JP5299017B2 - Polymer compound and polymer light emitting device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer compound which provides a long life light-emitting device when used as a light-emitting material for the light-emitting device. <P>SOLUTION: The polymer compound includes a repeating unit represented by formula (1), and has a number average molecular weight of 10<SP>3</SP>-10<SP>8</SP>in terms of polystyrene. In the formula (1), Ar<SB>1</SB>, Ar<SB>2</SB>, Ar<SB>3</SB>, Ar<SB>4</SB>, Ar<SB>5</SB>, Ar<SB>6</SB>, and Ar<SB>7</SB>represent each independently an arylene group or a divalent heterocyclic group, and E<SB>5</SB>and E<SB>6</SB>represent each independently an aryl group (A) or a univalent heterocyclic group (B). n represents 2, and l, m, n, o, and p represent 0. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a polymer compound and a polymer light-emitting device (hereinafter sometimes referred to as polymer LED) using the polymer compound.

の繰り返し単位を含む高分子化合物が開示されている（例えば、特許文献１参照）。 High-molecular-weight light-emitting materials have been studied in various ways because they are soluble in solvents and can form a light-emitting layer in a light-emitting element by a coating method, unlike low-molecular-weight materials. Polymer compounds containing one or two nitrogen atoms bonded to an aromatic ring are known.
For example, as a polymer compound containing two nitrogen atoms in which all three bonds are bonded to the aromatic ring in the repeating unit, the following formula

A polymer compound containing a repeating unit of is disclosed (for example, see Patent Document 1).

International Publication No. 99/54385 Pamphlet

However, when the known polymer compound is used as a light emitting material of a light emitting device, there is a problem that the life of the light emitting device is not yet sufficient.
An object of the present invention is to provide a polymer compound that gives a light-emitting element having a longer lifetime when used as a light-emitting material of the light-emitting element.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors, as a light-emitting material for a light-emitting element, include a polymer compound containing three or more nitrogen atoms in which all three bonds are bonded to an aromatic ring in a repeating unit. It has been found that the lifetime of the light emitting element is improved by using it, and the present invention has been completed.

〔式中、Ａｒ_１、Ａｒ_２、Ａｒ_３、Ａｒ_４、Ａｒ_５、Ａｒ_６およびＡｒ_７はそれぞれ独立に、アリーレン基または２価の複素環基を表し、Ｅ_１、Ｅ_２、Ｅ_３、Ｅ_４、Ｅ_５およびＥ_６はそれぞれ独立にアリール基（Ａ）または１価の複素環基（Ｂ）を表す。ｌ、ｍおよびｎはそれぞれ独立に0〜2の整数を表し、oおよびｐはそれぞれ独立に0または1を表し、ｌ＋ｍ＋ｎ＋ｏ＋pは２以上である。ただし、式中におけるＮの数の合計は３以上である。
Ａｒ_２、Ａｒ_４、Ａｒ_５、

がそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。〕 That is, the present invention relates to a polymer compound containing a repeating unit represented by the following formula (1) and having a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ .

[Wherein, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , Ar ₆ and Ar ₇ each independently represent an arylene group or a divalent heterocyclic group, and E ₁ , E ₂ , E ₃ , E ₄ , E ₅ and E ₆ each independently represents an aryl group (A) or a monovalent heterocyclic group (B). l, m and n each independently represent an integer of 0 to 2, o and p each independently represent 0 or 1, and l + m + n + o + p is 2 or more. However, the total number of N in the formula is 3 or more.
Ar ₂ , Ar ₄ , Ar ₅ ,

When there are a plurality of each, they may be the same or different. ]

  The polymer compound of the present invention provides a light-emitting element having a longer lifetime when used as a light-emitting material of the light-emitting element. Therefore, the polymer LED containing the polymer compound of the present invention can be used for a curved or flat light source, a segment type display element, a dot matrix flat panel display and the like for backlight or illumination of a liquid crystal display.

In the above formula (1), Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , Ar ₆ and Ar ₇ each independently represent an arylene group or a divalent heterocyclic group, and the arylene group, the 2 The valent heterocyclic group may have a substituent.

Here, the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and those having a condensed ring, two or more independent benzene rings or condensed rings directly or a group such as vinylene. The thing couple | bonded through is also included. The arylene group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, and a substituted amino group. , Silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano And an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a substituted amino group, a substituted silyl group, a substituted silyloxy group, and a monovalent heterocyclic group are preferable.

Carbon number of the part except the substituent in an arylene group is about 6-60 normally, Preferably it is 6-20. Moreover, the total carbon number including the substituent of an arylene group is about 6-100 normally.

  Examples of the arylene group include a phenylene group (for example, formulas 1 to 3 in the following figure), a naphthalene-diyl group (formulas 4 to 13 in the following figure), an anthracene-diyl group (formulas 14 to 19 in the following figure), and a biphenyl-diyl group (the following figure). Formulas 20-25), terphenyl-diyl groups (formulas 26-28 in the figure below), condensed ring compound groups (formulas 29-35 in the figure below), fluorene-diyl groups (formulas 36-38 in the figure below), indenofluorene -Diyl (lower figures 38A-38B), stilbene-diyl (formulas A-D in the lower figure), distilbene-diyl (formulas E, F in the lower figure) and the like. Of these, a phenylene group, a biphenyl-diyl group, a fluorene-diyl group, and a stilbene-diyl group are preferable.

