JP5018043B2 - Polymer compound and polymer light emitting device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel polymeric compound which is usable as a material of a light emitting layer, a hole injection layer, a hole transporting layer and the like, and to provide a polymeric light emitting element using the same. <P>SOLUTION: The polymeric compound is characterized by comprising a repeating unit represented by formula (1) wherein X denotes an atom or divalent group which forms a five-membered ring or six-membered ring together with two atoms on A ring and two atoms on B ring, the atom or the divalent group contains at least one atom selected from the group consisting of oxygen atom, sulfur atom, selenium atom and silicon atom, A ring and B ring denote an aromatic hydrocarbon ring or heterocyclic ring, Ar1 denotes a divalent organic group having a divalent aromatic hydrocarbon group or heterocyclic ring skeleton, Ar2 and Ar3 denote a monovalent organic group having a monovalent aromatic hydrocarbon group or heterocyclic ring skeleton, R<SP>*</SP>denotes a linkage group and h denotes 0 or 1. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

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

  High-molecular-weight light-emitting materials and charge transport materials are usually soluble in a solvent, and various studies have been made since an organic layer of a light-emitting element can be formed by a coating method. Among them, amine-containing polymers are used in light emitting layers, hole injection layers, and the like in order to improve device performance (Patent Document 1, Non-Patent Document 1).

JP 2005-302567 A Monthly display September 2005, page 3

  An object of the present invention is to provide a novel polymer compound that can be used as a material for a light emitting layer, a hole injection layer, a hole transport layer, and the like, and a polymer light emitting device using the polymer compound.

〔式中、ＸはＡ環上の２個の原子とＢ環上の２個の原子と一緒になって５員環または６員環を形成する原子または２価の基を表し、該原子または２価の基は、酸素原子、硫黄原子、セレン原子および珪素原子からなる群から選ばれる原子を少なくとも一つ含む。Ａ環およびＢ環は独立に置換基を有していてもよい芳香族炭化水素環または置換基を有していてもよい複素環を表し、複数の置換基が存在する場合には互いに結合して環を形成してもよく、Ａｒ１は置換基を有していてもよい２価の芳香族炭化水素基または複素環骨格を有する２価の有機基を表し、複数の置換基が存在する場合には互いに結合して環を形成してもよい。Ａｒ２およびＡｒ３は独立に置換基を有していてもよい１価の芳香族炭化水素基または複素環骨格を有する１価の有機基を表し、複数の置換基が存在する場合には互いに結合して環を形成してもよい。Ｒ^*は連結基を表し、ｈは０又は１を表す。複数存在するＲ^*は同一であっても異なっていてもよい。〕 As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention. That is, the present invention first provides a polymer compound comprising a repeating unit represented by the following general formula (1).

[In the formula, X represents an atom or a divalent group that forms a 5-membered ring or a 6-membered ring together with two atoms on the A ring and two atoms on the B ring; The divalent group contains at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom and a silicon atom. A ring and B ring independently represent an aromatic hydrocarbon ring which may have a substituent or a heterocyclic ring which may have a substituent, and when there are a plurality of substituents, they are bonded to each other. In the case where Ar1 represents a divalent aromatic hydrocarbon group which may have a substituent or a divalent organic group having a heterocyclic skeleton, and there are a plurality of substituents May be bonded to each other to form a ring. Ar2 and Ar3 each independently represent a monovalent aromatic hydrocarbon group which may have a substituent or a monovalent organic group having a heterocyclic skeleton, and when a plurality of substituents are present, they are bonded to each other. To form a ring. R ^* represents a linking group, and h represents 0 or 1. A plurality of R ^* may be the same or different. ]

  Second, the present invention provides a polymer composition comprising at least one material selected from a hole transporting material, an electron transporting material, and a light emitting material and the above polymer compound. .

〔式中、Ａｒ１、Ａｒ２、Ａｒ３、Ｒ^*及びｈは、上記のとおりである。〕
で表される２級アミン化合物と、下記一般式（５）：

〔式中、Ｘは上記のとおりであり、Ｚはハロゲン原子または−ＳＯ₂Ｒ⁹（ここで、Ｒ⁹は、アルキル基、アリール基またはアリールアルキル基を表す。）を表す。〕
で表される化合物とを、金属縮合剤および脱酸剤の存在下で反応させることを特徴とする上記高分子化合物の製造方法を提供する。 Thirdly, the present invention provides the following general formula (4):

[Wherein, Ar1, Ar2, Ar3, R ^* and h are as described above. ]
A secondary amine compound represented by the following general formula (5):

[Wherein, X is as defined above, and Z represents a halogen atom or —SO ₂ R ⁹ (wherein R ⁹ represents an alkyl group, an aryl group or an arylalkyl group). ]
And a compound represented by the formula (I) is reacted in the presence of a metal condensing agent and a deoxidizing agent.

  Fourthly, the present invention provides a liquid composition comprising the polymer compound and / or the polymer composition and a solvent.

  Fifth, the present invention provides a thin film characterized by containing the above polymer compound and / or the above polymer composition.

  Sixth, the present invention provides an organic transistor having the above-mentioned thin film.

  Seventhly, the present invention provides a polymer light emitting device comprising an electrode comprising an anode and a cathode, and an organic layer comprising the polymer compound and / or the polymer composition provided between the electrodes. I will provide a.

  Eighthly, the present invention provides a planar light source using the polymer light emitting device.

  Ninthly, the present invention provides a segment display device using the polymer light emitting device.

  Tenthly, the present invention provides a dot matrix display device using the above polymer light emitting device.

  Eleventhly, the present invention provides a liquid crystal display device characterized in that the polymer light emitting device is a backlight.

  The polymer compound of the present invention and the polymer composition containing the polymer compound are excellent in the maximum current efficiency, and the organic layer (light emitting layer, hole transport layer, hole injection layer, etc.) of the light emitting element, Useful as a layer material. Therefore, a polymer light emitting device can be produced using this polymer compound and / or polymer composition. The polymer light-emitting device of the present invention thus produced can be suitably used for curved or flat light sources for backlights or illumination of liquid crystal displays, segment type display devices, dot matrix flat panel displays, and the like. Moreover, the said high molecular compound can be easily manufactured by applying the manufacturing method of this invention. Furthermore, a thin film containing the polymer compound of the present invention can be easily produced by applying the liquid composition of the present invention.

Hereinafter, the present invention will be described in detail.
<Polymer compound>
The polymer compound of the present invention includes a repeating unit represented by the general formula (1).

-About X-
In the general formula (1), X is an atom or a divalent group (or a bivalent group that forms a 5- or 6-membered ring together with two atoms on the A ring and two atoms on the B ring (or Represents an atomic group). Specific examples of X include the following.

（式中、Ｒは独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、置換シリル基、シアノ基、ニトロ基、または複素環骨格を有する１価の有機基を表す。）

(Wherein R is independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an alkenyl group, an alkynyl group) Group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted silyl group, cyano group, It represents a monovalent organic group having a nitro group or a heterocyclic skeleton.)

  Examples of the halogen atom represented by R include fluorine, chlorine, bromine and iodine. Hereinafter, similarly, the group represented by R will be specifically described.

  The alkyl group may be linear, branched or cyclic, may have a substituent, and usually has about 1 to 20 carbon atoms. Specific examples thereof include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2- Examples include 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.

  The alkoxy group may be linear, branched or cyclic, may have a substituent, and usually has about 1 to 20 carbon atoms. Specific examples thereof include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-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, perfluorohexyl group, Examples include a perfluorooctyl group, a methoxymethyloxy group, and a 2-methoxyethyloxy group.

  The alkylthio group may be linear, branched or cyclic, may have a substituent, and usually has about 1 to 20 carbon atoms. Specific examples thereof include methylthio group, ethylthio group, propylthio group, i-propylthio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2 -Ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, trifluoromethylthio group and the like can be mentioned.

An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, having a condensed ring, or having two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene Is also included. The aryl group usually has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenyl group, a C _{1 to} C ₁₂ alkoxyphenyl group (“C _{1 to} C ₁₂ ” represents ₁ to ₁₂ carbon atoms, and the same shall apply hereinafter), C _{1 to} C _12. Examples include alkylphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, pentafluorophenyl group, etc., solubility in organic solvents, device characteristics, synthesis from the viewpoint of easiness, C ₁ -C ₁₂ alkoxyphenyl group, is C ₁ -C ₁₂ alkylphenyl group are preferable. Specific examples C ₁ -C ₁₂ alkoxyphenyl group, methoxyphenyl group, ethoxyphenyl group, propyloxyphenyl group, i- propyl group, a butoxyphenyl group, i- butoxyphenyl, t-butoxyphenyl group, Pentyloxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group, 3,7-dimethyloctyloxyphenyl Group, lauryloxyphenyl group and the like. Specific examples C ₁ -C ₁₂ alkylphenyl group include a methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, i- propylphenyl group, butylphenyl group, i- Examples include butylphenyl group, t-butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group and the like.

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

The arylthio group may have a substituent on the aromatic ring and usually has about 3 to 60 carbon atoms. Specific examples thereof include a phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group, a pentafluorophenylthio group.

The arylalkyl group may have a substituent and usually has about 7 to 60 carbon atoms. As specific examples, 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.

The arylalkoxy group may have a substituent and usually has about 7 to 60 carbon atoms. Specific examples thereof include phenyl-C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkoxy group, 1- naphthyl -C ₁ -C ₁₂ alkoxy groups, 2-naphthyl -C ₁ -C ₁₂ alkoxy group.

The arylalkylthio group may have a substituent and usually has about 7 to 60 carbon atoms. As specific examples, 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.

  The alkenyl group usually has about 2 to 20 carbon atoms. Specific examples thereof include a vinyl group, 1-propenyl group, 2-propenyl group, 3-propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, cyclohexenyl group and the like. Alkenyl groups also include alkadienyl groups such as 1,3-butadienyl groups.

  The alkynyl group usually has about 2 to 20 carbon atoms. Specific examples thereof include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptenyl group, octynyl group, and cyclohexylethynyl group. In addition, the alkynyl group includes an alkydenyl group such as a 1,3-butadiynyl group.

  The arylalkenyl group usually has about 8 to 50 carbon atoms. The aryl group (namely, aryl moiety) and alkenyl group (namely, alkenyl moiety) constituting the arylalkenyl group are the same as the above aryl group and alkenyl group. Specific examples of the arylalkenyl group include 1-arylvinyl group, 2-arylvinyl group, 1-aryl-1-propenyl group, 2-aryl-1-propenyl group, 2-aryl-2-propenyl group, 3- An aryl-2-propenyl group etc. are mentioned. Also included are arylalkadienyl groups such as 4-aryl-1,3-butadienyl groups.

