0 to 2, and b is preferably 0 or 1. More preferably 0. When a plurality of R ³ are present, they may be the same or different.

In Formula (2), X ¹ represents an oxygen atom or a sulfur atom, and is preferably a sulfur atom from the viewpoint of device characteristics.

In the formula (3), examples of the substituent represented by R ⁴ include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, 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, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group are considered from the viewpoints of solubility of the polymer compound in an organic solvent and ease of synthesis of the polymer compound. Group, arylalkyl group, arylalkoxy group, and monovalent heterocyclic group are preferable, and alkyl group, alkoxy group, aryl group, and monovalent heterocyclic group are more preferable. These groups are specifically the same as those described and exemplified as the substituent represented by R ¹ .

In the formula (3), c represents an integer of 0 to 2, and c is preferably 0. When a plurality of R ⁴ are present, they may be the same or different.

In the formula (3), X ² represents an oxygen atom or a sulfur atom, and is preferably a sulfur atom from the viewpoint of device characteristics.

In the formula (4), examples of the substituent represented by R ⁵ and R ⁶ 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, and an arylalkylthio group. Group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group , Carboxyl group, substituted carboxyl group, nitro group, cyano group and the like. A hydrogen atom contained in these substituents may be substituted with a fluorine atom. Among these substituents, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group are considered from the viewpoints of solubility of the polymer compound in an organic solvent and ease of synthesis of the polymer compound. Group, arylalkyl group, arylalkoxy group, and monovalent heterocyclic group are preferable, and alkyl group, alkoxy group, aryl group, and monovalent heterocyclic group are more preferable. These groups are specifically the same as those described and exemplified as the substituent represented by R ¹ .

In the formula (4), d independently represents an integer of 0 to 3, and d is preferably 0 or 1, and more preferably 0. When a plurality of R ⁵ are present, they may be the same or different.

In the formula (4), e represents an integer of 0 to 5, but e is preferably 0 to 3, and more preferably 1. When a plurality of R ⁶ are present, they may be the same or different.

In Formula (4), X ³ represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom from the viewpoint of device characteristics.

  As the structural unit represented by the above formula (4), the following formula (4-1):

で示されることが好ましい。

It is preferable that it is shown by.

  The ratio (M1 / M) of the number of moles (M1) of the structural unit represented by the above formula (1) to the total number (M) of moles of all the structural units possessed by the polymer compound of the present invention is x, The ratio (M2 / M) of the total number of moles (M2) of the structural units represented by the above formula (2) with respect to the total number of moles is represented by y and the above formula (3) with respect to the total number of moles of all structural units. The ratio (M3 / M) of the total number of moles (M3) of the structural units is z, and the ratio of the total number of moles (M4) of the structural units represented by the above formula (4) to the total number of moles of all the structural units ( When M4 / M) is w, it is preferably 0.01 ≦ x + y + z + w ≦ 1, more preferably 0.1 ≦ x + y + z + w ≦ 1, and 0.5 ≦ x + y + z + w ≦ from the viewpoint of life characteristics. 1 is more preferable, and 0.9 ≦ x + y + z + w ≦ 1 There it is more preferable.

  Further, the number of moles of the structural unit represented by the formula (1), the number of moles of the structural unit represented by the formula (2), the number of moles of the structural unit represented by the formula (3), and the structural unit represented by the formula (4) (X + w) / (x + y + z + w), which is the ratio of the sum of the number of moles of the structural unit represented by formula (1) and the number of moles of the structural unit represented by formula (4) to the total amount of moles of .Ltoreq. (X + w) / (x + y + z + w) .ltoreq.0.99, more preferably 0.3.ltoreq. (X + w) / (x + y + z + w) .ltoreq.0.99, more preferably from the viewpoint of life characteristics. 3 ≦ (x + w) / (x + y + z + w) ≦ 0.99, and particularly preferably 0.5 ≦ (x + w) / (x + y + z + w) ≦ 0.99.

  Furthermore, the number of moles of the structural unit represented by the formula (1), the number of moles of the structural unit represented by the formula (2), the number of moles of the structural unit represented by the formula (3), and the formula (4) W / (x + y + z + w), which is the ratio of the sum of the number of moles of the structural unit to the number of moles of the structural unit represented by the formula (4), is 0.01 ≦ w / (x + y + z + w) ≦ 0.99. preferable.

  When the polymer compound of the present invention is used for the hole transport layer, the structural unit represented by the formula (4) has a hole transport ability, and therefore more preferably 0.15 ≦ w / (x + y + z + w) ≦ 0.99. It is preferable that

  From the viewpoint of life characteristics, 0.3 ≦ x / (x + y + z + w) ≦ 0.82, 0.02 ≦ y / (x + y + z + w) ≦ 0.4, 0.01 ≦ z / (x + y + z + w) ≦ 0.2 and 0. It is preferable to satisfy all 15 ≦ w / (x + y + z + w) ≦ 0.67, and from the viewpoint of ease of synthesis, 0.3 ≦ x / (x + y + z + w) ≦ 0.7, 0.02 ≦ y / (x + y + z + w) More preferably, all of ≦ 0.4, 0.01 ≦ z / (x + y + z + w) ≦ 0.2 and 0.15 ≦ w / (x + y + z + w) ≦ 0.5 are satisfied.

The polymer compound of the present invention is represented by the structural unit represented by the formula (1), the structural unit represented by the formula (2), and the formula (3) as long as the light emission characteristics and the charge transport characteristics are not impaired. A structural unit other than the structural unit and the repetition represented by the formula (4) may be included.

  The structural units in the polymer compound may be linked with a 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、水素原子又は置換基を表し、置換基としては、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、ニトロ基、シアノ基があげられる。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 independently represents a hydrogen atom or a substituent, and examples of the substituent 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, and 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, and cyano group, 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 compound may be any of a random copolymer, a graft copolymer, an alternating copolymer, and a block copolymer. Further, a polymer having an intermediate structure thereof, for example, a random copolymer having a block property may be used. Furthermore, the case where there are branches in the main chain and there are 3 or more terminal portions and dendrimers are also included.

The number average molecular weight in terms of polystyrene of the polymer compound is usually about 1 × 10 ³ to 1 × 10 ⁸ , and 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 compound in an organic solvent, it is preferably 1 × 10 ^{5 to} 5 × 10 ⁶ . Whether a single polymer compound having a number average molecular weight and a weight average molecular weight in the range is used alone or in combination with two or more of the polymer compounds, the resulting device is highly luminescent. Efficiency. Further, from the viewpoint of improving the film formability of the polymer compound 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.

The polymer compound may be any of a random copolymer, a graft copolymer, an alternating copolymer, and a block copolymer. Further, a polymer having an intermediate structure thereof, for example, a random copolymer having a block property may be used. Furthermore, the case where there are branches in the main chain and there are 3 or more terminal portions and dendrimers are also included.

  When a group involved in polymerization (usually called a polymerization active group) remains in a group located at the molecular chain end of the polymer compound (that is, a terminal group), the composition is used in a light emitting device. Therefore, it is preferable to be protected with a stable group that does not participate in the 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 compound, 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 characteristic, the effect of increasing the compatibility and interaction between the polymer compounds, the anchor effect Etc.