In the present invention, the divalent heterocyclic group means a remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound, and the group may have a substituent.
Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic in the ring. Say things. An aromatic heterocyclic group is preferable.
Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, and a substituted amino group. , Silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano And an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a substituted amino group, a substituted silyl group, a substituted silyloxy group, and a monovalent heterocyclic group are preferable.
Carbon number of the part except the substituent in a bivalent heterocyclic group is about 3-60 normally.
Moreover, the total carbon number including the substituent of a bivalent heterocyclic group is about 3-100 normally.

Examples of the divalent heterocyclic group include the following.
Divalent heterocyclic group containing nitrogen as a hetero atom; pyridine-diyl group (formula 39 to 44 in the following figure), diazaphenylene group (formula 45 to 48 in the figure below), quinoline diyl group (formula 49 to 63 in the figure below), quinoxaline Diyl groups (formulas 64 to 68 in the lower figure), acridine diyl groups (formulas 69 to 72 in the lower figure), bipyridyldiyl groups (formulas 73 to 75 in the lower figure), phenanthroline diyl groups (formulas 76 to 78 in the lower figure), and the like.
Groups containing silicon, nitrogen, selenium and the like as a hetero atom and having a fluorene structure (formulas 79 to 93 in the following figure).
5-membered ring heterocyclic groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom: (formulae 94 to 98 in the following figure) and the like.
5-membered ring condensed hetero groups containing silicon, nitrogen, selenium and the like as a hetero atom: (Formulas 99 to 108 in the following figure).
A 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom and bonded in the α-position of the heteroatom to form a dimer or oligomer: (Formulas 109 to 113 in the figure below), etc. .
A 5-membered heterocyclic group containing silicon, nitrogen, sulfur, selenium or the like as a heteroatom, and a group bonded to the phenyl group at the α-position of the heteroatom: (formula 113 to 119 in the following figure).
Groups in which a phenyl group, a furyl group, or a thienyl group is substituted on a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur, etc. as a hetero atom: (Formula 120 to 125 in the following figure).

In the above formulas 1-125, 38A, 38B, A, B, C, D, E, and F, each R independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group. Group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy Represents a group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group.

  In the substituent which the arylene group or divalent heterocyclic group may have, the alkyl group may be linear, branched or cyclic. The number of carbon atoms is usually about 1 to 20, specifically, 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-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, Examples thereof include a perfluorooctyl group, and a methyl group, butyl group, t-butyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, and 3,7-dimethyloctyl group are preferable.

  The alkoxy group may be linear, branched or cyclic. The number of carbon atoms is usually about 1 to 20, specifically, methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyl. Oxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, Examples include perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group, methoxymethyloxy group, 2-methoxyethyloxy group, methoxy group, butoxy group, t-butoxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy , 3,7-dimethyl octyloxy group are preferable.

  The alkylthio group may be linear, branched or cyclic. The number of carbon atoms is usually about 1 to 20, specifically, methylthio group, ethylthio group, propylthio group, i-propylthio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexyl. Examples include thio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, trifluoromethylthio group, and the like. Methylthio group, butylthio group, t- A butylthio group, a hexylthio group, an octylthio group, a 2-ethylhexylthio group, a decylthio group, and a 3,7-dimethyloctylthio group are preferred.

An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. Here, the aromatic hydrocarbon includes those having a condensed ring and those having two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene. The number of carbon atoms is usually about 6 to 60, specifically, a phenyl group, C ₁ -C ₁₂ alkoxyphenyl group (C ₁ -C ₁₂ indicates that it is 1 to 12 carbon atoms. The same applies hereinafter . there), C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl, 2-naphthyl, 1-anthracenyl group, 9-anthracenyl group, a phenanthrene - yl group, a pyrene - yl group, perylene - yl group, a pentafluorophenyl group and the like, C ₁ -C ₁₂ alkoxyphenyl group, is C ₁ -C ₁₂ alkylphenyl group are preferable.
Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2 -Ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
Specific examples of C ₁ -C ₁₂ alkyl include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl, lauryl and the like are exemplified.

The aryloxy group, the carbon number of usually about 6 to 60, specifically, 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, C ₁ -C ₁₂ alkoxy phenoxy group, a C ₁ -C ₁₂ alkylphenoxy group are preferable.
Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2 -Ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ such as methyl as alkyl, ethyl, dimethyl, propyl, 2,4,6-trimethyl, methyl ethyl, i- propyl, butyl, i- butyl, t- butyl, pentyl, isoamyl, hexyl, Examples include heptyl, octyl, nonyl, decyl, dodecyl and the like.

The arylthio group, the carbon number of usually about 3 to 60, specifically, phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2 - naphthylthio group, pentafluorophenylthio group and the like, C ₁ -C ₁₂ alkoxyphenyl-thio group, a C ₁ -C ₁₂ alkyl phenylthio group are preferable.

Arylalkyl group has a carbon number of usually about 7 to 60, specifically, 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 and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group are preferable.

The arylalkoxy group usually has about 7 to 60 carbon atoms, and specifically includes a phenylmethoxy group, a phenylethoxy group, a phenylbutoxy group, a phenylpentyloxy group, a phenylhexyloxy group, a phenylheptyloxy group, a phenyl group. 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 groups such as octyloxy, 1-naphthyl -C ₁ -C ₁₂ alkoxy groups, 2-naphthyl -C ₁ -C ₁₂ alkoxy groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy group are preferable.