  The arylalkynyl group usually has about 8 to 50 carbon atoms. The aryl group (that is, aryl moiety) and alkynyl group (that is, alkynyl moiety) constituting the arylalkynyl group are the same as the above aryl group and alkynyl group. Specific examples of the arylalkynyl group include an arylethynyl group, a 3-aryl-1-propionyl group, and a 3-aryl-2-propionyl group. Also included are arylalkadiynyl groups such as 4-aryl-1,3-butadiynyl.

  The acyl group usually has about 2 to 20 carbon atoms. Specific examples thereof include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, trifluoroacetyl group, pentafluorobenzoyl group and the like.

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

  The amide group usually has about 2 to 20 carbon atoms. Specific examples thereof include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group, ditriamide. Examples include a fluoroacetamide group and a dipentafluorobenzamide group.

  As an acid imide group, the residue obtained by remove | excluding the hydrogen atom couple | bonded with the nitrogen atom from acid imide is mentioned, Usually, it is C2-C60 grade, Preferably it is 2-20. Specific examples of the acid imide group include the following groups. In specific examples, “Me” represents a methyl group, and hereinafter the same.

  An imine residue refers to 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 substituted with alkyl groups or the like. And a residue obtained by removing one hydrogen atom from the compound, usually having about 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms. Specific examples include groups represented by the following structural formulas.

（式中、Ｍｅはメチル基を表す。）

(In the formula, Me represents a methyl group.)

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 organic group having a heterocyclic skeleton. Note that the monovalent organic group having an alkyl group, an aryl group, an arylalkyl group, or a heterocyclic skeleton may have a substituent. The substituted amino group usually has about 1 to 40 carbon atoms. Specific examples thereof include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, t-butylamino. Group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group , cyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, bis (trifluoromethyl) amino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl Amino group, bis (C ₁ -C ₁₂ alkoxyphenyl) amino group, bis (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, Pirajiruamino group, triazyl amino group, phenyl -C 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, a bis (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, bis (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.

As the substituted silyloxy group, a silyloxy group (H ₃ SiO—) substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent organic group having a heterocyclic skeleton Etc. The alkyl group, aryl group, arylalkyl group, and monovalent organic group having a heterocyclic skeleton may be included. The substituted silyloxy group usually has about 1 to 60 carbon atoms, preferably 3 to 30 carbon atoms. Specific examples thereof include trimethylsilyloxy group, triethylsilyloxy group, tri-n-propylsilyloxy group, tri-i-propylsilyloxy group, t-butylsilyldimethylsilyloxy group, triphenylsilyloxy group, tri- Examples thereof include a p-xylylsilyloxy group, a tribenzylsilyloxy group, a diphenylmethylsilyloxy group, a t-butyldiphenylsilyloxy group, and a dimethylphenylsilyloxy group.

Examples of the substituted silylthio group include an alkyl group, an aryl group, an arylalkyl group, and a silylthio group (H ₃ SiS—) substituted with 1 to 3 groups selected from a monovalent organic group having a heterocyclic skeleton. Can be mentioned. The monovalent organic group having an alkyl group, an aryl group, an arylalkyl group, or a heterocyclic skeleton may have a substituent. The substituted silylthio group usually has about 1 to 60 carbon atoms, preferably 3 to 30 carbon atoms. Specific examples thereof include trimethylsilylthio group, triethylsilylthio group, tri-n-propylsilylthio group, tri-i-propylsilylthio group, t-butylsilyldimethylsilylthio group, triphenylsilylthio group, tri- Examples thereof include a p-xylylsilylthio group, a tribenzylsilylthio group, a diphenylmethylsilylthio group, a t-butyldiphenylsilylthio group, and a dimethylphenylsilylthio group.

As the substituted silylamino group, a silylamino group substituted with 1 to 6 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent organic group having a heterocyclic skeleton (that is, H ₃ SiNH- or ( H ₃ Si) ₂ N—) and the like. Note that the monovalent organic group having an alkyl group, an aryl group, an arylalkyl group, or a heterocyclic skeleton may have a substituent. The substituted silylamino group usually has about 1 to 120 carbon atoms, preferably 3 to 60 carbon atoms. Specific examples thereof include trimethylsilylamino group, triethylsilylamino group, tri-n-propylsilylamino group, tri-i-propylsilylamino group, t-butylsilyldimethylsilylamino group, triphenylsilylamino group, tri- p-xylylsilylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, t-butyldiphenylsilylamino group, dimethylphenylsilylamino group, bis (trimethylsilyl) amino group, bis (triethylsilyl) amino group, bis (Tri-n-propylsilyl) amino group, bis (tri-i-propylsilyl) amino group, bis (t-butyldimethylsilyl) amino group, bis (triphenylsilyl) amino group, bis (tri-p-xylylsilyl) Amino group, bis (tribenzylsilyl) Amino group, bis (diphenylmethylsilyl) amino group, bis (t-butyldiphenylsilyl) amino group, such as bis (dimethylphenylsilyl) amino group.

  The substituted silyl group represents a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. Carbon number is about 1-60 normally, Preferably it is 3-30. Note that the monovalent organic group having an alkyl group, an aryl group, an arylalkyl group, or a heterocyclic skeleton may have a substituent. Specific examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, tri-i-propylsilyl group, t-butyldimethylsilyl group, triphenylsilyl group, and tri-p-xylylsilyl group. , Tribenzylsilyl group, diphenylmethylsilyl group, t-butyldiphenylsilyl group, dimethylphenylsilyl group and the like.

In the description of R, the monovalent organic group having a heterocyclic skeleton refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 2 to 60 carbon atoms. Specific examples thereof include a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, an oxazolyl group, a thiazole group And thiadiazole group.

In X, —O—, —S—, —Se—, —SiR ₂ — or —CR ₂ O— is preferred, —O—, —S—, —CR ₂ O— is more preferred, —O— , -S- is more preferable.

-About A ring and B ring-
In the general formula (1), the A ring and the B ring independently represent an aromatic hydrocarbon ring or a heterocyclic ring which may have a substituent, and are bonded to each other when a plurality of substituents are present. To form a ring.

  As the aromatic hydrocarbon ring, a benzene ring alone or a condensed benzene ring is preferable, and examples thereof include a benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, phenanthrene ring, etc. Aromatic hydrocarbon rings, preferably benzene rings, naphthalene rings, anthracene rings, and phenanthrene rings, and more preferably benzene rings and naphthalene rings.

  As a combination of A ring and B ring, preferably a benzene ring and a naphthalene ring, a benzene ring and an anthracene ring, a benzene ring and a phenanthrene ring, a naphthalene ring and an anthracene ring, a combination of a naphthalene ring and a phenanthrene ring, an anthracene ring and a phenanthrene ring, etc. And a combination of a benzene ring and a naphthalene ring is more preferable, and a combination of both being a benzene ring is more preferable. In the illustration of the combination of these A ring and B ring, each ring may have a substituent.

  When the aromatic hydrocarbon ring has a substituent, from the viewpoints of solubility in an organic solvent, device characteristics, ease of synthesis, etc., the substituent is an alkyl group, an alkoxy group, an alkylthio group, an aryl group. , Aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group , An imine residue, an amide group, an acid imide group, a monovalent organic group having a heterocyclic skeleton, a carboxyl group, a substituted carboxyl group, and a cyano group are preferable.

  When the aromatic hydrocarbon ring has a substituent, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group , Amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent organic group having a heterocyclic skeleton, specific examples Is the same as described above for R.

  Examples of the substituted carboxyl group in the case where the aromatic hydrocarbon ring has a substituent include an alkyl group, an aryl group, an arylalkyl group, or a carboxyl group substituted with a monovalent organic group having a heterocyclic skeleton, The number of carbon atoms is usually about 2 to 60, preferably 2 to 48. Specific examples of the substituted carboxyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, i-propoxycarbonyl group, butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyl group. Siloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl Group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluoro Chi le oxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, and pyridyl oxycarbonyl group. Note that the monovalent organic group having an alkyl group, an aryl group, an arylalkyl group or a heterocyclic skeleton may have a substituent. In this case, the number of carbon atoms of the substituted carboxyl group depends on the number of carbon atoms of the substituent. Carbon number is not included.

Examples of the heterocyclic ring of the A ring and the B ring include those having a structure in which a carbon atom contained in the ring is replaced with a hetero atom, and specifically, C _4- which may have a substituent. C ₂₀ heterocycle is exemplified. When this C _{4 to} C ₂₀ heterocyclic ring is selected, the fluorescence intensity in the thin film state of the obtained compound and the controllability of the emission color in the visible light region from blue to red are more excellent.

  The heterocyclic rings of the A ring and the B ring may be substituted with an alkyl group, an alkoxy group, an alkylthio group, a halogen atom, or the like. Examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, Examples include 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, and perfluorooctyl group. . Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, Octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorohexyl group Examples include a fluorooctyl group, a methoxymethyloxy group, and a 2-methoxyethyloxy group. Examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, i-propylthio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2- Examples include ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, trifluoromethylthio group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Specific examples of the A ring and B ring heterocycle include thiophene ring, furan ring, pyridine ring, quinoline ring, quinoxaline ring, phenanthroline ring, phenothiazine ring, tetrahydrofuran ring, tetrahydrothiophene ring, tetrahydroindole ring, tetrahydropyran ring. , Hexahydropyridine ring, tetrahydrothiopyran ring, oxocan ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, crown ethers and the like.

-About Ar1-
In the general formula (1), Ar1 represents a divalent aromatic hydrocarbon group which may have a substituent or a divalent organic group having a heterocyclic skeleton, and when a plurality of substituents are present They may combine with each other to form a ring.

  The divalent organic hydrocarbon group having a divalent aromatic hydrocarbon group or heterocyclic skeleton of Ar1 refers to an atomic group formed by removing two hydrogen atoms from an aromatic hydrocarbon ring or heterocyclic ring.

  As the aromatic hydrocarbon ring, a benzene ring alone or a condensed benzene ring is preferable, and examples thereof include a benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, phenanthrene ring, etc. Preferably, a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring are mentioned, and a benzene ring and a naphthalene ring are more preferable. That is, specific examples of the divalent aromatic hydrocarbon group include groups selected from a phenylene group, a naphthylene group, an anthracene-diyl group, a tetracene-diyl group, a pentacene-diyl group, a pyrene-diyl group, and a phenanthrene-diyl group. Preferably, it is a phenylene group or a naphthylene group.

  When the aromatic hydrocarbon ring (or divalent aromatic hydrocarbon group) has a substituent, from the viewpoints of solubility in organic solvents, device characteristics, ease of synthesis, etc., the substituent is Alkyl group, alkoxy group, 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 Must be selected from silyl groups, halogen atoms, acyl groups, acyloxy groups, imine residues, amide groups, acid imide groups, monovalent organic groups having a heterocyclic skeleton, carboxyl groups, substituted carboxyl groups, and cyano groups. Is preferred. These substituents are the same as those specifically described and exemplified as substituents in the case where the aromatic hydrocarbon ring has a substituent in the terms of the A ring and the B ring.