また、Ｒ³およびＲ⁴はそれぞれ置換基を示し、これらは同一であっても異なっていてもよい。ｂおよびｃは、それぞれ独立に０〜２の整数を示す。Ｒ³およびＲ⁴がそれぞれ複数個存在する場合、それらは同一でも異なっていてもよい。Ｘ¹およびＸ²はそれぞれ独立に酸素原子または硫黄原子を示す。具体的には、それぞれ前記に説明し、例示したものと同じである。
From the viewpoint of device characteristics, it is preferable that the polymer compound has a controlled sequence rather than the formulas (1), (2), (3) and (4) being arranged completely at random. Specifically, it can be mentioned that the formula (2) is bonded (arranged) to both ends of the formula (3), that is, has a structure represented by the following formula (5).

R ³ and R ⁴ each represent a substituent, and these may be the same or different. b and c each independently represent an integer of 0 to 2. When a plurality of R ³ and R ⁴ are present, they may be the same or different. X ¹ and X ² each independently represent an oxygen atom or a sulfur atom. Specifically, they are the same as those described and exemplified above.

ｐ ： ｑ ： ｒ

ここに、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶はそれぞれ置換基を示し、これらは同一であっても異なっていてもよい。ａおよびｄは、それぞれ独立に０〜３の整数を示し、ｂおよびｃは、それぞれ独立に０〜２の整数を示し、ｅは０〜５の整数を示す。２個のＲ¹は、同一でも異なっていてもよく、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶がそれぞれ複数個存在する場合それらは同一でも異なっていてもよい。Ｘ¹、Ｘ²およびＸ³はそれぞれ独立に酸素原子または硫黄原子を示す。具体的には、それぞれ前記に説明し、例示したものと同じである。 The polymer compound of the present invention is represented by the following formula (6) containing the structural unit of the formula (1), the structure of the formula (5), and the structural unit of the formula (4) in a ratio of p: q: r. Examples thereof include high molecular compounds.
In addition, p, q, and r are ratios of the number of moles of Formula (1), Formula (5), and Formula (4) with respect to the total number of moles of Formula (1), Formula (5), and Formula (4), respectively. The above x, y, z and w satisfy the relationships of the following formulas (11) to (14).
x / (x + y + z + w) = p / (p + 3q + r) Formula (11)
y / (x + y + z + w) = 2q / (p + 3q + r) Formula (12)
z / (x + y + z + w) = q / (p + 3q + r) Formula (13)
w / (x + y + z + w) = r / (p + 3q + r) Formula (14)

p: q: r

Here, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a substituent, and these may be the same or different. a and d each independently represent an integer of 0 to 3, b and c each independently represent an integer of 0 to 2, and e represents an integer of 0 to 5. Two R ^{1 s} may be the same or different, and when there are a plurality of R ² , R ³ , R ⁴ , R ⁵ and R ^6, they may be the same or different. X ¹ , X ² and X ³ each independently represent an oxygen atom or a sulfur atom. Specifically, they are the same as those described and exemplified above.

のように、式（１）の構成単位と式（４）の構成単位とが結合してなる２価の基（ｂ）、式（１）の構成単位と式（5）の構造とが結合してなる２価の基（ｃ）が、ランダムに重合していることがさらに好ましい。
The polymer compound represented by the formula (6) may be a random polymer or a block polymer having the formula (1), the formula (5), and the formula (4). :

As shown, the divalent group (b) formed by combining the structural unit of the formula (1) and the structural unit of the formula (4), and the structural unit of the formula (1) and the structure of the formula (5) are combined. More preferably, the divalent group (c) thus formed is polymerized randomly.

  The ends of the polymer compounds (6) and (7) may be bonded to an aromatic terminal group, and are preferably bonded to a phenyl group from the viewpoint of ease of polymerization.

Examples of the method for producing the polymer compound include polymerization by Suzuki reaction (Chemical Review (Chem. Rev.), Vol. 95, page 2457 (1995)), polymerization by Grignard reaction (Kyoritsu Shuppan, Polymer Functional Materials Series Volume 2, Polymer Synthesis and Reaction (2), pp. 432-433), Polymerization by Yamamoto Polymerization Method (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), etc. .

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

In addition, from the viewpoint of improving film-forming properties and device characteristics when formed using the polymer compound of the present invention, the polymer compound of the present invention and other low-molecular organic compounds and / or polymer compounds are used. It may be used as a mixed polymer composition.
The polymer composition contains at least one polymer compound of the present invention, and may contain a hole transport material, an electron transport material and a light emitting material, a stabilizer, an antioxidant, and the like. Each of these optional components may be used alone or in combination of two or more.
The low molecular organic compound and the high molecular compound to be combined are not particularly limited, but those having a hole injection / transport property (hole transport material) and an electron injection / transport property (electron transport material) are preferably used.

Specifically, examples of the hole transport material that the polymer composition may contain include, for example, triphenylamine, tetraphenyldiamine, biscarbazolylbiphenyl, and derivatives thereof as low molecular organic compounds. Examples of the polymer compound include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, and 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, and the like.

Examples of the electron transport material include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, Examples include 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.

The content ratio of the material may be determined according to the use, but when the polymer composition 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.

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

  The polymer compound of the present invention is particularly useful for a light emitting device such as a polymer light emitting device as a liquid composition. The liquid composition of the present invention contains the polymer compound of the present invention and a solvent. 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 99.9% 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.

  As the solvent contained in the liquid composition, those capable of dissolving or dispersing components other than the solvent in the liquid 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 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 compound contained in the polymer composition of the present invention is 10 or less. It is preferable that it is 7 or less. These solubility parameters can be determined by the method described in “Solvent Handbook (Kodansha, 1976)”.

Furthermore, the liquid composition of the present invention may contain an additive and an antioxidant for adjusting the viscosity and / or surface tension.

  As an additive for adjusting the viscosity and / or surface tension which the liquid composition of the present invention may contain, for example, a high molecular weight compound (thickener) for increasing the viscosity, a poor solvent, a viscosity A low molecular weight compound for lowering, a surfactant for lowering surface tension, and the like 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, and is usually soluble in the solvent contained in the liquid composition. As the high molecular weight compound, for example, high molecular weight polystyrene, high molecular weight polymethyl methacrylate, or the like can be used. The high molecular weight compound has a polystyrene-equivalent weight average molecular weight of preferably 500,000 or more, more preferably 1,000,000 or more. A poor solvent can also be used as a thickener. That is, the viscosity of the composition can be increased by adding a small amount of a poor solvent to the solid content in the liquid composition. 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 liquid 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 liquid composition of the present invention is not particularly limited as long as it does not inhibit light emission or charge transport. Examples of the antioxidant include phenolic antioxidants and phosphorus antioxidants. By using an antioxidant, the storage stability of the liquid composition of the present invention can be improved.

Next, the thin film of the present invention will be described.
This thin film can be produced using the polymer compound.
Preferably, a layer containing the polymer compound is prepared, and the layer is usually heated to 50 ° C. or higher, and more preferably manufactured at a heating temperature of 50 ° C. or higher and 300 ° C. or lower. More preferably, it is manufactured at 50 ° C. or higher and 200 ° C. or lower.
If the heating temperature is too low, curing tends to be insufficient, and if it is too high, the device characteristics tend to deteriorate when the thin film is used in an electroluminescence device. The heating time is usually about 15 minutes to 1 hour, and examples of the heating method include a method of heating using an oven or a hot plate.
Heating can be performed in an inert gas atmosphere or in a vacuum, and preferably in a nitrogen atmosphere.
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. .

Next, the use of the polymer compound of the present invention will be described.
The polymer compound of the present invention usually emits fluorescence in a solid state and can be used as a polymer light emitter (that is, a light emitting material having a high molecular weight). Moreover, the polymer compound of the present invention has an excellent charge transporting 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 compound is a high-performance polymer light-emitting device that can be driven at a low voltage and a high luminous efficiency. Accordingly, the polymer compound of the present invention comprises 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 element), a dot matrix display device (for example, It is useful as a material for a display device such as 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).