Arylalkenyl group has a carbon number of usually about 8 to 60, specifically, a phenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, C ₁ ~ C ₁₂ alkylphenyl-C ₂ -C ₁₂ alkenyl group, 1-naphthyl-C ₂ -C ₁₂ alkenyl group, 2-naphthyl-C ₂ -C ₁₂ alkenyl group and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl group, C ₂ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkenyl groups are preferred.

The arylalkynyl group usually has about 8 to 60 carbon atoms, and specifically includes a phenyl-C ₂ -C ₁₂ alkynyl group, a C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkynyl group, a C _1- C ₁₂ alkylphenyl-C ₂ -C ₁₂ alkynyl group, 1-naphthyl-C ₂ -C ₁₂ alkynyl group, 2-naphthyl-C ₂ -C ₁₂ alkynyl group and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferable.

Arylalkylthio group has a carbon number of usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ ~ C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkylthio group, 1-naphthyl-C ₁ -C ₁₂ alkylthio group, 2-naphthyl-C ₁ -C ₁₂ alkylthio group and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group are preferable

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl The group or the monovalent heterocyclic group may have a substituent. The carbon number is usually about 1 to 60 without including the carbon number of the substituent.
Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, i-propylamino group, diisopropylamino group, butylamino group, i-butylamino 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, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di ( ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group , pyrimidylamino group, Pirajiruamino group, 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 groups, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino groups, 1-naphthyl - C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ alkylamino groups.

Examples of the substituted silyl group include 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. Degree. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
Specifically, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, t-butylsilyldimethylsilyl group, pentyldimethyl Silyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, a phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group, 1-naphthyl -C ₁ -C ₁₂ alkylsilyl group, 2-naphthyl C ₁ -C ₁₂ alkylsilyl group, a phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzylsilyl group, diphenylmethylsilyl group, t- butyl diphenyl silyl group, Examples thereof include a dimethylphenylsilyl group.

Examples of the substituted silyloxy group include a silyloxy group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. Degree.
Specifically, trimethylsilyloxy group, triethylsilyloxy group, tripropylsilyloxy group, tri-i-propylsilyloxy group, dimethyl-i-propylsilyloxy group, diethyl-i-propylsilyloxy group, t- Butylsilyldimethylsilyloxy group, pentyldimethylsilyloxy group, hexyldimethylsilyloxy group, heptyldimethylsilyloxy group, octyldimethylsilyloxy group, 2-ethylhexyl-dimethylsilyloxy group, nonyldimethylsilyloxy group, decyldimethylsilyloxy group Group, 3,7-dimethyloctyl-dimethylsilyloxy group, lauryldimethylsilyloxy group, phenyl-C1-C12 alkylsilyloxy group, C1-C12 alkoxyphenyl-C1-C12 alkylsilyloxy group, C1-C12 Alkylphenyl-C1-C12 alkylsilyloxy group, 1-naphthyl-C1-C12 alkylsilyloxy group, 2-naphthyl-C1-C12 alkylsilyloxy group, phenyl-C1-C12 alkyldimethylsilyloxy group, triphenylsilyloxy group Group, tri-p-xylylsilyloxy group, tribenzylsilyloxy group, diphenylmethylsilyloxy group, t-butyldiphenylsilyloxy group, dimethylphenylsilyloxy group, trimethoxysilyloxy group, triethoxysilyloxy group, Examples include tripropyloxysilyloxy group, tri-i-propylsilyloxy group, dimethyl-i-propylsilyloxy group, methyldimethoxysilyloxy group, ethyldimethoxysilyloxy group, and the like.

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

  Acyl groups usually have about 2 to 20 carbon atoms, and specific examples include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, benzoyl, trifluoroacetyl, and pentafluorobenzoyl groups. Is done.

  The acyloxy group usually has about 2 to 20 carbon atoms. Specifically, the acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetyloxy group, pentane Examples include a fluorobenzoyloxy group.

As the imine residue, an imine compound (refers to 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, and has about 2 to 20 carbon atoms, and specific examples thereof include the following groups.

  The amide group usually has about 2 to 20 carbon atoms, and specifically includes a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diamide group. Examples include an acetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group, a dipentafluorobenzamide group, and the like.

Examples of the acid imide group include residues obtained by removing the hydrogen atom bonded to the nitrogen atom from the acid imide, the number of carbons is about 4 to 20, and specific examples include the following groups. The

The monovalent heterocyclic group refers to a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and the group may have a substituent.
The carbon number of the unsubstituted monovalent heterocyclic group is usually about 4 to 60, and preferably 4 to 20.
The monovalent heterocyclic group, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are thienyl group, pyridyl group are preferable . C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

  The substituted carboxyl group usually has about 2 to 60 carbon atoms, and refers to a carboxyl group substituted with an alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group, such as a methoxycarbonyl group, an ethoxycarbonyl group, or a propoxycarbonyl group. Group, i-propoxycarbonyl group, butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2 -Ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoro Butoxycarbonyl group, perfluoro-butoxycarbonyl group, perfluorohexyloxy carbonyl group, perfluorooctyloxy carbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group, and the like. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The carbon number of the substituted carboxyl group does not include the carbon number of the substituent.

In the above example, one structural formula has a plurality of Rs, but they may be the same or different. In order to increase the solubility in a solvent, it is preferable that at least one of a plurality of Rs in one structural formula is other than a hydrogen atom, and the shape of a repeating unit including a substituent has little symmetry. Is preferred. Moreover, it is preferable that one or more of R in one structural formula is a group containing a cyclic or branched alkyl group. A plurality of R may be connected to form a ring.
In the above formula, in the substituent in which R contains an alkyl group, the alkyl group may be linear, branched or cyclic, or a combination thereof. - ethylhexyl group, 3,7-dimethyl octyl group, a cyclohexyl group, etc. 4-C ₁ ~C ₁₂ alkyl cyclohexyl groups.
Furthermore, the methyl group or methylene group of the alkyl group of the group containing the alkyl group may be replaced with a methyl group or methylene group substituted with a hetero atom or one or more fluorine atoms. Examples of these heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms and the like.
Furthermore, when R includes an aryl group or a heterocyclic group as a part thereof, they may further have one or more substituents.