  Ar1 represents the following general formula (3):

〔式中、Ｒ¹〜Ｒ⁴は独立に、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、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、複素環骨格を有する１価の有機基、カルボキシル基、置換カルボキシル基またはシアノ基を表し、Ｒ¹〜Ｒ⁴は互いに結合して環を形成していてもよい。〕
であることがより好ましい。

[Wherein R ^{1 to} R ⁴ are independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group. , 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 organic group having a heterocyclic skeleton, Represents a carboxyl group, a substituted carboxyl group or a cyano group, and R ^{1 to} R ⁴ may be bonded to each other to form a ring. ]
It is more preferable that

These groups represented by R ^{1 to} R ⁴ are the same as those specifically explained and exemplified as the substituents in the case where the aromatic hydrocarbon ring has a substituent in the above-mentioned A ring and B ring terms. It is.

Examples of the heterocyclic ring constituting the divalent organic group having a heterocyclic skeleton of Ar1 include those having a structure in which a carbon atom contained in the ring is replaced by a heteroatom. Specifically, the heterocyclic ring has a substituent. C ₄ -C ₂₀ heterocycles which may be used are exemplified. More specifically, thiophene ring, furan ring, pyridine ring, quinoline ring, quinoxaline ring, phenanthroline ring, phenothiazine ring and the like are exemplified.

  When the divalent aromatic hydrocarbon group represented by Ar1 or the divalent organic group having a heterocyclic skeleton has a substituent, the viewpoint of solubility in organic solvent, device characteristics, easiness of synthesis, etc. To alkyl group, alkoxy group, 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, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group and cyano group are preferable. . These substituents are the same as those specifically described and exemplified as substituents in the case where the aromatic hydrocarbon ring has a substituent in the terms of the A ring and the B ring.

-About Ar2 and Ar3-
In the general formula (1), Ar2 and Ar3 independently represent a monovalent aromatic hydrocarbon group which may have a substituent or a monovalent organic group having a heterocyclic skeleton, and a plurality of substituents When present, they may combine with each other to form a ring.

  The monovalent aromatic hydrocarbon group or the monovalent organic group having a heterocyclic skeleton of Ar2 and Ar3 refers to an atomic group formed by removing one hydrogen atom from an aromatic hydrocarbon ring or a heterocyclic ring. The aromatic hydrocarbon ring and the heterocyclic ring are the same as those specifically explained and exemplified in the above Ar1 section.

Further, examples of the linking group represented by R ^*, e.g., an alkylene group, such as an alkenylene group and the like, quaternary carbon atoms therein -O -, - S -, - CO -, - CO 2 -, It may be substituted with —SO—, —SO ₂ —, —SiR ¹ R ² —, NR ³ —, —BR ⁴ —, —PR ⁵ —, and —P (═O) —.

-Specific examples of polymer compounds-
Specific examples of the polymer compound containing the repeating unit represented by the general formula (1) include the following, but these examples do not limit the scope of the present invention. In these exemplifications, n is a positive integer, and is usually a positive integer that falls within the range of the weight average molecular weight in terms of polystyrene described later. R is as described above, a is 0 to 3, b is 0 to 4, c is 0 to 5, d is 0 to 7, e is 0 to 2, and f is an integer of 0 to 6. When a plurality of a to f are present, they may be the same or different.

-Molecular weight of polymer compounds-
The weight average molecular weight in terms of polystyrene of the polymer compound of the present invention is usually about 10 ³ to 10 ⁸ , and 5 × 10 ^{4 to} 5 from the viewpoint of film formability and current efficiency when used in an element. × 10 ⁶ is preferable, and 10 ^{5 to} 5 × 10 ⁶ is more preferable. When the weight average molecular weight satisfies such a preferable range, the resulting polymer compound can produce a device with high current efficiency even when used alone in a device or when two or more types are mixed and used in a device. Become.

-Applications of polymer compounds-
The polymer compound of the present invention usually emits fluorescence or phosphorescence in a solid state and can be used as a polymer light emitter (high molecular weight light-emitting material). Further, the polymer compound has an excellent charge transport ability, and can be suitably used as a material for a polymer light emitting device or a charge transport material.

  Further, the polymer compound of the present invention includes a laser dye, an organic solar cell material, an organic semiconductor for an organic transistor, a conductive thin film material such as an organic semiconductor thin film, and a luminescent thin film material that emits fluorescence or phosphorescence. It can also be preferably used as a material used in the production of polymer field effect transistors.

  The polymer compound of the present invention may be used in any state for various uses including the above-mentioned uses. For example, even when used in the state of a polymer compound, the polymer composition, liquid composition, etc. described later are used. It may be used after the state. This will be specifically described below.

-Method for producing polymer compound-
The polymer compound of the present invention may be produced by any method, but can be preferably produced by the following method. That is, the following general formula (4):

〔式中、Ａｒ１、Ａｒ２およびＡｒ３は、上記のとおりである。〕
で表される２級アミン化合物と、下記一般式（５）：

[Wherein, Ar1, Ar2 and Ar3 are as described above. ]
A secondary amine compound represented by the following general formula (5):

〔式中、Ｘは上記のとおりであり、Ｚはハロゲン原子または−ＳＯ₂Ｒ⁵（ここで、Ｒ⁵は、アルキル基、アリール基またはアリールアルキル基を表す。）を表す。〕
で表される化合物とを、金属縮合剤および脱酸剤の存在下で反応させることにより、上記一般式（１）で表される繰り返し単位を含む本発明の高分子化合物を作製することができる。

[Wherein, X is as defined above, and Z represents a halogen atom or —SO ₂ R ⁵ (wherein R ⁵ represents an alkyl group, an aryl group, or an arylalkyl group). ]
Is reacted with a compound represented by the formula (1) in the presence of a metal condensing agent and a deoxidizing agent to produce the polymer compound of the present invention containing the repeating unit represented by the general formula (1). .

  In the general formula (5), Z is preferably a halogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of reactivity, a chlorine atom and a bromine atom are preferable, and a bromine atom is more preferable.

The alkyl group, aryl group, and arylalkyl group represented by R ⁵ are the same as those specifically described and exemplified as the alkyl group, aryl group, and arylalkyl group represented by R in the above section X. The same thing.

  As the metal condensing agent, transition metals or transition metal compounds such as Cu, Fe, Co, Ni, Cr, V, Pd, Pt, and Ag are used, and Cu, Pd and compounds thereof are preferable, and Pd and compounds thereof are used. Is more preferable, and a palladium catalyst is more preferable.

  The amount of the metal condensing agent used is usually 0.001 mol or more per 1 mol of the secondary amine compound. The upper limit is not limited, but is preferably 0.1 mol or less from the viewpoint of raw material costs.

  Examples of the deoxidizer include carbonates, bicarbonates, hydroxides, and alkoxides of alkali metals and alkaline earth metals. Among these, sodium carbonate, potassium carbonate, sodium hydroxide, hydroxide Potassium, sodium methoxide, sodium ethoxide, potassium t-butoxide, sodium t-butoxide, cesium carbonate and the like are preferable.

  Although the usage-amount of the said deoxidizer is not specifically limited, Usually, it is 2-20 mol with respect to 1 mol of secondary amine compounds represented by the said Formula (4).

  Moreover, it is preferable to add a neutral ligand to this reaction from a viewpoint of a polymerization degree improvement. The neutral ligand is a ligand having no anion or cation. Specifically, 2,2′-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline, N, N′— Nitrogen-containing ligands such as tetramethylethylenediamine, triphenylphosphine, tolylphosphine, tributylphosphine, tri-t-butylphosphine, triphenoxyphosphine, 1,2-bisdiphenylphosphinoethane, 1,3-bisdiphenylphosphine Examples include tertiary phosphine ligands such as finopropane. When Pd or a compound thereof is used as the metal condensing agent, a tertiary phosphine ligand is preferable as a neutral ligand in view of the degree of polymerization.

  This reaction is usually performed in a solvent. Solvents used include aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamide, dimethyl sulfoxide, toluene, xylene, mesitylene, benzene , Aromatic hydrocarbon solvents such as n-butylbenzene, aliphatic hydrocarbon solvents such as tetralin and decalin, ether solvents such as tetrahydrofuran, 1,4-dioxane, dibutyl ether, tert-butyl methyl ether and dimethoxyethane And ester solvents such as ethyl acetate, butyl acetate and methyl benzoate, and alkyl halide solvents such as chloroform and dichloroethane. Among these, aromatic hydrocarbon solvents such as toluene and xylene are preferable from the viewpoint of increasing the molecular weight.

  The reaction temperature of this reaction is not particularly limited, and is usually about 0 to 200 ° C, and preferably about 20 to 160 ° C from the viewpoint of low heating costs. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed.

  The reaction time for this reaction is usually about 0.25 to 200 hours, and preferably about 0.25 to 50 hours from the viewpoint of productivity and the like.

-Polymer composition-
The polymer compound of the present invention can be mixed with at least one material selected from a hole transporting material, an electron transporting material, and a light emitting material to obtain a polymer composition. That is, the polymer composition of the present invention comprises the polymer compound of the present invention and at least one material selected from a hole transporting material, an electron transporting material, and a light emitting material. . In addition, the hole transport material, the electron transport material, and the light emitting material are as described in detail in the section of the polymer light emitting device described later. This polymer composition is particularly suitable for improving processability due to the effect of stabilizing the film quality or for improving device performance such as charge injection and transportability.

  In this polymer composition, the total amount and ratio of the materials are not particularly limited, and vary depending on the use of the polymer composition. For example, when used as a material for a polymer light emitting device, the blending amount and ratio described in the section of the polymer light emitting device described below may be used.

-Interlayer-
The polymer compound and / or polymer composition of the present invention can be used as an interlayer material. That is, the interlayer material contains the polymer compound and / or polymer composition of the present invention. In this specification, “interlayer material” means a material used for an interlayer layer. The “interlayer layer” is a polymer light-emitting device described later, and is provided between the hole injection layer and the light-emitting layer when the polymer light-emitting device has a hole injection layer and a light-emitting layer. Means a layer (usually a hole transport layer).

  In the interlayer material, optional components other than the polymer compound and polymer composition may be blended. For example, additives such as a crosslinking agent, a charge transport material, a light emitting material, a surfactant, and a stabilizer are blended. May be. This optional component is preferably 0 to 400 parts by weight, more preferably 0 to 150 parts by weight with respect to 100 parts by weight of the total amount of the polymer compound and the polymer composition.