で示される繰り返し単位を含む高分子化合物等が挙げられる。 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 polymer compound of the present invention. The organic layer may be any of a light emitting layer, a hole transport layer, an electron transport layer, and the like.
From the viewpoint of device characteristics such as lifetime, luminance or luminous efficiency, the organic layer is preferably a hole transport layer, and in this case, the light emitting layer contains a compound that emits light in a red region (600 nm to 800 nm). More preferably.
As the compound that emits light in the red region (region where the peak top of the emission spectrum is 600 nm to 800 nm), known compounds can be used. The compound may be a low molecular compound or a high molecular compound, but is preferably a high molecular compound. For example, the following formulas (f), (g) and (h):

And a polymer compound containing a repeating unit represented by the formula:

In the formulas (f), (g) and (h), R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each represent a substituent, which may be the same or different. Good. f shows the integer of 0-3, g shows the integer of 0-3, h shows the integer of 0-5, i and j show the integer of 0-2 each independently. Two R ^{8 s} may be the same or different, and when there are a plurality of R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ and R ^12, they may be the same or different. X ⁴ and X ⁵ each independently represent an oxygen atom or a sulfur atom, preferably a sulfur atom.

In the above formulas (f), (g) and (h), examples of the substituent represented by R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² include an alkyl group, an alkoxy group, an alkylthio group, Aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, Examples include 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, and a cyano group. A hydrogen atom contained in these substituents may be substituted with a fluorine atom. Among these substituents, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group are considered from the viewpoints of solubility of the polymer compound in an organic solvent and ease of synthesis of the polymer compound. Group, arylalkyl group, arylalkoxy group, and monovalent heterocyclic group are preferable, and alkyl group, alkoxy group, aryl group, and monovalent heterocyclic group are more preferable. These groups are specifically the same as those described and exemplified as the substituent represented by R ¹ .

  In the formulas (f), (g), and (h), f represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0. Although g shows the integer of 0-4, Preferably it is 0 or 1, More preferably, it is 0. h represents an integer of 0 to 5, preferably 1 to 3, and more preferably 1. i represents an integer of 0 to 2, and is preferably 0. j represents an integer of 0 to 2, and is preferably 0 or 1.

The polymer compound may contain a repeating unit other than (f), (g) and (h). The polymer compound may be any of a random copolymer, a graft copolymer, an alternating copolymer, and a block copolymer. Further, a polymer having an intermediate structure thereof, for example, a random copolymer having a block property may be used. Furthermore, the case where there are branches in the main chain and there are 3 or more terminal portions and dendrimers are also included.

  When the molar ratios of the formulas (f), (g) and (h) to the total number of moles of all repeating units of the polymer compound are f1, g1, and h1, respectively, 0.01 ≦ f1 + g1 + h1 ≦ 1 It is preferable that 0.1 ≦ f 1 + g 1 + h 1 ≦ 1.

  The molar ratios f1, g1, and h1 of the formulas (f), (g), and (h) with respect to the total number of moles of all repeating units of the polymer compound are 0.01 ≦ f1 ≦ 0.99, respectively. 0.01 ≦ g1 ≦ 0.99 and 0.01 ≦ h1 ≦ 0.99 are preferable.

Moreover, when using the high molecular compound of this invention for a positive hole transport layer, it is preferable that this positive hole transport layer is in contact with the light emitting layer from a viewpoint of an element characteristic improvement.
Moreover, it is preferable that a light emitting layer contains the high molecular compound which has at least 1 of the structural unit contained in the high molecular compound of this invention, and the structural unit shown by said Formula (1), said Formula (2) It is more preferable to contain a polymer compound containing the structural unit shown and the structural unit represented by the formula (3).

In addition, the polymer compound used for the light emitting layer includes a constituent unit represented by the formula (1), a constituent unit represented by the formula (2), and a constituent unit represented by the formula (3). Also good.

  The light emitting layer refers to a layer having a function of emitting light. The hole transport layer is a layer having a function of transporting holes provided between the anode and the light emitting layer. An electron carrying layer means the layer which has the function to convey the electron provided between the cathode and the light emitting layer. 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.

  A method for forming the light emitting layer is not limited, and examples thereof include a method by film formation 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.

  A material used for the light-emitting layer refers to a light-emitting material that exhibits fluorescence and phosphorescence. As the light emitting material, known materials can be used. In the low molecular weight compound, for example, a metal having a metal complex of naphthalene derivative, anthracene, anthracene derivative, perylene, perylene derivative, polymethine dye, xanthene dye, coumarin dye, cyanine dye, 8-hydroxyquinoline as a ligand. Complexes, metal complexes having 8-hydroxyquinoline derivatives as ligands, other fluorescent metal complexes, aromatic amines, tetraphenylcyclopentadiene, tetraphenylcyclopentadiene derivatives, tetraphenylcyclobutadiene, tetraphenylcyclobutadiene derivatives, stilbene Type, silicon-containing aromatic series, oxazole series, furoxan series, thiazole series, tetraarylmethane series, thiadiazole series, pyrazole series, metacyclophane series, acetylene series and the like. Specific examples include those described in JP-A-57-51781, JP-A-59-194393, and the like. Examples of the polymer compound generally include conjugated polymers, such as a phenylene vinylene copolymer and a fluorene copolymer. Specifically, Applied Physics Letters 58, 1982 (1991). , Special Table 2002-536492, Special Table 2005-515264, etc. are mentioned. Examples of the phosphorescent compound include metal complexes in which the central metal is a transition metal or a lanthanoid. Specifically, for example, Nature, (1998), 395, 151, Appl. Phys. Lett. (1999), 75 (1), 4, Proc. SPIE-Int. Soc. Opt. Eng. (2001), 4105 (Organic Light-Emitting Materials and Devices IV), 119, J. Am. Chem. Soc., (2001), 123, 4304, Appl. Phys. Lett., (1997), 71 (18), 2596, Syn. Met., (1998), 94 (1), 103, Syn. Met., (1999), 99 (2 ), 1361, Adv. Mater., (1999), 11 (10), 852, Jpn.J.Appl.Phys., 34, 1883 (1995), WO0141512, WO03033617, 04-2 2004), WO2005113704, WO2006014599 and the like are exemplified.

  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 polymer light-emitting device of the present invention has a hole transport layer, the polymer compound of the present invention can be used for the hole transport layer. In addition, a hole transporting material (a low molecular weight or high molecular weight material) can also be 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 polymer composition described above.

  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, the polymer compound of the present invention can be used for the hole transport layer. In addition, an electron transport material (including low molecular weight and high molecular weight materials) can also be 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 polymer composition described above.

  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 polymer compound 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 polymer compound of the present invention is contained in a hole injection layer and / or an electron injection layer.

  When the polymer compound or polymer composition of the present invention is used for a hole injection layer, it is preferably used simultaneously with an electron accepting compound. When the polymer compound or polymer composition of the present invention is used in 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.