〔式中、Ｒa、Ｒb、Ｒc、およびＲdはそれぞれ独立に、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、シリルオキシ基、置換シリルオキシ基、ハロゲン原子、アシル基、アシルオキシ基、イミノ基、アミド基、イミド基、1価の複素環基、カルボキシル基、置換カルボキシル基またはシアノ基を表す。ｑは１〜３の整数を表す。Ｒa、Ｒb、Ｒc、およびＲdがそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。また、ＲaとＲb、ＲcとＲdはそれぞれ、それらが結合するベンゼン環上の炭素原子と一緒になって芳香環を形成していてもよい。〕 In the repeating unit represented by the above formula (1), Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , Ar ₆ and Ar ₇ are each independently a group represented by the following formula (2). preferable.

[In the formula, Ra, Rb, Rc and Rd are each independently a hydrogen atom, 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, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy group, imino group, amide group, imide group, monovalent Represents a heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. q represents an integer of 1 to 3. When a plurality of Ra, Rb, Rc, and Rd are present, they may be the same or different. Ra and Rb, and Rc and Rd may each form an aromatic ring together with the carbon atom on the benzene ring to which they are bonded. ]

In the group represented by the above formula (2), the aromatic ring that forms an aromatic ring together with the carbon atom on the benzene ring to which Ra and Rb, Rc and Rd are bonded includes a benzene ring, a naphthalene ring, and an anthracene ring. Aromatic hydrocarbon rings such as tetracene ring, pentacene ring, pyrene ring and phenanthrene ring; and heteroaromatic rings such as pyridine ring, bipyridine ring, phenanthroline ring, quinoline ring, isoquinoline ring, thiophene ring, furan ring and pyrrole ring And a benzene ring, a naphthalene ring, and a pyridine ring are preferable.

  The aromatic ring is independently 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, an amino group, Substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy group, imino residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl And may have a substituent selected from the group consisting of a group and a cyano group. Moreover, when there are a plurality of substituents, they may be the same or different.

In the above formula (1), E ₁ , E ₂ , E ₃ , E ₄ , E ₅ and E ₆ each independently represents an aryl group or a monovalent heterocyclic group. The aryl group and the monovalent heterocyclic group may have a substituent.
Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylthio group, an arylalkenyl group, an arylalkynyl group, an arylalkylthio group, an amino group, and a substituted amino group. , Silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy group, imino residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group and cyano Groups.

Here, the aryl group, monovalent heterocyclic group, and substituent have the same meaning as described above.

In addition, when E ₁ , E ₂ , E ₃ , E ₄ , E ₅ , E ₆ have a substituent other than a halogen atom and a cyano group among the above substituents, these substituents are bonded to each other to form a ring May be formed.

In the above formula (1), the aryl group (A) preferably has one or more substituents on the carbon atom selected by the following (C).
(C): The highest occupied molecular orbital of an arylamine compound in which the bond in (A) is substituted with an amino group and all the substituents are substituted with hydrogen atoms is determined by the AM1 method which is a semi-empirical molecular orbital method.
Any one of the highest occupied molecular orbitals is selected, and the sum of squares of the atomic orbital coefficients corresponding to each of the carbon atoms to which the hydrogen atom is bonded, which the arylamine compound has, is calculated.
From the carbon atom bonded to the hydrogen atom of the arylamine compound, the carbon atom of the number of substituents is selected in descending order of the sum of the squares of the atomic orbital coefficients, and the corresponding aryl group (A) The carbon atom is a carbon atom having a substituent.

Here, the value (ρ _m ^HOMO ) of the sum of the squares of the atomic orbital coefficients of the highest occupied molecular orbitals (HOMO) of the carbon atoms in (C) is the AM1 method (Dewar, M), which is a semi-empirical molecular orbital method. J. S. et al, J. Am. Chem. Soc., 107, 3902 (1985)).

ρ _m ^HOMO = Σ _u (C _mu ^HOMO ) ² [Formula 1]

Here, m is a symbol representing the carbon atom, and u is a symbol representing an atomic orbital considered for the carbon atom by the AM1 method. C _mu ^HOMO represents an atomic orbital coefficient represented by HOMO of the carbon atom.

  In addition, the comparison of the sum of the squares of the atomic orbital coefficients is performed with two significant figures. In the case where there are a plurality of the same value of the sum of the squares of the atomic orbital coefficients in two significant digits, either of them may be selected as the carbon atom having a substituent.

  Here, the case of a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 2-pyrenyl group will be specifically described as the aryl group having a substituent on the carbon atom selected by (C). That is, for the amine compound in which all the substituents of the aryl group are substituted with hydrogen atoms and the amino group is bonded to the bond, the structure is optimized by the AM1 method using the molecular orbit calculation program WinMOPAC 3.0 Professional (MOPAC2000 V1.3) (Keyword: AM1 PRECISE EF VECTORS). The carbon atom position number of each amine compound is shown in the figure below. The calculation results are shown in Table 1.