-Liquid composition-
The polymer compound and / or polymer composition of the present invention is dissolved or dispersed in a solvent (in the description of the liquid composition, “solvent” includes not only a solvent but also a dispersion medium). It can be prepared as a composition. That is, the liquid composition of the present invention comprises the polymer compound and / or polymer composition of the present invention and a solvent, and is liquid at 25 ° C. Each of these polymer compounds and polymer compositions may be used alone or in combination of two or more. In addition, the liquid composition of the present invention is preferably in a state where the polymer compound and / or polymer composition is completely dissolved in a solvent, but is dispersed in the solvent as long as the action and effect of the present invention are not impaired. Even if it is in a dissolved state or partly undissolved, it does not matter. The liquid composition of the present invention is sometimes called an ink composition. This liquid composition is useful for producing a thin film for a polymer light emitting device, and is particularly useful in that the thin film can be formed by a method such as a printing method or a spin coating method.

  The polymer compound and polymer composition of the present invention contained in the liquid composition may be one type or two or more types, and contain a polymer compound other than the polymer compound of the present invention as long as the device characteristics and the like are not impaired. May be.

  As the solvent contained in the liquid composition, those capable of dissolving or uniformly dispersing the polymer compound and polymer composition of the present invention are preferable. Examples of the solvent include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene and other chlorine solvents, tetrahydrofuran, dioxane and other ether solvents, 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, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxy Polyhydric alcohols and derivatives thereof such as tan, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, 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 can be used individually by 1 type or in combination of 2 or more types. Among these solvents, the solvent has a structure containing at least one benzene ring, has a melting point of 0 ° C. or lower (typically 0 to −100 ° C.), and a boiling point of 100 ° C. or higher (typically 100 to 200). It is preferable to include one or more organic solvents that are at the same temperature.

  As the type of solvent, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ester solvents, ketone solvents are preferable from the viewpoints of solubility in organic solvents, uniformity during film formation, viscosity characteristics, and the like. . Moreover, it is preferable that the kind of the solvent contained in a liquid composition is two or more types from viewpoints, such as film forming property and an element characteristic.

  In addition to the polymer compound and polymer composition of the present invention, the liquid composition of the present invention includes, as an optional component, for example, a hole transport material, an electron transport material, a luminescent material, a stabilizer, a viscosity and / or Alternatively, an additive for adjusting the surface tension may be included. As this additive, a thickener for increasing the viscosity (usually high molecular weight compounds, poor solvents, etc.), a low molecular weight compound for decreasing the viscosity, a surfactant for decreasing the surface tension, and the like are appropriately combined. Can be used.

The high molecular weight compound as the thickener may be any compound that is soluble in the same solvent as the polymer compound and polymer composition of the present invention and does not inhibit light emission or charge transport. For example, high molecular weight polystyrene, polymethyl methacrylate, or the like can be used. When the polymer compound of the present invention has a high molecular weight (for example, a polystyrene-equivalent weight average molecular weight of about 2 × 10 ⁵ to 2 × 10 ⁶ ), the viscosity of the liquid composition is increased. Can do.

  When a poor solvent is used as the thickener, it is a solid content in the liquid composition (that is, a solid component other than the solvent contained in the composition (a solid component at 25 ° C.)), which is usually a polymer. Viscosity can be increased by adding a small amount of a poor solvent to a compound, a polymer composition, and optional components such as additives included in some cases. When a poor solvent is added for this purpose, the type and amount of the solvent may be selected within a range in which the solid content in the liquid composition does not precipitate. Specifically, 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 total weight of the liquid composition.

  The liquid composition may contain an antioxidant in order to improve storage stability. The antioxidant is not particularly limited as long as it is soluble in the same solvent as the polymer compound and polymer composition of the present invention and does not inhibit light emission or charge transport, such as a phenol-based antioxidant and a phosphorus-based antioxidant. Is exemplified.

  Furthermore, the liquid composition may contain water, a metal, and a salt thereof in a range of 1 to 1000 ppm on a weight basis with respect to the obtained liquid composition. Specific examples of the metal include lithium, sodium, calcium, potassium, iron, copper, nickel, aluminum, zinc, chromium, manganese, cobalt, platinum, iridium and the like. Moreover, silicon, phosphorus, fluorine, chlorine, and bromine may be contained in a range of 1 to 1000 ppm on a weight basis with respect to the obtained liquid composition.

  The total weight of the polymer compound of the present invention and the polymer composition in the liquid composition is a component other than the solvent (that is, the polymer composition, the polymer compound, and optionally added optional components, When an optional component contains a poor solvent, the poor solvent is not contained in components other than the solvent.) The weight is usually 20 wt% to 100 wt%, preferably 40 wt% to 100 wt%. % By weight.

  The proportion of the solvent that is an essential component in the liquid composition is usually 1% to 99.9% by weight, preferably 60% to 99.5% by weight, based on the total weight of the liquid composition. More preferably, it is 80 to 99.0% by weight.

  The viscosity of the liquid composition varies depending on the printing method to be applied. However, when the liquid composition is applied to a method in which the liquid composition passes through a discharge device, such as an ink jet printing method, in order to prevent clogging or flight bending at the time of discharge. Furthermore, it is preferable that it is the range of 2-20 mPa * s in 25 degreeC, It is more preferable that it is the range of 5-20 mPa * s, It is further more preferable that it is the range of 7-20 mPa * s.

-Thin film-
Next, the thin film of the present invention will be described.
The thin film of the present invention contains the polymer compound and / or polymer composition of the present invention. This thin film may be produced by any method, but preferably it can be produced by a printing method using the liquid composition described above. Examples of the thin film include a light-emitting thin film, a conductive thin film, and an organic semiconductor thin film. The “thin film” usually means a film having a thickness of 0.1 to 10,000 nm, preferably 1 to 1000 nm.

  In the case of producing a thin film using the liquid composition, for example, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, A thin film can be produced by spray coating, screen printing, flexographic printing, offset printing, inkjet printing, or the like. Among these, the liquid composition is preferably formed by a screen printing method, a flexographic printing method, an offset printing method, or an inkjet printing method, and more preferably formed by an inkjet printing method.

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

  The conductive thin film preferably has a surface resistance of 1 KΩ / □ or less, more preferably 100Ω / □ or less, and even more preferably 10Ω / □ or less. The lower limit is not particularly limited, but is typically about 1Ω / □. The electrical conductivity can be increased by doping the thin film with a Lewis acid, an ionic compound, or the like.

In the organic semiconductor thin film, the higher one of the electron mobility and the hole mobility is preferably 10 ⁻⁵ cm ² / V / second or more, and more preferably 10 ⁻³ cm ² / V / second or more. It is preferably 10 ⁻¹ cm ² / V / second or more. The upper limit is not particularly limited, but is about 1000 cm ² / V / second.

By using the thin film of the present invention as an organic semiconductor thin film, an organic transistor having the thin film can be produced. The production method is not particularly limited. For example, 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, An organic transistor can be manufactured.

-Polymer light emitting device-
Next, the polymer light-emitting device (also referred to as polymer LED) 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 containing the polymer compound and / or polymer composition of the present invention provided between the electrodes. The organic layer means a layer containing an organic substance and is not particularly limited. Specifically, for example, a light emitting layer, a hole injection layer, an electron injection layer (in this specification, a hole injection layer and an electron injection layer) Are collectively referred to as “charge injection layer”), hole transport layer, electron transport layer (in this specification, the hole transport layer and the electron transport layer are collectively referred to as “charge transport layer”). And the like. The polymer compound of the present invention can be used for one or two or more kinds of these light emitting layer, hole injection layer, hole transport layer, electron injection layer, electron transport layer, etc. Therefore, it is preferably used for the hole injection layer and the hole transport layer.

  The polymer light-emitting device of the present invention has a voltage of 3.5 V or more (typically about 3.5 to 15 V, more typically 5 V) between the anode and the cathode from the viewpoint of device brightness and the like. The maximum external quantum yield when applying is preferably 1% or more, and more preferably 1.5% or more.

  The structure of the polymer light emitting device of the present invention is not particularly limited. For example, (1) an electrode composed of an anode and a cathode, a light emitting layer provided between the electrodes, and the polymer compound and / or polymer of the present invention. A polymer light emitting device having a hole transport layer containing the composition, (2) an electrode composed of an anode and a cathode, a light emitting layer provided between the electrodes, a hole transport layer, the hole transport layer, and the A polymer light-emitting device having a hole injection layer containing the polymer compound and / or polymer composition of the present invention provided between the anode and (3) an electrode comprising an anode and a cathode; Polymer light emission comprising a light emitting layer and a hole injection layer provided, and a hole transport layer comprising the polymer compound and / or polymer composition of the present invention provided between the light emitting layer and the hole injection layer An element etc. are mentioned as a typical thing.

  In addition, for example, a polymer light emitting device in which an electron transport layer is provided between a cathode and a light emitting layer; a polymer light emitting device in which a hole transport layer is provided between an anode and a light emitting layer; a cathode and light emission Examples thereof include a polymer light emitting device in which an electron transport layer is provided between the layers and a hole transport layer is provided between the anode and the light emitting layer.

  Further, it may be a polymer light emitting device provided with an electron injection layer and a hole injection layer. For example, a polymer light emitting device provided with a charge injection layer adjacent to the cathode; a charge injection layer adjacent to the anode Examples thereof include a polymer light emitting device provided.

  Further, it may be a polymer light emitting device provided with an insulating layer having a function of facilitating charge injection. For example, a polymer light emitting device provided with an insulating layer adjacent to the cathode; an insulating layer adjacent to the anode A polymer light emitting device provided with In the polymer light-emitting device of the present invention, the average thickness of the insulating layer is preferably 0.5 mm at the lower limit and 4.0 mm at the upper limit.

  Regarding the structure of the polymer light-emitting device of the present invention, the order and number of layers to be laminated and the thickness of each layer may be appropriately adjusted in consideration of the light emission efficiency and the device life. Moreover, the light emitting layer, the hole transport layer, the electron transport layer, the hole injection layer, the electron injection layer, and the insulating layer may each be composed of two or more layers.

More specifically, for example, as follows.
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 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 ) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode 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 transporting layer / light emitting layer / electron transporting layer / insulating layer / cathode (where “/” means that each layer is adjacent)

  Hereinafter, the layers that the polymer light emitting device may have will be described in detail.

-Light emitting layer A light emitting layer means the layer which has the function to light-emit. When the light emitting layer contains the polymer compound of the present invention (that is, when the organic layer is a light emitting layer), the light emitting layer further comprises a hole transporting material, an electron transporting material, and a light emitting material. One or two or more selected materials may be included. Here, the luminescent material means a material that exhibits fluorescence and / or phosphorescence.

When the polymer light emitting device of the present invention has a light emitting layer, a light emitting material other than the polymer compound of the present invention may be used for the light emitting layer.