  Specifically, in the method for producing a polymer compound of the present invention, a compound having a plurality of substituents involved in polymerization, which is a monomer, is dissolved in an organic solvent as necessary, for example, using an alkali or a suitable catalyst. The organic solvent can be used at a melting point or higher and a boiling point or lower. For example, “Organic Reactions”, Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965, “Organic Synthesis”, Collective Vol. (Collective Volume VI), 407-411, John Wiley & Sons, Inc., 1988, Chemical Review (Chem. Rev.), 95, 2457 (1995), Journal of Organometallic. Chemistry (J. Organomet. Chem.), 576, 147 (1999), Macromolecular Chemistry Mac Molecular Symposium (Makromol., Macromol.Symp.), Vol. 12, page 229 (1987) may be a known method described, for example.

  In the method for producing the polymer compound of the present invention, the polymerization can be carried out by using a known condensation reaction depending on the substituent that can participate in the polymerization.

  A copolymer can be produced by carrying out the polymerization in the presence of a compound having two or more substituents that can participate in the polymerization. A polymer compound having a branched structure can be produced by copolymerizing a compound having three or more substituents that can participate in polymerization.

When the polymer compound of the present invention forms a double bond in polymerization, for example, the method described in JP-A-5-202355 can be mentioned. That is, polymerization by Wittig reaction of a compound having a formyl group and a compound having a phosphonium methyl group, or a compound having a formyl group and a phosphonium methyl group, by Heck reaction between a compound having a vinyl group and a compound having a halogen atom. Polymerization, polycondensation of compounds having two or more monohalogenated methyl groups by dehydrohalogenation method, polycondensation of compounds having two or more sulfonium methyl groups by decomposing sulfonium salt, having a formyl group Examples include a method such as polymerization by a Knoevenagel reaction between a compound and a compound having a cyano group, and a method such as polymerization by a McMurry reaction of a compound having two or more formyl groups.
When the polymer compound of the present invention forms a triple bond in the main chain by condensation polymerization, for example, Heck reaction and Sonogashira reaction can be used.

Further, when a double bond or triple bond is not generated, for example, a method of polymerizing from a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a Ni (0) complex, FeCl ₃ or the like Examples thereof include a method of polymerizing with an oxidizing agent, a method of electrochemically oxidatively polymerizing, a method of decomposing an intermediate polymer having an appropriate leaving group, and the like.

  Among these, polymerization by Wittig reaction, polymerization by Heck reaction, polymerization by Knoevenagel reaction, polymerization method by Suzuki coupling reaction, polymerization method by Grignard reaction, and polymerization method by nickel zero-valent complex control the molecular weight. From the viewpoint of ease and ease of control of the composition ratio in the case of copolymerization, it is preferable.

Among them, a production method in which substituents that can participate in polymerization are each independently selected from a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an aryl alkyl sulfonate group, and condensation polymerization is performed in the presence of a nickel zero-valent complex or a palladium catalyst is preferable.
As raw material compounds, dihalogenated compounds, bis (alkyl sulfonate) compounds, bis (aryl sulfonate) compounds, bis (aryl alkyl sulfonate) compounds or halogen-alkyl sulfonate compounds, halogen-aryl sulfonate compounds, halogen-aryl alkyl sulfonate compounds, Examples include alkyl sulfonate-aryl sulfonate compounds, alkyl sulfonate-aryl alkyl sulfonate compounds, and aryl sulfonate-aryl alkyl sulfonate compounds.

  In this case, for example, a halogen-alkyl sulfonate compound, a halogen-aryl sulfonate compound, a halogen-aryl alkyl sulfonate compound, an alkyl sulfonate-aryl sulfonate compound, an alkyl sulfonate-aryl alkyl sulfonate compound, or an aryl sulfonate-aryl alkyl sulfonate compound is used as a raw material compound. Thus, a method for producing a polymer compound in which the direction and sequence of repeating units are controlled can be mentioned.

Further, the substituents that can participate in the polymerization are each independently selected from a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an arylalkyl sulfonate group, —B (OH) ₂ , or a borate group, and all the raw material compounds have. The ratio of the total number of moles of halogen atoms, alkyl sulfonate groups, aryl sulfonate groups and arylalkyl sulfonate groups (J) to the total number of moles of —B (OH) ₂ and borate groups (K) is substantially 1 (usually K / J is in the range of 0.7 to 1.2), and a production method in which condensation polymerization is performed using a nickel catalyst or a palladium catalyst is preferable.
Specific combinations of raw material compounds include a combination of a dihalogenated compound, a bis (alkyl sulfonate) compound, a bis (aryl sulfonate) compound or a bis (aryl alkyl sulfonate) compound and a diboric acid compound or a diboric acid ester compound. .
Also, halogen-boric acid compounds, halogen-boric acid ester compounds, alkyl sulfonate-boric acid compounds, alkyl sulfonate-boric acid ester compounds, aryl sulfonate-boric acid compounds, aryl sulfonate-boric acid ester compounds, arylalkyl sulfonate-borates Examples include acid compounds, arylalkyl sulfonate-boric acid compounds, and arylalkyl sulfonate-boric acid ester compounds.

  In this case, for example, as a raw material compound, a halogen-boric acid compound, a halogen-boric acid ester compound, an alkyl sulfonate-boric acid compound, an alkyl sulfonate-boric acid ester compound, an aryl sulfonate-boric acid compound, an aryl sulfonate-boric acid ester compound, A method of producing a polymer compound in which the direction and sequence of the repeating unit are controlled by using an arylalkyl sulfonate-boric acid compound, an arylalkyl sulfonate-boric acid compound, and an arylalkyl sulfonate-boric acid ester compound can be mentioned.

  The organic solvent varies depending on the compound and reaction to be used, but it is generally preferable that the solvent to be used is sufficiently deoxygenated and the reaction proceeds in an inert atmosphere in order to suppress side reactions. Similarly, it is preferable to perform a dehydration treatment. However, this is not the case in the case of a two-phase reaction with water, such as the Suzuki coupling reaction.

  The solvent varies depending on the compound and reaction used, but saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, carbon tetrachloride, chloroform, dichloromethane and chlorobutane. , Halogenated saturated hydrocarbons such as bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, methanol, ethanol, propanol, Alcohols such as isopropanol, butanol and t-butyl alcohol, carboxylic acids such as formic acid, acetic acid and propionic acid, dimethyl ether and diethyl ether Ethers such as methyl-t-butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, trimethylamine, triethylamine, amines such as N, N, N ′, N′-tetramethylethylenediamine, pyridine, N, N-dimethylformamide, N, Examples include amides such as N-dimethylacetamide, N, N-diethylacetamide, and N-methylmorpholine oxide, and a single solvent or a mixed solvent thereof may be used.

  In order to make it react, an alkali and a suitable catalyst are added suitably. These may be selected according to the reaction used. The alkali or catalyst is preferably one that is sufficiently dissolved in the solvent used in the reaction. As a method of mixing the alkali or catalyst, slowly add the alkali or catalyst solution while stirring the reaction solution under an inert atmosphere such as argon or nitrogen, or conversely, slowly add the reaction solution to the alkali or catalyst solution. And the method of adding.

  When the polymer compound of the present invention is used for a polymer LED or the like, its purity affects the performance of the device such as light emission characteristics. Therefore, after the monomer before polymerization is purified by a method such as distillation, sublimation purification, recrystallization, It is preferable to polymerize. Further, after the polymerization, it is preferable to carry out a purification treatment such as reprecipitation purification and fractionation by chromatography.