For each carbon atom of Table 1 by comparing the values of (atomic orbital coefficient) 2 of the sum [rho _m ^HOMO, a carbon atom bearing a substituent in the order of the values of the [rho _m ^HOMO is larger.
For example, in the case of a phenyl group, when the carbon atom position numbers are arranged in descending order of the value of ρ _m ^HOMO , 4> 2, 6> 3,5. In the phenyl group having a substituent on the carbon atom selected by (C), in the case of one substituent, the carbon atom position number is 4, and in the case of two, it is 4 and 2, or 4 and 6, In some cases, it is a phenyl group having substituents at 4, 2 and 6. In the case of four substituents, the ρ _m ^HOMO values of carbon atom position numbers 3 and 5 are the same, so that the phenyl group has a substituent at carbon atom position numbers 4, 2, 6 and 3 or 5. In the case of 5 substituents, it is a phenyl group having substituents at carbon atom position numbers 4, 2, 6, 3 and 5.

Further, in the case of a 1-naphthyl group, 4>2>5>8>7>3> 6 is obtained by arranging the carbon atom position numbers in descending order of the ρ _m ^HOMO value. The 1-naphthyl group having a substituent on the carbon atom selected by (C) is carbon atom position number 4 in the case of one substituent, 4 and 2 in the case of 2, and 4 in the case of 3. 1-naphthyl group having substituents at 2 and 5; Similarly, in the case of 4 or more substituents, the carbon atom position numbers are selected in the order from the largest ρ _m ^HOMO value, and the 1-naphthyl group has a substituent at the carbon atom position number.

Further, for example, in the case of a 2-naphthyl group, 1>6>8>4>5>3> 7 is obtained by arranging the carbon atom position numbers in descending order of the ρ _m ^HOMO value. The 2-naphthyl group having a substituent on the carbon atom selected by (C) has 1 and 6 in the case of 1 carbon atom position number in the case of 1 substituent and 1 in the case of 3 , 6 and 8 are 2-naphthyl groups having a substituent. In the case of 4 substituents, it is a 2-naphthyl group having substituents at 1, 6, 8 and 4. Similarly, in the case of 5 or more substituents, carbon atom position numbers are selected in descending order of the ρ _m ^HOMO value, and the 2-naphthyl group has a substituent at the carbon atom position number.

Finally, in the case of a 2-pyrenyl group, 1, 3>7> 5 and 9>4,10> 6,8 when the carbon atom position numbers are arranged in descending order of the ρ _m ^HOMO value. The 2-pyrenyl group having a substituent on the carbon atom selected by (C) is carbon atom position number 1 or 3 in the case of one substituent, 1 and 3, and in the case of 3, It is a 2-pyrenyl group having a substituent at 1, 3 and 7. In the case of 4 substituents, the value of ρ _m ^HOMO of carbon atom position numbers 5 and 9 is the same, so that 2-pyrenyl group having a substituent at carbon atom position numbers 1, 3, 7 and 5 or 9 is there. In the case of 5 substituents, it is a 2-pyrenyl group having a substituent at carbon atom position numbers 1, 3, 7, 5 and 9. Similarly, in the case of 6 or more substituents, a carbon atom position number is selected in order from the largest ρ _m ^HOMO value, and the 2-pyrenyl group having a substituent at the carbon atom position number.

式中、Ｒ_１は、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、シリルオキシ基、置換シリルオキシ基、1価の複素環基またはハロゲン原子を表し、中でも、アルキル基、アルコキシ基が好ましい。Ｒ_１が複数存在する場合、それらは同一でも異なっていてもよい。ｒは、０〜５の整数を表し、１以上であることが好ましい。 The aryl group (A) is more preferably a group independently represented by the following formula (3).

In the formula, R ₁ is 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 It represents an amino group, a silyl group, a substituted silyl group, a silyloxy group, a substituted silyloxy group, a monovalent heterocyclic group or a halogen atom, and among them, an alkyl group and an alkoxy group are preferable. When a plurality of R ₁ are present, they may be the same or different. r represents an integer of 0 to 5, and is preferably 1 or more.

Among the groups of formula (3), a group in which R ₁ is substituted at the para position with respect to the bond is preferred, r is 3, and R ₁ is in the para position with respect to the bond. A group substituted at two ortho positions is particularly preferable from the viewpoint of the result of (C) and improvement of solubility and sterically protecting the nitrogen atom.

In the formula (1), l, m and n each independently represent an integer of 0 to 2, and o and p each independently represent 0 or 1. l + m + n + o + p is 2 or more. However, the total number of N in the formula is 3 or more.
Further, l + m + n + o + p is preferably 6 or less.

がそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。 The repeating unit represented by the above formula (1) preferably has one or more substituents from the viewpoint of solubility.
In the above formula (1), Ar ₂ , Ar ₄ , Ar ₅ ,

When there are a plurality of each, they may be the same or different.

Among the repeating units of the formula (1), it is preferable that Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar _5, Ar ₆ and Ar ₇ are each independently an arylene group, and n is 1 or more. More preferred.
Among them, the arylene group is preferably a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenyldiyl group, a substituted or unsubstituted fluorene-diyl group, or a substituted or unsubstituted stilbene-diyl group. More preferred is a phenylene group.

  Specific examples of the repeating unit represented by the above formula (1) include the following repeating units.

n = 0:

n = 1:

n = 2:

〔式中、Meはメチル基、Buはブチル基を示す。〕

[In the formula, Me represents a methyl group, and Bu represents a butyl group. ]

The polymer compound of the present invention may contain two or more repeating units represented by the formula (1).
In the polymer compound of the present invention, the amount of the repeating unit represented by the formula (1) is usually 1 to 100 mol%, preferably 10 to 90%, based on all repeating units of the polymer compound of the present invention. Mol%.