  The hole transporting material is as described in the section of the hole transport layer described later, and the electron transporting material is as described in the section of the electron transport layer described later.

  When the polymer compound of the present invention and the hole transporting material are mixed, the mixing ratio of the hole transporting material is usually 1% by weight to 80% by weight with respect to the entire mixture obtained. Preferably they are 5 weight%-60 weight%.

  When the polymer compound of the present invention and the electron transporting material are mixed, the mixing ratio of the electron transporting material is usually 1% by weight to 80% by weight with respect to the entire mixture obtained, preferably 5% to 60% by weight.

  When the polymer compound of the present invention and the luminescent material are mixed, the mixing ratio of the luminescent material is usually 1% by weight to 80% by weight, preferably 5% by weight with respect to the entire mixture obtained. % To 60% by weight.

  When mixing the polymer compound of the present invention and two or more materials selected from a luminescent material, a hole transporting material and an electron transporting material, the mixing ratio of the luminescent material to the entire mixture obtained Is usually 1 wt% to 50 wt%, preferably 5 wt% to 40 wt%, and the mixing ratio of the hole transporting material and the electron transporting material is the sum of them, usually 1 wt% -50% by weight, preferably 5-40% by weight, and the content of the polymer compound and polymer composition of the present invention is 99% -20% by weight based on the total mixture obtained. is there.

  The light emitting layer may be formed by any method. For example, a method of forming a film from a solution (for example, the above liquid composition) obtained by dissolving a polymer compound in a solvent can be mentioned. The film formation method from the solution (for example, the above liquid composition) includes spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, and dip coating. , Spray coating methods, screen printing methods, flexographic printing methods, offset printing methods, inkjet printing methods, and other coating methods can be used, and in terms of easy pattern formation and multi-color coating, screen printing methods, Printing methods such as flexographic printing, offset printing, and inkjet printing are preferred.

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

-Hole transport layer A hole transport layer means the layer which has the function to convey a hole. When the polymer light emitting device of the present invention has a hole transport layer, a hole transport material other than the polymer compound of the present invention may be used for the hole transport layer. Examples of the hole transporting material include polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in a side chain or a main chain, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, Examples include polyaniline or a derivative thereof, polythiophene or a derivative thereof, polypyrrole or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, poly (2,5-thienylene vinylene) or a derivative thereof.

  Specifically, as the hole transporting material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, and JP-A-2-209988 are disclosed. Examples described in JP-A-3-37992 and JP-A-3-152184 are exemplified.

  Among these, as the hole transporting material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, polyaniline or a derivative thereof, Polymeric hole transport materials such as polythiophene or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, poly (2,5-thienylene vinylene) or derivatives thereof are preferred, and polyvinylcarbazole or derivatives thereof are more preferred. Polysilane or a derivative thereof, or a polysiloxane derivative having an aromatic amine in the side chain or main chain.

  Further, the hole transporting material may be a low molecular compound. Examples of the low molecular weight compound include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives and the like. When a low molecular weight compound is used as the hole transporting material, it is preferably dispersed in a polymer binder.

  As the polymer binder, those that do not significantly inhibit charge transport are preferable, and those that do not strongly absorb visible light are preferably used. Examples of the polymer binder include poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like. .

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

  Examples of the polysilane or a derivative thereof include compounds described in Chem. Rev. 89, 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 or a derivative thereof has almost no hole transporting property in the siloxane skeleton structure, those having the structure of the low molecular weight hole transporting material in the side chain or main chain are preferably used. Particularly, those having a hole transporting aromatic amine in the side chain or main chain are exemplified.

  In the production of the hole transport layer, when the polymer compound of the present invention and the hole transport material are mixed, the mixing ratio of the hole transport material to the entire mixture obtained is usually 0. 01 to 80% by weight, preferably 0.1 to 60% by weight.

  The thin film used as the hole transport layer may be produced by any method. For example, in the case of a low molecular weight hole transport material, a method of film formation from a mixed solution with a polymer binder is exemplified. In the case of a molecular weight hole transporting material, a method by film formation from a solution is exemplified. Further, when the polymer compound of the present invention is used for a hole transport layer, a method of film formation from a solution (for example, the above liquid composition) obtained by dissolving the polymer compound in a solvent is exemplified. .

  As the solvent used for the film formation from the solution, a solvent capable of dissolving or uniformly dispersing the hole transporting material and the polymer binder 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 Polyhydric alcohols and derivatives thereof such as ethylene, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, 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 solvents can be used alone or in combination.

  The method for forming a film from the solution is not particularly limited. For example, from a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, and a wire bar coating method. Application methods such as dip coating, spray coating, screen printing, flexographic printing, offset printing, and ink jet printing 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. However, at least a thickness that does not cause pinholes is required. If it is too thick, the driving voltage of the element becomes high, which is not preferable. Therefore, the thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

-Electron transport layer The electron transport layer means a layer having a function of transporting electrons. When the polymer light-emitting device of the present invention has an electron transport layer, an electron transport material other than the polymer compound of the present invention may be used for the electron transport layer. As the electron transporting material, known materials can be used, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof. , Fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof, and the like.

  Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992, The thing etc. which are described in the same 3-152184 gazette are illustrated.

  Among these, oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinone or derivatives thereof, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof are preferable, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

  In the preparation of the electron transporting layer, when the polymer compound of the present invention and the electron transporting material are mixed, the mixing ratio of the electron transporting material is usually 0.01 to the total obtained mixture. 80% by weight, preferably 0.1 to 60% by weight.

  The thin film used as the electron transporting layer may be produced by any method. For example, in the case of a low molecular weight electron transporting material, a vacuum deposition method from a powder or a film deposition method from a solution or a molten state is exemplified. In the case of a high molecular weight electron transporting material, a method of forming a film from a solution or a molten state is exemplified. In film formation from a solution or a molten state, a polymer binder may be used in combination.

  Polymer binders include poly (p-phenylene vinylene) or its derivatives, poly (2,5-thienylene vinylene) or its derivatives, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, etc. Is exemplified.

  As a solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing an electron transporting material and a polymer binder is preferable. The solvent is the same as that specifically described and exemplified as the solvent that can dissolve or uniformly disperse the hole transporting material and the polymer binder in the above-mentioned section of the hole transport layer. These solvents can be used alone or in combination.

  The method for forming a film from a solution or a molten state is not particularly limited. For example, as a method for forming a film from a solution or a molten state of a hole transporting material in the above-described item of the hole transport layer, Same as described and illustrated.

  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. At least, the thickness should be such that no pinholes are generated. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  Also, among the charge transport layers (hole transport layer, electron transport layer) provided adjacent to the electrode, the one having the function of improving the charge injection efficiency from the electrode and having the effect of lowering the driving voltage of the element is In particular, it may be generally called a charge injection layer (a hole injection layer, an electron injection layer).

  Furthermore, the charge injection layer or the insulating layer may be provided adjacent to the electrode in order to improve the adhesion with the electrode or the charge injection from the electrode, and also improve the adhesion at the interface and prevent mixing. For example, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.

・ Charge injection layer (hole injection layer, electron injection layer)
The charge injection layer means a layer having a function of improving adhesion with the electrode or improving charge injection from the electrode. The hole injection layer and the electron injection layer, which are charge injection layers, can contain the polymer compound and / or polymer composition of the present invention. The thickness of the charge injection layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.

  When the polymer compound 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 of the present invention is used for an electron transport layer, it is preferably used at the same time as an electron donating compound. Here, in order to use simultaneously, there exist methods, such as mixing, copolymerization, and introducing as a side chain.

  Specific examples of the charge injection layer acting as a hole injection layer / electron transport layer include a layer containing a conductive polymer; provided between the anode and the hole transport layer, and included in the anode material and the hole transport layer. A layer containing a material having an ionization potential of an intermediate value with respect to the hole transporting material; provided between the cathode and the electron transporting layer and between the cathode material and the electron transporting material contained in the electron transporting layer. Examples thereof include a layer containing a material having a value electron affinity.

In the case where 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. in order to reduce the leakage current is more preferably less 10 ^-5 S / cm or more and 10 ² S / cm, more preferably less 10 ^-5 S / cm or more and 10 ¹ S / cm. Usually, in order to set the electric conductivity of the conductive polymer to 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, the 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 the anion include polystyrene sulfonate ion, alkylbenzene sulfonate ion, camphor sulfonate ion and the like, and examples of the cation include lithium ion, sodium ion, potassium ion and tetrabutylammonium ion.

  The material used for the charge injection layer may be appropriately selected in relation to the material of the electrode and the adjacent layer. Besides the polymer compound of the present invention, polyaniline and its derivative, polythiophene and its derivative, polypyrrole and its derivative , 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 ( Examples thereof include copper phthalocyanine) and carbon. Moreover, you may mix | blend DPHA (dipentaerythritol hexaacrylate) etc. as a crosslinking agent.

  In the production of the charge injection layer, the polymer compound of the present invention is made of other materials (for example, electron accepting compounds, electron donating compounds, materials other than the polymer compound of the present invention used for the charge injection layer, crosslinking agents, etc.) In the case of mixing with, the mixing ratio of the polymer compound of the present invention is usually 20 to 99.9% by weight, preferably 40 to 99% by weight, with respect to the entire mixture obtained.

-Insulating layer An insulating layer means the layer which has a function which improves the adhesiveness with an electrode, or improves the charge injection from an electrode. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials.

-Substrate The substrate used to form the polymer light-emitting device of the present invention may be any substrate that does not change when forming an electrode and forming an organic layer, such as glass, plastic, polymer film, A substrate of a material such as silicon is exemplified. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

・ Electrodes (anode, cathode)
Of the electrodes constituting the polymer light-emitting device of the present invention, at least one of the anode and the cathode is usually transparent or translucent. In particular, the anode side is preferably transparent or translucent.

  As the material of 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 thereof such as indium / tin / Films (e.g., NESA) created using conductive glass composed of oxide (ITO), indium, zinc, oxide, etc., gold, platinum, silver, copper, etc. are used. ITO, indium, zinc, oxide Tin oxide is preferred. Examples of methods for producing an anode using these materials include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. Further, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.

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

  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 the material of 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 their Two or more of these alloys, or 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 selected 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 material layer. The protective layer which protects may be mounted | worn. In order to stably use the polymer light emitting device for a long period of time, it is preferable to attach a protective layer and / or a protective cover in order to protect the device from the outside.

  As the protective layer, polyparaxylylene, acrylic resin, epoxy resin, 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 in which the protective cover is bonded to the element substrate with a heat effect resin or a photo-curing resin and sealed is preferable. Used. 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.