  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 Compound 2 Under an inert atmosphere, 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dihexylfluorene (1.91 g), 2,7 -Dibromo-9,9-dihexylfluorene (0.79 g), bis (4-bromophenyl)-(4-secondarybutylphenyl) -amine (0.092 g), 4,7-dibromo-2,1,3- Benzothiadiazole (0.35 g), 4,7-bis (5-bromo-4-methyl-2-thienyl) -2,1,3-benzothiadiazole (0.49 g), bis (triphenylphosphine) palladium dichloride ( 8.4 mg), Aliquat 336 (0.52 g), and toluene (40 ml) were mixed and heated to 105 ° C. To this reaction solution, a 2M Na ₂ CO ₃ aqueous solution (11 ml) was added dropwise and refluxed for 4 hours. After the reaction, phenylboric acid (50 mg) was added, and the mixture was further refluxed for 3 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 80 ° C. for 4 hours. After cooling, the mixture was washed 3 times with water (50 ml), 3 times with 3% aqueous acetic acid (50 ml) and 3 times with water (50 ml), and purified by passing through an alumina column and a silica gel column. The obtained toluene solution was added dropwise to methanol (3 L) and stirred for 3 hours, and then the obtained solid was collected by filtration and dried. The yield of the obtained polymer compound 2 was 2.1 g.
The polymer compound 2 had a polystyrene-equivalent number average molecular weight of 7.5 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 1.8 × 10 ⁵ .
In addition, 4,7-dibromo-2,1,3-benzothiadiazole was synthesized by the method described in US Pat. No. 3,577,427, and 4,7-bis (5-bromo-4-methyl-2-thienyl) -2,1, 3-Benzothiadiazole was synthesized by the method described in WO2000046321, and bis (4-bromophenyl)-(4-secondarybutylphenyl) -amine was synthesized by the method described in WO2002045184.

＝ ７０ ：１２．５ ：２．５ ：１５
From the charging ratio of the starting materials, the polymer compound 2 is required to have repeating units represented by the following formula in the proportions shown below.

= 70: 12.5: 2.5: 15

Synthesis Example 2 Synthesis of Polymer Compound 3 Under an inert atmosphere, 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (4.26 g), 3,7 -Dibromo-N- (4-n-butylphenyl) phenoxazine (3.60 g), 4,7-dibromo-2,1,3-benzothiazole (0.12 g), palladium acetate (5.4 mg), tris (3-Methoxyphenyl) phosphine (33.8 mg), Aliquat 336 (1.30 g, manufactured by Aldrich) and toluene (61 ml) were mixed and heated to 105 ° C. To this reaction solution, 2M Na ₂ CO ₃ aqueous solution (19 ml) was added dropwise and refluxed for 2 hours. After the reaction, phenylboric acid (0.15 g) was added, and the mixture was further refluxed for 2 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the mixture was washed 3 times with water (100 ml), 3 times with 3% aqueous acetic acid (100 ml) and 3 times with water (100 ml), and purified by passing through an alumina column and a silica gel column. The obtained toluene solution was added dropwise to methanol (1600 ml) and stirred for 1 hour, and then the obtained solid was collected by filtration and dried. The yield of the obtained polymer compound 3 was 4.19 g.
The polymer compound 3 had a polystyrene equivalent number average molecular weight of 9.9 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 1.1 × 10 ⁵ .
In addition, 4,7-dibromo-2,1,3-benzothiadiazole was synthesized by the method described in US Pat. No. 3,577,427.
3,7-Dibromo-N- (4-n-butylphenyl) phenoxazine was synthesized by the method described in JP2004137456.

＝ ５０ ：４７．５ ：２．５
From the charge ratio of the starting materials, the polymer compound 3 is required to have a structural unit represented by the following formula at a ratio shown below.

= 50: 47.5: 2.5

<Synthesis Example 3> Synthesis of polymer compound 4 Under an inert atmosphere, 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (7.54 g), 3,7 -Dibromo-N- (4-N-butylphenyl) -phenoxazine (6.54 g), palladium acetate (3.4 mg), tri (2-methylphenyl) phosphine (46.7 mg), Aliquat 336 (2.2 g) , Toluene (106 ml) was mixed and heated to 105 ° C. To this reaction solution, 2M Na ₂ CO ₃ aqueous solution (33 ml) was added dropwise and refluxed for 3 hours. After the reaction, phenylboric acid (202 mg) was added, and the mixture was further refluxed for 3 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 80 ° C. for 4 hours. After cooling, the mixture was washed 3 times with water (200 ml), 3 times with 3% aqueous acetic acid (200 ml) and 3 times with water (200 ml), and purified by passing through an alumina column and silica gel column. The obtained toluene solution was added dropwise to methanol (3 L) and stirred for 3 hours, and then the obtained solid was collected by filtration and dried. The yield of the obtained polymer compound 4 was 8.3 g.
The polymer compound had a polystyrene equivalent number average molecular weight of 2.7 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 5.5 × 10 ⁴ .

＝５０ ： ５０

From the charge ratio of the starting materials, the polymer compound 4 is required to have the structural units represented by the following formula in the proportions shown below.

= 50: 50

<Example 1>
[Synthesis of Polymer Compound 1]
Under an inert atmosphere, 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (7.57 g), 3,7-dibromo-N- (4-n-butyl) Phenyl) phenoxazine (6.38 g), 4,7-bis- (5-bromo-2-thienyl) -2,1,3-benzothiazole (0.53 g), dichlorobis (triphenylphosphine) palladium complex (11 mg ), Aliquat 336 (2.30 g, manufactured by Aldrich) and toluene (107 ml) were mixed and heated to 105 ° C. 2M Na ₂ CO ₃ aqueous solution (37 ml) was added dropwise to the reaction solution, and the mixture was refluxed for 4 hours. After the reaction, phenylboric acid (0.21 g) was added, and the mixture was further refluxed for 2 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the mixture was washed 3 times with water (150 ml), 3 times with 3% aqueous acetic acid (150 ml) and 3 times with water (150 ml), and purified by passing through an alumina column and a silica gel column. The obtained toluene solution was added dropwise to methanol (3000 ml) and stirred for 1 hour, and then the obtained solid was collected by filtration and dried. The yield of the obtained polymer compound 1 was 8.83 g.
The polymer compound 1 had a polystyrene equivalent number average molecular weight of 5.9 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 1.4 × 10 ⁵ .
4,7-bis (5-bromo-2-thienyl) -2,1,3-benzothiadiazole was synthesized by the method described in WO2000046321.
3,7-Dibromo-N- (4-n-butylphenyl) phenoxazine was synthesized by the method described in JP2004137456.

＝ ５０ ：４７．５ ：２．５

また、下記式で示される構成単位を、下に示す割合で有するものであると求められる。

＝ ５０ ：５： ２．５ ：４７．５
From the charge ratio of the starting materials, the polymer compound 1 is required to have a divalent group represented by the following formula at a ratio shown below,

= 50: 47.5: 2.5

Moreover, it is calculated | required as having the structural unit shown by a following formula in the ratio shown below.

= 50: 5: 2.5: 47.5

.
(Production of light emitting element)
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer) is applied to a glass substrate with an ITO film having a thickness of 150 nm by sputtering, and the thickness is about 60 nm by spin coating. And then dried on a hot plate at 200 ° C. for 10 minutes. Next, the polymer compound 1 was dissolved in mixed xylene at a concentration of 1.5% by weight. After the film was formed by spin coating using the obtained xylene solution, the oxygen concentration and the water concentration were 10 ppm or less (weight basis). ) Under a nitrogen atmosphere at 200 ° C. for 1 hour. After drying, mixed xylene was used in the air to rinse the soluble component, so that the thickness was about 10 nm. Next, the polymer compound 2 was dissolved in mixed xylene at a concentration of 1.5% by weight, and a film was formed to about 80 nm by spin coating using the obtained xylene solution. And it dried at 130 degreeC for 1 hour in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited at about 5 nm and then aluminum was vapor-deposited at about 80 nm as a cathode. After vapor deposition, a polymer light emitting device was produced by sealing using a glass substrate. The element configuration is
ITO / BaytronP (about 60 nm) / polymer compound 1 (10 nm: hole transport layer) / polymer compound 2 (about 80 nm: light emitting layer) / Ba / Al
Met.