  Examples of the repeating unit other than the repeating unit represented by the formula (1) that can be contained in the polymer compound of the present invention include the repeating units represented by the following formulas (4), (5), (6), and (7). Is preferred.

−Ａｒ_１６−Ｘ_２− （６）

−Ｘ_３− （７）

〔式中、Ａｒ_１３、Ａｒ_１４、Ａｒ_１５、およびＡｒ_１６はそれぞれ独立にアリーレン基、２価の複素環基または金属錯体構造を有する２価の基を示す。Ｘ_１、Ｘ_２およびＸ_３はそれぞれ独立に−ＣＲ_２＝ＣＲ_３−、−Ｃ≡Ｃ−、−Ｎ（Ｒ_４）−、または−（ＳｉＲ_５Ｒ_６）_ｂ−を示す。Ｒ_２およびＲ_３は、それぞれ独立に水素原子、アルキル基、アリール基、１価の複素環基、カルボキシル基、置換カルボキシル基、またはシアノ基を示す。Ｒ_４、Ｒ_５およびＲ_６は、それぞれ独立に水素原子、アルキル基、アリール基、１価の複素環基またはアリールアルキル基を示す。Ａｒ₁₄、Ｘ₁、Ｒ₅、およびＲ₆がそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。〕
-Ar ₁₃ - (4)

—Ar ₁₆ —X ₂ — (6)

-X _3- (7)

[Wherein, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ , and Ar ₁₆ each independently represent an arylene group, a divalent heterocyclic group, or a divalent group having a metal complex structure. X ₁ , X ₂ and X ₃ each independently represent —CR ₂ ═CR ₃ —, —C≡C—, —N (R ₄ ) —, or — (SiR ₅ R ₆ ) _b —. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, or a cyano group. R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or an arylalkyl group. When there are a plurality of Ar ₁₄ , X ₁ , R ₅ , and R ₆ , they may be the same or different. ]

  The arylene group, divalent heterocyclic group, alkyl group, aryl group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, and arylalkyl group are as described above.

In the present invention, the divalent group having a metal complex structure is a remaining divalent group obtained by removing two hydrogen atoms from an organic ligand of a metal complex having an organic ligand.
The carbon number of the organic ligand is usually about 4 to 60. For example, 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, 2-phenyl-benzothiazole and derivatives thereof. Derivatives, 2-phenyl-benzoxazole and its derivatives, porphyrin and its derivatives and the like.
Examples of the central metal of the complex include aluminum, zinc, beryllium, iridium, platinum, gold, europium, and terbium.
Examples of the metal complex having an organic ligand include a low-molecular fluorescent material, a metal complex known as a phosphorescent material, and a triplet light-emitting complex.

Specific examples of the divalent group having a metal complex structure include the following (126 to 132).

  In the example shown by the above formulas 126 to 132, R is the same as that of the above formulas 1 to 125.

  As the repeating unit other than the repeating unit represented by the formula (1) that can be contained in the polymer compound of the present invention, the repeating unit represented by the above formulas (4) and (5) is more preferable.

  Specific examples of the repeating unit represented by the above formula (5) include the repeating units represented by the following figures (133 to 140).

In the above formula, R is the same as that in formulas 1-132. In the above example, one structural formula has a plurality of Rs, but they may be the same or different groups. In order to increase the solubility in a solvent, it is preferable to have at least one other than a hydrogen atom, and it is preferable that the symmetry of the shape of the repeating unit including a substituent is small.
Furthermore, in the above formula, when R contains an aryl group or a heterocyclic group as a part thereof, they may further have one or more substituents.
In the above-mentioned formula, in the substituent in which R contains an alkyl chain, they may be linear, branched or cyclic, or a combination thereof, and when they are not linear, for example, isoamyl group, 2-ethylhexyl group, 3,7-dimethyl octyl group, a cyclohexyl group, etc. 4-C ₁ ~C ₁₂ alkyl cyclohexyl groups. In order to enhance the solubility of the polymer compound in the solvent, it is preferable that at least one alkyl chain having a cyclic or branched structure is contained.
A plurality of R may be connected to form a ring. Moreover, the carbon atom which the group of Formula 1-140 has may be substituted with the nitrogen atom, the oxygen atom, or the sulfur atom, and the hydrogen atom may be substituted with the fluorine atom.

In addition, the high molecular compound of this invention may contain repeating units other than the repeating unit shown by Formula (1)-Formula (7) in the range which does not impair a fluorescence characteristic and a charge transport characteristic. In addition, these repeating units and other repeating units may be linked by non-conjugated units, or the repeating units may contain those non-conjugated parts. Examples of the binding structure include those shown below and combinations of two or more of the following. Here, R is a group selected from the same substituents as described above, and Ar represents a hydrocarbon group having 6 to 60 carbon atoms.

  The polymer compound of the present invention may be a random, block or graft copolymer, or may be a polymer having an intermediate structure thereof, such as a random copolymer having a block property. Good. From the viewpoint of obtaining a polymer light emitter having a high quantum yield of light emission, a random copolymer having a block property and a block or graft copolymer are preferable to a completely random copolymer. A case in which the main chain is branched and there are three or more terminal portions and dendrimers are also included.