-Characteristics and Applications The polymer light-emitting device of the present invention is a high-performance polymer light-emitting device that can be driven with low voltage and high current efficiency. The polymer light-emitting element includes, for example, a planar light source (for example, a curved or planar light source for illumination), a segment display device (for example, a device using a segment type display element), a dot matrix display device ( For example, it can be used as a backlight of a dot matrix flat panel display), a liquid crystal display device (for example, a liquid crystal display), or the like. In order to obtain planar light emission using the polymer light emitting device, the planar anode and cathode may be arranged so as to overlap each other. In order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element, an organic layer of a non-light-emitting portion is formed extremely thick and substantially non-light-emitting. And a method of forming either 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 polymeric fluorescent substances 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 driven actively in combination with TFTs. 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. Furthermore, the planar light-emitting element is a self-luminous thin type, 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 be used as a curved light source or display device.

-Polymer field effect transistor-
Next, the case where the polymer compound of the present invention is used for the production of a polymer field effect transistor will be described.
The polymer field effect transistor has a source electrode, a drain electrode, a gate electrode, an active layer containing the polymer compound of the present invention, and an insulating layer as a structure. A source electrode and a drain electrode are provided in contact with the active layer containing the polymer compound of the present invention, and a gate electrode is provided with an insulating layer in contact with the active layer interposed therebetween. The polymer compound and / or polymer composition of the present invention can be used for the active layer.

  The polymer field effect transistor is usually formed on a support substrate. The material of the support substrate is not particularly limited as long as the characteristics as the polymer field effect transistor are not impaired, and examples thereof include a glass substrate, a flexible film substrate, and a plastic substrate.

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

  In forming the active layer, it is very advantageous and preferable to use an organic solvent-soluble polymer material (for example, the polymer compound of the present invention). As a film formation method from a solution in which the polymer material is dissolved in an organic solvent, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating A coating method such as a coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, or an inkjet printing method can be used.

  As the polymer field-effect transistor, a sealed polymer field-effect transistor formed by sealing an unsealed polymer field-effect transistor is preferable. Thereby, since the polymer field effect transistor is cut off from the atmosphere, it is possible to suppress deterioration in characteristics.

  Examples of the sealing method include a method of covering with a UV curable resin, a thermosetting resin, an inorganic SiONx film, and the like, and a method of bonding a glass plate or film with a UV curable resin, a thermosetting resin, or the like. In order to effectively cut off from the atmosphere, after producing an unsealed polymer field effect transistor, without exposing the process until sealing, for example, in a dry nitrogen atmosphere, in a vacuum, etc. Preferably it is done.

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

-Number average molecular weight and weight average molecular weight-
For the number average molecular weight and the weight average molecular weight, 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 compound 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 (trade name, manufactured by Tosoh) and one TSKgel SuperH2000 (trade name, 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 monomer (compound 2E) used for the synthesis of polymer compound 1-
Compound 2A

  Under an inert atmosphere, in a 300 ml three-necked flask, 5.00 g (29 mmol) of 1-naphthaleneboronic acid, 6.46 g (35 mmol) of 2-bromobenzaldehyde, 10.0 g (73 mmol) of potassium carbonate, 36 ml of toluene, 36 ml of ion-exchanged water And argon bubbling was performed for 20 minutes with stirring at room temperature. Next, 16.8 mg (0.15 mmol) of tetrakis (triphenylphosphine) palladium was added, and argon was bubbled for 10 minutes while stirring at room temperature. Thereafter, the temperature in the system was raised to 100 ° C. and reacted for 25 hours. After cooling to room temperature, the organic layer was extracted with toluene. The obtained organic layer was dried over sodium sulfate, and then the solvent was distilled off. Purification by a silica gel column using a mixed solvent of toluene: cyclohexane = 1: 2 as a developing solvent gave 5.18 g (yield 86%) of Compound 2A as white crystals.

¹ H-NMR (300 MHz / CDCl ₃ ):
δ 7.39-7.62 (m, 5H), 7.70 (m, 2H), 7.94 (d, 2H), 8.12 (dd, 2H), 9.63 (s, 1H)
MS (APCI (+)): (M + H) ^<+> 233

Compound 2B

  Under an inert atmosphere, 8.00 g (34.4 mmol) of Compound 2A and 46 ml of dehydrated THF were placed in a 300 ml three-necked flask and cooled to -78 ° C. Subsequently, 52 ml of n-octylmagnesium bromide (1.0 mol / l THF solution) was added dropwise over 30 minutes. After completion of dropping, the temperature was raised to 0 ° C., stirred for 1 hour, then warmed to room temperature and stirred for 45 minutes. The reaction was terminated by adding 20 ml of 1N hydrochloric acid in an ice bath, and the organic layer was extracted with ethyl acetate. The obtained organic layer was dried over sodium sulfate. Subsequently, after distilling off the solvent from the dried organic layer, 7.64 g (yield 64%) of Compound 2B was palely purified by purifying with a silica gel column using a mixed solvent of toluene: hexane = 10: 1 as a developing solvent. Obtained as a yellow oil. Although two peaks were observed in the HPLC measurement, they were judged to be a mixture of isomers because they were the same mass number in the LC-MS measurement.

・ Compound 2C

  Under an inert atmosphere, 5.00 g (14.4 mmol) of Compound 2B (mixture of isomers) and 74 ml of dehydrated dichloromethane were placed in a 500 ml three-necked flask, and stirred and dissolved at room temperature. Then, an etherate complex of boron trifluoride was added dropwise at room temperature over 1 hour, and after completion of the addition, the mixture was stirred at room temperature for 4 hours. While stirring, 125 ml of ethanol was slowly added. When the exotherm subsided, the organic layer was extracted with chloroform, the organic layer was washed with water twice, and the washed organic layer was dried over magnesium sulfate. Next, after the solvent was distilled off from the dried organic layer, the residue was purified by a silica gel column using hexane as a developing solvent to obtain 3.22 g (yield 68%) of Compound 2C as a colorless oil.

¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 3H), 1.03-1.26 (m, 14H), 2.13 (m, 2H), 4.05 (t, 1H), 7.35 (dd, 1H), 7 .46-7.50 (m, 2H), 7.59-7.65 (m, 3H), 7.82 (d, 1H), 7.94 (d, 1H), 8.35 (d, 1H) ), 8.75 (d, 1H)
MS (APCI (+)): (M + H) ^<+> 329

・ Compound 2D

  Under an inert atmosphere, 20 ml of ion-exchanged water was placed in a 200 ml three-necked flask, and 18.9 g (0.47 mol) of sodium hydroxide was added little by little with stirring to dissolve. After cooling the obtained aqueous solution to room temperature, 20 ml of toluene, 5.17 g (15.7 mmol) of Compound 2C and 1.52 g (4.72 mmol) of tributylammonium bromide were added, and the temperature was raised to 50 ° C. Next, n-octyl bromide was added dropwise, and after completion of the addition, the reaction was carried out at 50 ° C. for 9 hours. After completion of the reaction, the organic layer was extracted with toluene, and the organic layer was washed twice with water. The organic layer washed with water was dried over sodium sulfate. After the solvent was distilled off from the dried organic layer, it was purified by a silica gel column using hexane as a developing solvent to obtain 5.13 g (yield 74%) of Compound 2D as a yellow oil.

¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.52 (m, 2H), 0.79 (t, 6H), 1.00-1.20 (m, 22H), 2.05 (t, 4H), 7.34 (d, 1H), 7 40 to 7.53 (m, 2H), 7.63 (m, 3H), 7.83 (d, 1H), 7.94 (d, 1H), 8.31 (d, 1H), 8. 75 (d, 1H)
MS (APCI (+)): (M + H) ^<+> 441

Compound 2E

  Under an air atmosphere, 4.00 g (9.08 mmol) of Compound 2D and 57 ml of a mixed solvent of acetic acid: dichloromethane = 1: 1 were placed in a 50 ml three-necked flask, and dissolved by stirring at room temperature. Next, while adding 7.79 g (20.0 mmol) of benzyltrimethylammonium tribromide and stirring, zinc chloride was added until the benzyltrimethylammonium tribromide was completely dissolved. After stirring at room temperature for 20 hours, the reaction was stopped by adding 10 ml of 5% by weight aqueous sodium hydrogen sulfite solution. Subsequently, the organic layer was extracted with chloroform, and the organic layer was washed twice with an aqueous potassium carbonate solution. The washed organic layer was dried over sodium sulfate. The solvent was distilled off from the dried organic layer. Next, after purification twice with a flash column using hexane as a developing solvent, recrystallization with a mixed solvent of ethanol: hexane = 1: 1, followed by recrystallization with a mixed solvent of ethanol: hexane = 10: 1. Then, 4.13 g (yield 76%) of compound 2E was obtained as white crystals.

¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.60 (m, 2H), 0.91 (t, 6H), 1.01-1.38 (m, 22H), 2.09 (t, 4H), 7.62-7.75 (m, 3H), 7.89 (s, 1H), 8.20 (d, 1H), 8.47 (d, 1H), 8.72 (d, 1H)
MS (APPI (+)): (M + H) ^<+> 598

< Synthesis Example 2 >
-Synthesis of polymer compound 1-
After charging 22.5 g of compound 2E and 17.6 g of 2,2′-bipyridyl in a reaction vessel, the inside of the reaction system was replaced with nitrogen gas. To this, 1500 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, 31 g of bis (1,5-cyclooctadiene) nickel (0) was added to the obtained mixed solution, and the mixture was stirred at room temperature for 10 minutes and then reacted at 60 ° C. for 3 hours. This reaction was performed in a nitrogen gas atmosphere.

  After the reaction, the obtained reaction solution was cooled, and then a mixed solution of 25% by weight ammonia water 200 ml, methanol 900 ml and ion-exchanged water 900 ml was poured into this solution and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. The precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution thus obtained was filtered to remove insoluble matters, and the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was washed with a 1N aqueous hydrochloric acid solution, allowed to stand and separated, and then the toluene solution was recovered. Next, the recovered toluene solution was washed with about 3 wt% aqueous ammonia, allowed to stand and liquid-separated, and then the toluene solution was recovered. Next, the recovered toluene solution was washed with ion-exchanged water, allowed to stand and separated, and then the toluene solution was recovered. Next, this recovered toluene solution was poured into methanol to re-precipitate.

Next, the produced precipitate was recovered, and the precipitate was washed with methanol, and then the washed precipitate was dried under reduced pressure to obtain 6.0 g of a polymer. This polymer is referred to as polymer compound 1. The thus obtained polymer compound 1 had a polystyrene equivalent weight average molecular weight of 8.2 × 10 ⁵ and a number average molecular weight of 1.0 × 10 ⁵ .