When a voltage of 6.0 V was applied to the obtained polymer light-emitting device, fluorescence having a peak top of the emission wavelength of 665 nm was emitted, and the luminance at that time was 1289 cd / m ² . The luminous efficiency was 3.2 V and the maximum value was 0.86 cd / A. Furthermore, the reduction time (life) to a luminance of 95% at an initial luminance of 1000 cd / m ² was 146 hours.

<Comparative Example 1>
(Production of light emitting element)
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer) is applied to a glass substrate with an ITO film having a thickness of 150 nm by sputtering, and the thickness is about 60 nm by spin coating. And then dried on a hot plate at 200 ° C. for 10 minutes. Next, the polymer compound 2 was dissolved in mixed xylene at a concentration of 1.5% by weight, and a film was formed to about 80 nm by spin coating using the obtained xylene solution. And it dried at 130 degreeC for 1 hour in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited at about 5 nm and then aluminum was vapor-deposited at about 80 nm as a cathode. After vapor deposition, a polymer light emitting device was produced by sealing using a glass substrate. The element configuration is
ITO / BaytronP (about 60 nm) / polymer compound 2 (about 80 nm: light emitting layer) / Ba / Al
Met.

When a voltage of 6.0 V was applied to the obtained polymer light-emitting device, fluorescence with a peak top of the emission wavelength of 665 nm was emitted, and the luminance at that time was 1568 cd / m ² , but the luminous efficiency was 4.6 V. The maximum value was 0.52 cd / A. Further, the reduction time (life) to 95% luminance at an initial luminance of 1000 cd / m ² was 11.3 hours.

<Comparative example 2>
(Production of light emitting element)
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer) is applied to a glass substrate with an ITO film having a thickness of 150 nm by sputtering, and the thickness is about 60 nm by spin coating. And then dried on a hot plate at 200 ° C. for 10 minutes. Next, the polymer compound 3 was dissolved in mixed xylene at a concentration of 1.5% by weight, and after the film was formed by spin coating using the obtained xylene solution, the oxygen concentration and the water concentration were 10 ppm or less (weight basis). ) Under a nitrogen atmosphere at 200 ° C. for 1 hour. After drying, mixed xylene was used in the air to rinse the soluble component, so that the thickness was about 10 nm. Next, the polymer compound 2 was dissolved in mixed xylene at a concentration of 1.5% by weight, and a film was formed to about 80 nm by spin coating using the obtained xylene solution. And it dried at 130 degreeC for 1 hour in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited at about 5 nm and then aluminum was vapor-deposited at about 80 nm as a cathode. After vapor deposition, a polymer light emitting device was produced by sealing using a glass substrate. The element configuration is
ITO / BaytronP (about 60 nm) / polymer compound 3 (10 nm: hole transport layer) / polymer compound 2 (about 80 nm: light emitting layer) / Ba / Al
Met.

When a voltage of 6.0 V was applied to the obtained polymer light-emitting device, fluorescence having a peak top of the emission wavelength of 665 nm was emitted, and the luminance at that time was 923 cd / m ² . The luminous efficiency was 2.8 V, showing the maximum value, 0.95 cd / A. Further, the reduction time (life) to a luminance of 95% at an initial luminance of 1000 cd / m ² was 17.8 hours.

<Comparative Example 3> Production of Light Emitting Element A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is spin-coated with a suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer). By the method, a film was formed to a thickness of about 60 nm and dried on a hot plate at 200 ° C. for 10 minutes. Next, the polymer compound 4 was dissolved in mixed xylene at a concentration of 1.5% by weight, and after the film was formed by spin coating using the obtained xylene solution, the oxygen concentration and the water concentration were 10 ppm or less (weight basis). ) Under a nitrogen atmosphere at 200 ° C. for 1 hour. After drying, mixed xylene was used in the air to rinse the soluble component, so that the thickness was about 10 nm. Next, the polymer compound 2 was dissolved in mixed xylene at a concentration of 1.5% by weight, and a film was formed to about 80 nm by spin coating using the obtained xylene solution. And it dried at 130 degreeC for 1 hour in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited at about 5 nm and then aluminum was vapor-deposited at about 80 nm as a cathode. After vapor deposition, a polymer light emitting device was produced by sealing using a glass substrate. The element configuration is
ITO / BaytronP (about 60 nm) / polymer compound 4 (10 nm: hole transport layer) / polymer compound 2 (about 80 nm: light emitting layer) / Ba / Al

When a voltage of 6.0 V was applied to the obtained polymer light emitting device, fluorescence with a peak top of the emission wavelength of 665 nm was emitted, and the luminance at that time was 1226 cd / m ² . Also, the luminous efficiency was 2.8 V, showing the maximum value, and was 0.99 cd / A. Further, the reduction time (life) to a luminance of 95% at an initial luminance of 1000 cd / m ² was 91.5 hours.

<Example 2>
[Synthesis of Polymer Compound 5]
Under an inert atmosphere, 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (7.49 g), 3,7-dibromo-N- (4-n-butyl) Phenyl) phenoxazine (6.38 g), 4,7-bis- (5-bromo-2-thienyl) -2,1,3-benzothiazole (0.33 g), palladium acetate (3.2 mg) tri (2 -Methylphenyl) phosphine (44.5 mg), Aliquat 336 (2.3 g, manufactured by Aldrich) and toluene (110 ml) were mixed and heated to 105 ° C. To this reaction solution was added dropwise 2M Na ₂ CO ₃ aqueous solution (34 ml), and the mixture was refluxed for 4 hours. After the reaction, phenylboric acid (0.21 g) was added, and the mixture was further refluxed for 2 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the mixture was washed 3 times with water (150 ml), 3 times with 3% aqueous acetic acid (150 ml) and 3 times with water (150 ml), and purified by passing through an alumina column and a silica gel column. The obtained toluene solution was added dropwise to methanol (3000 ml) and stirred for 1 hour, and then the obtained solid was collected by filtration and dried. The yield of the obtained polymer compound 5 was 8.83 g.
The polymer compound 5 had a polystyrene equivalent number average molecular weight of 6.7 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 1.8 × 10 ⁵ .
4,7-bis (5-bromo-2-thienyl) -2,1,3-benzothiadiazole was synthesized by the method described in WO2000046321.
3,7-Dibromo-N- (4-n-butylphenyl) phenoxazine was synthesized by the method described in JP2004137456.

＝ ５０ ：４５ ：５

また、高分子化合物５は、下記式で示される構成単位を、下に示す割合で有するものであると求められる。

＝ ５０ ：１０ ：５ ：４５
From the charge ratio of the starting materials, the polymer compound 5 is required to have a divalent group represented by the following formula in the ratio shown below,

= 50: 45: 5

Moreover, the high molecular compound 5 is calculated | required as what has a structural unit shown by a following formula in the ratio shown below.