  In addition, the terminal group of the polymer compound of the present invention may be protected with a stable group, because if the polymerization active group remains as it is, there is a possibility that the light emission characteristics and lifetime when the device is made will be reduced. . Those having a conjugated bond continuous with the conjugated structure of the main chain are preferable, and examples thereof include a structure in which an aryl group or a heterocyclic group is bonded via a carbon-carbon bond. Specific examples include substituents described in Chemical formula 10 of JP-A-9-45478.

The number average molecular weight in terms of polystyrene of the polymer compound of the present invention is 10 ³ to 10 ^8.
And preferably 10 ⁴ to 10 ⁶ .

  Examples of the good solvent for the polymer compound of the present invention include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, and n-butylbenzene. Although depending on the structure and molecular weight of the polymer compound, it can usually be dissolved in these solvents in an amount of 0.1% by weight or more.

式中、Ａｒ_１、Ａｒ_２、Ａｒ_３、Ａｒ_４、Ａｒ_５、Ａｒ_６、Ａｒ_７およびｌ、ｎ、ｍ、ｏ、pは前記と同じである。Y_１およびY_２はそれぞれ独立に縮合重合可能な置換基を示す。 The polymer compound of the present invention can be produced by condensation polymerization using a compound represented by the following formula (8) as one of raw materials.

In the formula, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , Ar ₆ , Ar ₇ and l, n, m, o, and p are the same as described above. Y ₁ and Y ₂ each independently represent a substituent capable of condensation polymerization.

  Here, as a substituent capable of condensation polymerization, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a boric acid ester group, a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, and a monohalogenated methyl group , Boric acid group, formyl group, cyano group, vinyl group and the like.

  Here, examples of the alkyl sulfonate group include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group. Examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group. Examples of the aryl sulfonate group include Examples thereof include a benzyl sulfonate group.

式中、Ｍｅはメチル基を、Ｅｔはエチル基を示す。 Examples of the borate group include groups represented by the following formula.

In the formula, Me represents a methyl group, and Et represents an ethyl group.

Examples of the sulfonium methyl group include groups represented by the following formula.
_{^{-CH 2 S + Me 2 X -}} , -CH 2 S + Ph 2 X -
(X represents a halogen atom, and Ph represents a phenyl group.)

Examples of the phosphonium methyl group include groups represented by the following formula.
_{^{-CH 2 P + Ph 3 X -}} (X represents a halogen atom.)

Examples of the phosphonate methyl group include groups represented by the following formula.
—CH ₂ PO (OR ′) ₂ (R ′ represents an alkyl group, an aryl group, or an arylalkyl group.)

  Examples of the monohalogenated methyl group include a methyl fluoride group, a methyl chloride group, a methyl bromide group, and a methyl iodide group.

  Preferred substituents that can be subjected to condensation polymerization vary depending on the type of polymerization reaction. For example, when a zero-valent nickel complex such as Yamamoto coupling reaction is used, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an aryl alkyl sulfonate group. Is mentioned. In the case of using a nickel catalyst or a palladium catalyst such as a Suzuki coupling reaction, an alkyl sulfonate group, a halogen atom, a boric acid ester group, a boric acid group, and the like can be given.

  In addition, when the polymer compound of the present invention has a repeating unit other than the repeating unit represented by the above formula (1), two condensation-polymerizable substitutions that become a repeating unit other than the above formula (1) What is necessary is just to perform condensation polymerization in the presence of a compound having a group.

Y_７−Ａｒ_１６−Ｘ_２−Y_８ （１１）

Y_９−Ｘ_３−Y_１０ （１２）
〔式中、Ａｒ_１３、Ａｒ_１４、Ａｒ_１５、Ａｒ_１６、Ｘ_１、Ｘ_２、Ｘ_３は前記の通りである。Y_３、Y_４、Y_５、Y_６、Y_７、Y_８、Y_９、Y_１０はそれぞれ独立に縮合重合可能な置換基を示す。〕 Examples of the compound having two condensation-polymerizable substituents that are repeating units other than the repeating unit represented by the formula (1) include compounds represented by the following formulas (9) to (12).
In addition to the compound represented by the above formula (8), in addition to the unit represented by the above formula (1), the compounds represented by any of the following formulas (9) to (12) are subjected to condensation polymerization, in order. A polymer compound having one or more units of (4), (5), (6) or (7) can be produced.

Y ₃ -Ar ₁₃ -Y ₄ (9)

_{Y 7 -Ar 16 -X 2 -Y 8} (11)

_{Y 9 -X 3 -Y 10 (12} )
[In formula, Ar < ₁₃ >, Ar < ₁₄ >, Ar < ₁₅ >, Ar < ₁₆ >, X < ₁ >, X < ₂ >, X < ₃ > is as above-mentioned. Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ and Y ₁₀ each independently represent a substituent capable of condensation polymerization. ]

In the method for producing a polymer compound of the present invention, as a method for condensation polymerization, a known condensation reaction is used depending on the substituent capable of condensation polymerization of the compounds represented by the above formulas (8) to (12). Can be manufactured.
When the polymer compound of the present invention forms a double bond in condensation polymerization, for example, a method described in JP-A-5-202355 can be mentioned. That is, polymerization by Wittig reaction of a compound having a formyl group and a compound having a phosphonium methyl group, or a compound having a formyl group and a phosphonium methyl group, by Heck reaction between a compound having a vinyl group and a compound having a halogen atom. Polymerization, polycondensation of compounds having two or more monohalogenated methyl groups by dehydrohalogenation method, polycondensation of compounds having two or more sulfonium methyl groups by decomposing sulfonium salt, having a formyl group Examples include a method such as polymerization by a Knoevenagel reaction between a compound and a compound having a cyano group, and a method such as polymerization by a McMurry reaction of a compound having two or more formyl groups.
When the polymer compound of the present invention forms a triple bond in the main chain by condensation polymerization, for example, Heck reaction and Sonogashira reaction can be used.