-Evaluation of fluorescence characteristics of polymer compound 1-
A 0.8 wt% toluene solution of the obtained polymer compound 1 was spin coated on a quartz plate to prepare a thin film of polymer compound 1. The fluorescence spectrum of this thin film was measured using a fluorescence spectrophotometer (manufactured by JOBINYVON-SPEX, trade name: Fluorolog) at an excitation wavelength of 350 nm. In order to obtain the relative fluorescence intensity in the thin film, the spectrophotometer (trade name: Cary 5E, manufactured by Varian, Inc.) was obtained by integrating the fluorescence spectrum plotted in wavenumber with the intensity of Raman line of water as standard. The value assigned by the absorbance at the excitation wavelength was measured using.
The thus obtained polymer compound 1 had a fluorescence peak wavelength of 450 nm and a fluorescence intensity of 5.4.

<Synthesis Example 3 >
-Synthesis of monomer (compound 3E) used for the synthesis of polymer compound 2-
Compound 3A

  Under an inert atmosphere, 7 g of 2,8-dibromodibenzothiophene and 280 ml of THF were placed in a 1 l four-necked flask, stirred at room temperature, dissolved, and then cooled to -78 ° C. 29 ml of n-butyllithium (1.6 mol / l hexane solution) was added dropwise. After completion of dropping, the mixture was stirred for 2 hours while maintaining the temperature, and 13 g of trimethoxyboronic acid was added dropwise. After completion of dropping, the temperature was slowly raised to room temperature. After stirring at room temperature for 3 hours, disappearance of the raw material was confirmed by TLC. The reaction was terminated by adding 100 ml of 5% by weight sulfuric acid and stirred at room temperature for 12 hours. Water was added for washing, and the organic layer was extracted. After replacing the solvent with ethyl acetate, 5 ml of 30 wt% aqueous hydrogen peroxide was added and stirred at 40 ° C. for 5 hours. Thereafter, the organic layer was extracted, washed with a 10% by weight aqueous solution of ammonium iron (II) sulfate, dried, and the solvent was removed to obtain 4.43 g of a brown solid. By-products such as dimers were also produced from LC-MS measurement, and the purity of compound 3A was 77% (LC area percentage; hereinafter, the purity of the compound is simply indicated as “LC area percentage”. ).

MS (APCI (-)) :( M-H) - 215

Compound 3B

  Under an inert atmosphere, 4.43 g of compound 3A, 25.1 g of n-octyl bromide, and 12.5 g (23.5 mmol) of potassium carbonate were placed in a 200 ml three-necked flask, and 50 ml of methyl isobutyl ketone was added as a solvent. The mixture was heated at reflux for 6 hours. After completion of the reaction, the solvent was removed, the organic layer and the aqueous layer were separated with chloroform and water, the organic layer was extracted, and the organic layer was further washed twice with water. After drying over anhydrous sodium sulfate, purification was performed with a silica gel column (developing solvent: toluene / cyclohexane = 1/10) to obtain 8.49 g (LC area percentage 97%, yield 94%) of compound 3B.

¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.91 (t, 6H), 1.31-1.90 (m, 24H), 4.08 (t, 4H), 7.07 (dd, 2H), 7.55 (d, 2H), 7 .68 (d, 2H)

・ Compound 3C

  In a 100 ml three-necked flask, 6.67 g of compound 3B and 40 ml of acetic acid were placed, and the temperature was raised to 140 ° C. in an oil bath. Next, 13 ml of 30% by weight hydrogen peroxide water was added from the condenser, and after vigorous stirring for 1 hour, the reaction was terminated by pouring into 180 ml of cold water. After extracting with chloroform and drying the obtained organic layer, the solvent was removed to obtain 6.96 g (LC area percentage 90%, yield 97%) of compound 3C.

¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 6H), 1.26 to 1.87 (m, 24H), 4.06 (t, 4H), 7.19 (dd, 2H), 7.69 (d, 2H), 7 .84 (d, 2H)
MS (APCI (+)): (M + H) ^<+> 473

・ Compound 3D

  Under an inert atmosphere, 3.96 g of compound 3C and 15 ml of a mixed solution of acetic acid / chloroform (1: 1) (volume basis) were added to a 200 ml four-necked flask and stirred at 70 ° C. to dissolve. Next, 6.02 g of bromine was dissolved in 3 ml of an acetic acid / chloroform = 1: 1 mixture (volume basis), and the mixture was stirred for 3 hours. A sodium thiosulfate aqueous solution was added to the resulting solution to remove unreacted bromine, and the organic layer and the aqueous layer were separated with chloroform and water, and the organic layer was extracted and dried. By removing the solvent from the dried organic layer and purifying with a silica gel column (developing solvent: chloroform / hexane = 1/4), 4.46 g (LC area percentage 98%, yield 84%) of compound 3D was obtained. Obtained.

¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.95 (t, 6H), 1.30 to 1.99 (m, 24H), 4.19 (t, 4H), 7.04 (s, 2H), 7.89 (s, 2H)
MS (FD ⁺ ) M ⁺ 630

Compound 3E

  Under an inert atmosphere, 3.9 g of compound 3D and 50 ml of diethyl ether were placed in a 200 ml three-necked flask, heated to 40 ° C. and stirred. To the resulting solution, 1.17 g of lithium aluminum hydride was added little by little and allowed to react for 5 hours. Excess lithium aluminum hydride was decomposed by adding water little by little and washed with 5.7 ml of 36 wt% hydrochloric acid. The organic layer and the aqueous layer were separated with chloroform and water, and the organic layer was extracted and dried. The solvent was removed from the dried organic layer and purified by a silica gel column (developing solvent: chloroform / hexane = 1/5) to obtain 1.8 g (LC area percentage 99%, yield 49%) of compound 3E. Obtained.

¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 6H), 1.26 to 1.97 (m, 24H), 4.15 (t, 4H), 7.45 (s, 2H), 7.94 (s, 2H)
MS (FD ⁺ ) M ⁺ 598

  According to the MS (APCI (+)) method, peaks were detected at 615 and 598.

<Example 1 >
-Synthesis of polymer compound 2-
After charging 0.52 g of N, N′-diphenyl-1,4-phenylenediamine, 1.22 g of compound 3E and 0.58 g of sodium t-butoxy, the inside of the reaction system was replaced with nitrogen gas. After adding 0.05 g of tris (dibenzylideneacetone) dipalladium (0) to this, 0.02 g of tri-t-butylphosphine was added to this mixed solution and reacted at 100 ° C. for 8 hours. The reaction was performed in a nitrogen gas atmosphere. After completion of the reaction, this solution was cooled to room temperature, and then the cooled solution was poured into a mixed solution of 20 ml of ion-exchanged water and 20 ml of methanol and stirred. After stirring, the aqueous layer was removed, 1 g of radiolite was added and stirred, the resulting mixture was filtered on silica-activated alumina, and the filtrate was recovered. The collected filtrate was poured into 45 g of methanol and stirred. Next, the produced precipitate was recovered by filtration and dried under reduced pressure. After drying, 0.86 g of polymer was obtained. This polymer is referred to as polymer compound 2. The weight average molecular weight in terms of polystyrene of the polymer compound 2 was 3.7 × 10 ⁴ , and the number average molecular weight was 1.0 × 10 ⁴ .

-Evaluation of fluorescence characteristics of polymer compound 2-
The fluorescent property evaluation of the polymer compound 2 thus obtained was performed in the same manner as in Example 1. Polymer compound 2 had a fluorescence peak wavelength of 462 nm and a fluorescence intensity of 1.2.

<Synthesis Example 4 >
-Synthesis of monomer (compound 4D) used for the synthesis of polymer compound 3-
Compound 4A

  Under an inert atmosphere, 23.2 g (137.9 mmol) of benzofuran and 232 g of acetic acid were placed in a 1 l three-necked flask, stirred and dissolved at room temperature, and then heated to 75 ° C. After the temperature rise, 92.6 g (579.3 mmol) of bromine diluted with 54 g of acetic acid was added dropwise. After completion of the dropwise addition, the mixture was stirred for 3 hours while maintaining the temperature and allowed to cool. After confirming disappearance of the raw material by TLC, sodium thiosulfate water was added to terminate the reaction, and the mixture was stirred at room temperature for 1 hour. After stirring, filtration was performed, and the cake was separated by filtration, further washed with sodium thiosulfate water and water, and then dried. The obtained crude product was recrystallized from hexane to obtain Compound 4A. The yield was 21.8 g, and the yield was 49%.

¹ H-NMR (300 MHz / CDCl ₃ ):
δ 7.44 (d, 2H), 7.57 (d, 2H), 8.03 (s, 2H)

Compound 4B

  Under an inert atmosphere, 16.6 g (50.9 mmol) of Compound 4A and 293 g of tetrahydrofuran were placed in a 500 ml four-necked flask and cooled to -78 ° C. To the resulting solution, 80 ml of n-butyllithium (<1.6 mol / l hexane solution, 127.3 mmol) was added dropwise and stirred for 1 hour while maintaining the temperature. The obtained reaction liquid was dropped into a 1000 ml four-necked flask in an inert atmosphere, and 31.7 g (305.5 mmol) of trimethoxyboronic acid and 250 ml of tetrahydrofuran were added and cooled to -78 ° C. After completion of the dropwise addition, the temperature was slowly returned to room temperature, stirred for 2 hours at room temperature, and disappearance of the raw material was confirmed by TLC. After completion of the reaction, the obtained reaction solution was poured into a 2000 ml beaker containing 30 g of concentrated sulfuric acid and 600 ml of water to complete the reaction. To the resulting solution was added 300 ml of toluene, the organic layer was extracted, and further washed with water. After distilling off the solvent, 8 g of the solution and 160 ml of ethyl acetate were placed in a 300 ml four-necked flask, and then 7.09 g of 30 wt% hydrogen peroxide solution was added and stirred at 40 ° C. for 2 hours. The reaction solution thus obtained was poured into an aqueous solution of 71 g of ammonium iron (II) sulfate and 500 ml of water in a 1000 ml beaker. After stirring the obtained solution, the organic layer was extracted, and the organic layer was washed with water. The solvent was removed from the washed organic layer to obtain 6.72 g of a crude compound 4B.

MS spectrum: M ⁺ 200.0

Compound 4C

  Under an inert atmosphere, 2.28 g (11.4 mmol) of compound 4B and 23 g of N, N-dimethylformamide were placed in a 200 ml four-necked flask, stirred and dissolved at room temperature, and then 9.45 g (68.3 mmol) of potassium carbonate was added. The temperature was raised to ° C. After the temperature increase, a solution obtained by diluting 6.60 g (34.2 mmol) of n-octyl bromide with 11 g of N, N-dimethylformamide was added dropwise. After completion of the dropwise addition, the temperature was raised to 60 ° C., the mixture was stirred for 2 hours while maintaining the temperature, and disappearance of the raw material was confirmed by TLC. The reaction was terminated by adding 20 ml of water, then 20 ml of toluene was added, the organic layer was extracted, and the organic layer was washed twice with water. The washed organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off. The obtained crude product was purified with a silica gel column to obtain Compound 4C. The yield was 1.84 g, and the yield was 38%.