= 50: 10: 5: 45

.
(Production of light emitting element)
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer) is applied to a glass substrate with an ITO film having a thickness of 150 nm by sputtering, and the thickness is about 60 nm by spin coating. And then dried on a hot plate at 200 ° C. for 10 minutes. Next, the polymer compound 5 was dissolved in mixed xylene at a concentration of 1.5% by weight, and after forming a film by spin coating using the obtained xylene solution, the oxygen concentration and the water concentration were 10 ppm or less (weight basis). ) Under a nitrogen atmosphere at 200 ° C. for 1 hour. After drying, mixed xylene was used in the air to rinse the soluble component, so that the thickness was about 10 nm. Next, the polymer compound 2 was dissolved in mixed xylene at a concentration of 1.5% by weight, and a film was formed to about 80 nm by spin coating using the obtained xylene solution. And it dried at 130 degreeC for 1 hour in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited at about 5 nm and then aluminum was vapor-deposited at about 80 nm as a cathode. After vapor deposition, a polymer light emitting device was produced by sealing using a glass substrate. The element configuration is
ITO / BaytronP (about 60 nm) / polymer compound 5 (10 nm: hole transport layer) / polymer compound 2 (about 80 nm: light emitting layer) / Ba / Al
Met.

When a voltage of 6.0 V was applied to the obtained polymer light emitting device, fluorescence with a peak top of the emission wavelength of 665 nm was emitted, and the luminance at that time was 758 cd / m ² . The light emission efficiency was 4.6V and the maximum value was 0.57 cd / A. Furthermore, the reduction time (life) to a luminance of 95% at an initial luminance of 1000 cd / m ² was 304 hours.

<Example 3>
[Synthesis of Polymer Compound 6]
To a 200 mL separable flask connected to a Dimroth, 2.13 g (4.0 mmol) of 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene, 3,7-dibromo- N- (4-n-butylphenyl) phenoxazine 1.42 g (3.0 mmol), 4,7-bis- (5-bromo-2-thienyl) -2,1,3-benzothiazole 0.46 g (1 0.0 mmol), 0.52 g of Aliquat 336, and 40 ml of toluene were added. Under a nitrogen atmosphere, the monomer solution was heated, and 0.6 mg of palladium acetate and 3.4 mg of tris (o-tolyl) phosphine were added at 95 ° C. To this solution, 10.9 g of a 17.5% by weight aqueous sodium carbonate solution was added dropwise and heated to 105 ° C., followed by stirring for 6 hours. Next, 244 mg of phenylboric acid and 40 mL of toluene were added, and the mixture was stirred at 105 ° C. for 6 hours. Further, 2.43 g of sodium N, N-diethyldithiocarbamate trihydrate and 24 mL of ion-exchanged water were added and stirred at 65 ° C. for 2 hours. After the organic layer was separated from the aqueous layer, the organic layer was washed with ion-exchanged water 50 mL (twice), 3 wt% aqueous acetic acid solution 50 mL (twice) and ion-exchanged water 50 mL (twice) in this order. The organic layer was dropped into 650 mL of methanol to precipitate a polymer, and the precipitate was filtered and dried to obtain a solid. This solid is dissolved in 120 mL of toluene, and the solution is passed through a silica gel / alumina column through which toluene is passed in advance. This solution is dropped into 650 mL of methanol to precipitate a polymer, and the precipitate is filtered and dried. 2.35 g of 6 was obtained. The polystyrene-reduced number average molecular weight was 7.0 × 10 ⁴ , and the polystyrene-reduced weight average molecular weight was 1.7 × 10 ⁵ .
4,7-bis (5-bromo-2-thienyl) -2,1,3-benzothiadiazole was synthesized by the method described in WO2000046321.
3,7-Dibromo-N- (4-n-butylphenyl) phenoxazine was synthesized by the method described in JP2004137456.

＝ ５０ ：３７．５ ：１２．５

また、下記式で示される構成単位を、下に示す割合で有するものであると求められる。

＝ ５０ ：２５ ：１２．５ ：３７．５
From the charge ratio of the starting materials, the polymer compound 6 is required to have a divalent group represented by the following formula in the ratio shown below,

= 50: 37.5: 12.5

Moreover, it is calculated | required as having the structural unit shown by a following formula in the ratio shown below.

= 50: 25: 12.5: 37.5

.
(Production of light emitting element)
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer) is applied to a glass substrate with an ITO film having a thickness of 150 nm by sputtering, and the thickness is about 60 nm by spin coating. And then dried on a hot plate at 200 ° C. for 10 minutes. Next, the polymer compound 6 was dissolved in mixed xylene at a concentration of 1.5% by weight. After the film was formed by spin coating using the obtained xylene solution, the oxygen concentration and water concentration were 10 ppm or less (weight basis). ) Under a nitrogen atmosphere at 200 ° C. for 1 hour. After drying, mixed xylene was used in the air to rinse the soluble component, so that the thickness was about 10 nm. Next, the polymer compound 2 was dissolved in mixed xylene at a concentration of 1.5% by weight, and a film was formed to about 80 nm by spin coating using the obtained xylene solution. And it dried at 130 degreeC for 1 hour in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited at about 5 nm and then aluminum was vapor-deposited at about 80 nm as a cathode. After vapor deposition, a polymer light emitting device was produced by sealing using a glass substrate. The element configuration is
ITO / BaytronP (about 60 nm) / polymer compound 6 (10 nm: hole transport layer) / polymer compound 2 (about 80 nm: light emitting layer) / Ba / Al
Met.

When a voltage of 6.0 V was applied to the obtained polymer light-emitting device, fluorescence with a peak top of the emission wavelength of 665 nm was emitted, and the luminance at that time was 710 cd / m ² . The luminous efficiency was 4.6 V and showed the maximum value, which was 0.53 cd / A. Further, the reduction time (life) to 95% luminance at an initial luminance of 1000 cd / m ² was 455 hours.

<Example 4>
[Synthesis of Polymer Compound 7]
To a 200 mL separable flask connected to a Dimroth, 2.13 g (4.0 mmol) of 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene, 3,7-dibromo- N- (4-n-butylphenyl) phenoxazine 1.33 g (2.8 mmol), 4,7-bis- (5-bromo-2-thienyl) -2,1,3-benzothiazole 0.55 g (1 .2 mmol), 0.52 g of Aliquat 336, and 40 ml of toluene were added. Under a nitrogen atmosphere, the monomer solution was heated, and 0.6 mg of palladium acetate and 3.4 mg of tris (o-tolyl) phosphine were added at 95 ° C. To this solution, 10.9 g of a 17.5% by weight aqueous sodium carbonate solution was added dropwise and heated to 105 ° C., followed by stirring for 6 hours. Next, 244 mg of phenylboric acid and 40 mL of toluene were added, and the mixture was stirred at 105 ° C. for 6 hours. Further, 2.43 g of sodium N, N-diethyldithiocarbamate trihydrate and 24 mL of ion-exchanged water were added and stirred at 65 ° C. for 2 hours. After the organic layer was separated from the aqueous layer, the organic layer was washed with ion-exchanged water 50 mL (twice), 3 wt% aqueous acetic acid solution 50 mL (twice) and ion-exchanged water 50 mL (twice) in this order. The organic layer was dropped into 650 mL of methanol to precipitate a polymer, and the precipitate was filtered and dried to obtain a solid. This solid is dissolved in 120 mL of toluene, and the solution is passed through a silica gel / alumina column through which toluene is passed in advance. This solution is dropped into 650 mL of methanol to precipitate a polymer, and the precipitate is filtered and dried. 2.35 g of 7 was obtained. The number average molecular weight in terms of polystyrene was 7.7 × 10 ⁴ , and the weight average molecular weight in terms of polystyrene was 1.8 × 10 ⁵ .
4,7-bis (5-bromo-2-thienyl) -2,1,3-benzothiadiazole was synthesized by the method described in WO2000046321.
3,7-Dibromo-N- (4-n-butylphenyl) phenoxazine was synthesized by the method described in JP2004137456.