MS spectrum: M ⁺ 425.3

Compound 4D

  Under an inert atmosphere, 7.50 g (17.7 mmol) of Compound 4C and N, N-dimethylformamide were placed in a 500 ml four-necked flask, stirred at room temperature, dissolved, and then cooled in an ice bath. After cooling, a solution prepared by diluting 6.38 g (35.9 mmol) of N-bromosuccinimide with 225 ml of N, N-dimethylformamide was added dropwise. After completion of dropping, the mixture was stirred for 1 hour in an ice bath, stirred for 18.5 hours at room temperature, heated to 40 ° C., stirred for 6.5 hours while maintaining the temperature, and disappearance of the raw materials was confirmed by liquid chromatography. . The solvent was removed from the resulting reaction solution, and 75 ml of toluene was added and dissolved therein, and then the organic layer was washed with water three times. After drying over anhydrous sodium sulfate, the solvent was distilled off. About 4% of the obtained crude product was purified by silica gel column and liquid chromatography fractionation to obtain Compound 4D. The yield was 0.326g.

¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 6H), 1.26 to 1.95 (m, 24H), 4.11 (t, 4H), 7.34 (s, 2H), 7.74 (s, 2H)

MS spectrum: M ⁺ 582.1

<Example 2 >
-Synthesis of polymer compound 3-
After charging 0.52 g of N, N′-diphenyl-1,4-phenylenediamine, 1.19 g of compound 4D and 0.58 g of sodium t-butoxy, the inside of the reaction system was replaced with nitrogen gas. To this was added 0.05 g of tris (dibenzylideneacetone) dipalladium (0), and then 0.02 g of tri-t-butylphosphine was added to the mixture, followed by reaction at 100 ° C. for 8 hours. The reaction was performed in a nitrogen gas atmosphere. After the reaction, this solution was cooled to room temperature, and then the cooled solution was poured into a mixed solution of 20 ml of ion-exchanged water and 20 ml of methanol and stirred. After stirring, the aqueous layer was removed, 1 g of radiolite was added and stirred, filtered on silica-activated alumina, and the filtrate was recovered. The collected filtrate was poured into 45 g of methanol and stirred. Next, the produced precipitate was recovered by filtration and dried under reduced pressure. After drying, 0.97 g of polymer was obtained. This polymer is referred to as polymer compound 4. The polymer compound 3 had a polystyrene equivalent weight average molecular weight of 2.8 × 10 ⁴ and a number average molecular weight of 6.1 × 10 ³ .

-Evaluation of fluorescence characteristics of polymer compound 3-
The fluorescent property evaluation of the polymer compound 4 thus obtained was performed in the same manner as in Example 1. Polymer compound 3 had a fluorescence peak wavelength of 467 nm and a fluorescence intensity of 1.1.

<Example 3>
-Preparation of hole injection layer 1-
2% by weight of polymer compound 2 with respect to toluene, and 25% by weight of DPHA (dipentaerythritol hexaacrylate (product name: KAYARAD DPHA) manufactured by Nippon Kayaku Co., Ltd.) as a crosslinking agent are added with respect to polymer compound 1. The resulting solution was filtered through a 0.2 micron diameter Teflon (registered trademark) filter to prepare a coating solution. This coating solution was formed by spin coating at 1000 rpm on a glass substrate provided with an ITO film having a thickness of 150 nm by a sputtering method. The film thus obtained was baked under baking conditions of 300 ° C./20 minutes in a nitrogen atmosphere to obtain a hole injection layer 1 having a post-baking film thickness of about 50 nm.

<Example 4>
-Production of hole injection layer 2-
2% by weight of polymer compound 3 with respect to toluene, and 25% by weight of DPHA (dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA)) as a crosslinking agent are added with respect to polymer compound 1. The resulting solution was filtered through a 0.2 micron diameter Teflon (registered trademark) filter to prepare a coating solution. This coating solution was formed by spin coating at 1000 rpm on a glass substrate provided with an ITO film having a thickness of 150 nm by a sputtering method. The film thus obtained was baked under baking conditions of 300 ° C./20 minutes in a nitrogen atmosphere to obtain a hole injection layer 2 having a post-baking film thickness of about 50 nm.

-Creation of PEDOT hole injection layer-
A glass substrate having an ITO film with a thickness of 150 nm formed by sputtering is formed by spin coating using a solution of PEDOT: poly (ethylenedioxythiophene) / polystyrene sulfonic acid (trade name: Baytron, manufactured by Starck). The film thus obtained was dried on the hot plate at 200 ° C. for 10 minutes in the air to obtain a PEDOT hole injection layer having a thickness of 50 nm.

< Reference example >
-Preparation of solution composition 1 for light emitting layer-
Polymer compound 1 is 0.5% by weight with respect to toluene, and DCBP (4,4'-bis (9-carbazoyl) -biphenyl (manufactured by Dojindo Laboratories)) as a charge transport additive is high. After 160 wt% of the molecular compound 1 was mixed and dissolved, the obtained solution was filtered through a 0.2 micron diameter Teflon (registered trademark) filter to prepare a composition 1 for a light emitting layer.

<Examples 5 and 6, Comparative Example 1>
-Creation and evaluation of light-emitting elements-
A hole injection layer was laminated on the anode as shown in Table 1, and the solution composition for the light emitting layer was coated thereon with a thickness of about 70 nm by spin coating. After drying this at 90 ° C. under reduced pressure for 1 hour, 4 nm of lithium fluoride was deposited as a cathode buffer layer, 5 nm of calcium was deposited as a cathode, and then 100 nm of aluminum was deposited to produce a polymer light emitting device. The degree of vacuum at the time of vapor deposition was in the range of 1 × 10 ^{−3 to} 9 × 10 ⁻³ Pa in any case. The luminance of EL light emission from the polymer light emitter was measured by applying voltage stepwise to the polymer light emitting device having a light emitting portion of 2 mm × 2 mm (area 4 mm ² ) obtained in this way. A current efficiency value was obtained. Table 1 shows the maximum value of the current efficiency of the obtained polymer light emitting device and the y value of the CIE chromaticity coordinates of EL emission.

<Evaluation>
As can be seen from Table 1, the polymer light-emitting devices prepared in Examples 5 and 6 having the hole injection layer containing the polymer compound of the present invention do not use the hole injection layer containing the polymer compound of the present invention. Compared with the polymer light emitting device of Comparative Example 1, a marked improvement in the maximum current efficiency was observed. Therefore, the polymer compound of the present invention can be preferably used as a hole injection layer or the like.

Claims (17)

A polymer compound comprising a repeating unit represented by the following general formula (1) :

[In the formula, X represents an atom or a divalent group that forms a 5-membered ring or a 6-membered ring together with two atoms on the A ring and two atoms on the B ring; The divalent group contains at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom and a silicon atom. A ring and B ring independently represent an aromatic hydrocarbon ring which may have a substituent or a heterocyclic ring which may have a substituent, and when there are a plurality of substituents, they are bonded to each other. In the case where Ar1 represents a divalent aromatic hydrocarbon group which may have a substituent or a divalent organic group having a heterocyclic skeleton, and there are a plurality of substituents May be bonded to each other to form a ring. Ar2 and Ar3 each independently represent a monovalent aromatic hydrocarbon group which may have a substituent or a monovalent organic group having a heterocyclic skeleton, and when a plurality of substituents are present, they are bonded to each other. To form a ring. R ^* represents a linking group, and h represents 0 or 1. A plurality of R ^* may be the same or different. ]
A polymer compound, wherein the repeating unit represented by the general formula (1) is any one of the repeating units shown below.

[Where,
R is independently hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl Group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted silyl group, cyano group, nitro group, or Represents a monovalent organic group having a heterocyclic skeleton,
R ′ is independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group Group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent organic group having a heterocyclic skeleton, carboxyl group, substituted carboxyl group and cyano group To express.
n is a positive integer, a is 1 to 3, b is 0 to 4, and c is an integer of 0 to 5. When a plurality of ac are present, each may be the same or different. ] The polymer compound according to claim 1, wherein the weight average molecular weight in terms of polystyrene is 10 ³ to 10 ⁸ . A hole transport material, electron transport material and a polymeric composition characterized by containing a polymer compound according at least one material selected from the group consisting of light emitting material as in claim 1 or 2. The following general formula (4):

[Wherein, Ar1, Ar2, Ar3, R ^* and h are as described above. ]
A secondary amine compound represented by the following general formula (5):

[Wherein, X is as defined above, and Z represents a halogen atom or —SO ₂ R ⁵ (wherein R ⁵ represents an alkyl group, an aryl group, or an arylalkyl group). ]
Method for producing a polymer according to claim 1 or 2 and a compound represented by in, characterized in that the reaction in the presence of a metal condensing agent and deoxidizing agents. The production method according to claim 4 , wherein the metal condensing agent is a palladium catalyst. A liquid composition comprising the polymer compound according to claim 1 or 2 or the polymer composition according to claim 3 and a solvent. A thin film comprising the polymer compound according to claim 1 or 2 or the polymer composition according to claim 3 . An organic transistor comprising the thin film according to claim 7 . An electrode comprising an anode and a cathode, and an organic layer comprising the polymer compound according to claim 1 or 2 or an organic layer comprising the polymer composition according to claim 3 provided between the electrodes. Molecular light emitting device. The polymer light emitting device according to claim 9 , wherein the organic layer is a light emitting layer. An electrode comprising an anode and a cathode, a light-emitting layer provided between the electrodes, and a hole transport layer containing the polymer compound according to claim 1 or 2 or the polymer composition according to claim 3 The polymer light-emitting device according to claim 9 . The electrode comprising an anode and a cathode, a light emitting layer and a hole transport layer provided between the electrodes, and the polymer compound according to claim 1 or 2 provided between the hole transport layer and the anode polymer light-emitting device according to claim 9, characterized in that it comprises a hole injection layer comprising a polymer composition according to claim 3. An electrode comprising an anode and a cathode, a light emitting layer and a hole injection layer provided between the electrodes, and the polymer compound according to claim 1 or 2 provided between the light emitting layer and the hole injection layer polymer light-emitting device according to claim 9, characterized in that it comprises a hole transport layer comprising a polymer composition according to claim 3. A planar light source using the polymer light emitting device according to any one of claims 9 to 13 . A segment display device using the polymer light emitting device according to any one of claims 9 to 13 . A dot matrix display device comprising the polymer light emitting device according to any one of claims 9 to 13 . A liquid crystal display device comprising the polymer light emitting device according to any one of claims 9 to 13 as a backlight.