＝ ５０ ：３５ ：１５

また、下記式で示される構成単位を、下に示す割合で有するものであると求められる。

＝５０ ：３０ ：１５ ：３５
From the charge ratio of the starting materials, the polymer compound 7 is required to have a divalent group represented by the following formula at a ratio shown below,

= 50: 35: 15

Moreover, it is calculated | required as having the structural unit shown by a following formula in the ratio shown below.

= 50: 30: 15: 35

.
(Production of light emitting element)
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer) is applied to a glass substrate with an ITO film having a thickness of 150 nm by sputtering, and the thickness is about 60 nm by spin coating. And then dried on a hot plate at 200 ° C. for 10 minutes. Next, the polymer compound 7 was dissolved in mixed xylene at a concentration of 1.5% by weight, and after the film was formed by spin coating using the obtained xylene solution, the oxygen concentration and the water concentration were 10 ppm or less (weight basis). ) Under a nitrogen atmosphere at 200 ° C. for 1 hour. After drying, mixed xylene was used in the air to rinse the soluble component, so that the thickness was about 10 nm. Next, the polymer compound 2 was dissolved in mixed xylene at a concentration of 1.5% by weight, and a film was formed to about 80 nm by spin coating using the obtained xylene solution. And it dried at 130 degreeC for 1 hour in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited at about 5 nm and then aluminum was vapor-deposited at about 80 nm as a cathode. After vapor deposition, a polymer light emitting device was produced by sealing using a glass substrate. The element configuration is
ITO / BaytronP (about 60 nm) / polymer compound 7 (10 nm) / polymer compound 2 (about 80 nm) / Ba / Al
Met.

When a voltage of 6.0 V was applied to the obtained polymer light emitting device, fluorescence with a peak top of the emission wavelength of 665 nm was emitted, and the luminance at that time was 705 cd / m ² . The luminous efficiency was 4.8 V, showing the maximum value, which was 0.51 cd / A. Furthermore, the reduction time (life) to a luminance of 95% at an initial luminance of 1000 cd / m ² was 516 hours.

<Example 5>
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer) is applied to a glass substrate with an ITO film having a thickness of 150 nm by sputtering, and the thickness is about 60 nm by spin coating. And then dried on a hot plate at 200 ° C. for 10 minutes. Next, the polymer compound 7 was dissolved in mixed xylene at a concentration of 1.7% by weight, and a film was formed to about 80 nm by spin coating using the obtained xylene solution. And it dried at 130 degreeC for 1 hour in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited at about 5 nm and then aluminum was vapor-deposited at about 80 nm as a cathode. After vapor deposition, a polymer light emitting device was produced by sealing using a glass substrate. The element configuration is
ITO / BaytronP (about 60 nm) / polymer compound 7 (80 nm: light emitting layer) / Ba / Al
Met.
When a voltage of 6.0 V was applied to the obtained polymer light emitting device, red light was emitted with a peak top of the emission wavelength of 670 nm, and the luminance at that time was 87 cd / m ² . The light emission efficiency was 10 V, 0.03 cd / A.

Claims (12)

Number of polystyrene equivalents including a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), a structural unit represented by the following formula (3), and a structural unit represented by the following formula (4) A high molecular compound having an average molecular weight of 10 ³ to 10 ⁸ ,
The ratio of the number of moles of the structural unit represented by formula (1) to the total number of moles of all the structural units possessed by the polymer compound is x, the ratio of the number of moles of the structural unit represented by formula (2) is y, and the formula ( When the ratio of the number of moles of the structural unit represented by 3) is z and the ratio of the number of moles of the structural unit represented by formula (4) is w, 0.5 ≦ x + y + z + w ≦ 1,
0.3 ≦ x / (x + y + z + w) ≦ 0.82, 0.02 ≦ y / (x + y + z + w) ≦ 0.4, 0.01 ≦ z / (x + y + z + w) ≦ 0.2 and 0.15 ≦ w / (x + y + z + w) ) ≦ 0.67,
A structural unit represented by the following formula (5) in which a structural unit represented by the formula (2) is bonded to both sides of the structural unit represented by the formula (3);
When the ratio of the structural unit represented by Formula (1), the structural unit represented by Formula (5), and the structural unit represented by Formula (4) is p: q: r, 0.3 ≦ p / ( Polymer compound satisfying p + 3q + r) ≦ 0.82, 0.01 ≦ q / (p + 3q + r) ≦ 0.2 and 0.15 ≦ r / (p + 3q + r) ≦ 0.5 .

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a substituent, and these may be the same or different. a and d each independently represent an integer of 0 to 3, b and c each independently represent an integer of 0 to 2, and e represents an integer of 0 to 5. Two R ^{1 s} may be the same or different, and when there are a plurality of R ² , R ³ , R ⁴ , R ⁵ and R ^6, they may be the same or different. X ¹ , X ² and X ³ each independently represent an oxygen atom or a sulfur atom. ]

[Wherein R ³ and R ⁴ each represent a substituent, and these may be the same or different. b and c each independently represent an integer of 0 to 2. When a plurality of R ³ and R ⁴ are present, they may be the same or different. X ¹ and X ² each independently represent an oxygen atom or a sulfur atom. ] The polymer compound according to claim 1, wherein the formula (4) is the formula (4-1).

(X ³ and R ⁶ have the same meaning as described above.) The polymer compound according to claim 1 or 2, wherein X ³ in the formula (4) is an oxygen atom. 0.3 ≦ x / (x + y + z + w) ≦ 0.7, 0.02 ≦ y / (x + y + z + w) ≦ 0.4, 0.01 ≦ z / (x + y + z + w) ≦ 0.2 and 0.15 ≦ w / (x + y + z + w) ) meets ≦ 0.5,
0.3 ≦ p / (p + 3q + r) ≦ 0.7,0.01 ≦ q / (p + 3q + r) ≦ 0.2 and 0.15 ≦ r / (p + 3q + r) of claims 1 to 3 satisfying the ≦ 0.5 The high molecular compound in any one . Liquid composition containing a polymer compound and a solvent according to any one of claims 1 to 4. The manufacturing method of the thin film which creates the layer containing the high molecular compound in any one of Claims 1-4 , and heats this layer to 50 degreeC or more. The polymer light emitting element which has an electrode which consists of an anode and a cathode, and the organic layer which is provided between this electrode and contains the polymer compound in any one of Claims 1-4 . The polymer light-emitting device according to claim 7 , wherein the organic layer containing the polymer compound according to any one of claims 1 to 4 is a light-emitting layer. Electrodes consisting of an anode and a cathode, a light-emitting layer between the electrodes, further polymer light emitting device having an organic layer containing the polymer compound according to claim 1 provided in the light emitting layers and an anode . The polymer light-emitting device according to claim 9 , wherein the organic layer containing the polymer compound according to any one of claims 1 to 4 is a hole transport layer. The polymer light-emitting device according to claim 9 or 10 , wherein the light-emitting layer contains a polymer compound that emits light in a red region (600 to 800 nm). Emitting layer is a structural unit represented by the formula (1), the formula (2) according to claim 9 or 10, wherein comprising a polymer compound containing a constitutional unit represented by the structural unit and the formula (3) indicated by Polymer light emitting device.