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

  Among these, polymerization by Wittig reaction, polymerization by Heck reaction, polymerization by Knoevenagel reaction, polymerization method by Suzuki coupling reaction, polymerization method by Grignard reaction, polymerization method by nickel zero-valent complex, and polymerization by Sonogashira reaction It is preferable because the structure can be easily controlled.

More specifically, the reaction conditions will be described.
In the case of Wittig reaction, Horner reaction, Knoevengel reaction, etc., the reaction is carried out using an alkali equivalent to or more, preferably 1 to 3 equivalents of the functional group of the compound. Examples of the alkali include, but are not limited to, metal alcoholates such as potassium tert-butoxide, sodium tert-butoxide, sodium ethylate and lithium methylate, hydride reagents such as sodium hydride, and amides such as sodium amide. Etc. can be used. As the solvent, N, N-dimethylformamide, tetrahydrofuran, dioxane, toluene and the like are used. The reaction can be allowed to proceed at a reaction temperature of usually from room temperature to about 150 ° C. The reaction time is, for example, 5 minutes to 40 hours, but may be any time that allows sufficient polymerization to proceed, and it is not necessary to leave the reaction for a long time after the reaction is completed. is there. If the reaction concentration is too dilute, the reaction efficiency is poor. If the concentration is too high, it becomes difficult to control the reaction. Therefore, the concentration may be appropriately selected within the range of about 0.01 wt% to the maximum concentration to be dissolved. The range is from 1 wt% to 30 wt%. The Wittig reaction is described in “Organic Reactions”, Vol. 14, pages 270-490, John Wiley & Sons, Inc., 1965, and the like. Knoevenagel, Wittig, and dehydrohalogenation reactions are described in Macromolecular Chemistry Macromolecular Symposium (Makromol. Chem., Macromol. Symp.), Vol. 12, 229 (1987).

  In the case of the Heck reaction, the monomer is reacted using a palladium catalyst in the presence of a base such as triethylamine. A relatively high boiling point solvent such as N, N-dimethylformamide or N-methylpyrrolidone is used, the reaction temperature is about 80 to 160 ° C., and the reaction time is about 1 to 100 hours. The Heck reaction is described in, for example, Polymer, Vol. 39, pages 5241-5244 (1998).

  In the case of the Sonogashira reaction, generally, a palladium catalyst and cuprous iodide are used, and in the presence of a base such as triethylamine, N, N-dimethylformamide, an amine solvent or an ether solvent, The monomer is reacted. Depending on the reaction conditions and the reactivity of the polymerizable substituent of the monomer, the reaction temperature is usually about −50 to 120 ° C., and the reaction time is about 1 to 100 hours. The Sonogashira reaction is described, for example, in Tetrahedron Letters, 40, 3347-3350 (1999), Tetrahedron Letters, 16, 4467-4470 (1975).

In the case of the Suzuki reaction, for example, palladium [tetrakis (triphenylphosphine)], palladium acetates and the like are used as a catalyst, an inorganic base such as potassium carbonate, sodium carbonate, and barium hydroxide, an organic base such as triethylamine, and cesium fluoride. The inorganic salt such as is added in an amount of not less than an equivalent amount, preferably 1 to 10 equivalents, relative to the monomer. An inorganic salt may be used as an aqueous solution and reacted in a two-phase system. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. Although depending on the solvent, a temperature of about 50 to 160 ° C. is preferably used. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 1 hour to 200 hours.
The Suzuki reaction is described in, for example, Chemical Review (Chem. Rev.), Vol. 95, page 2457 (1995).

The case where a zerovalent nickel complex is used will be described. There are a method of using a zero-valent nickel complex as a zero-valent nickel complex and a method of reacting a nickel salt in the presence of a reducing agent to generate zero-valent nickel in the system.
Examples of the zero-valent nickel complex include bis (1,5-cyclooctadiene) nickel (0), (ethylene) bis (triphenylphosphine) nickel (0), tetrakis (triphenylphosphine) nickel, Bis (1,5-cyclooctadiene) nickel (0) is preferred from the viewpoint of versatility and low cost.

Moreover, it is preferable from a viewpoint of a yield improvement to add a neutral ligand.
Here, the neutral ligand is a ligand having no anion or cation, and 2,2′-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline, N, N′-tetramethylethylenediamine. Nitrogen-containing ligands such as triphenylphosphine, tolylphosphine, tributylphosphine, triphenoxyphosphine, and the like, and nitrogen-containing ligands are preferred in terms of versatility and low cost. 2,2′-bipyridyl is particularly preferable in terms of high reactivity and high yield. In particular, from the viewpoint of improving the yield of the polymer, a system in which 2,2′-bipyridyl is added as a neutral ligand to a system containing bis (1,5-cyclooctadiene) nickel (0) is preferable. In the method of producing zero-valent nickel in the system, nickel chloride, nickel acetate and the like can be cited as nickel salts. Examples of the reducing agent include zinc, sodium hydride, hydrazine and derivatives thereof, lithium aluminum hydride and the like, and ammonium iodide, lithium iodide, potassium iodide and the like are used as additives as necessary.

In the production method of the present invention, Y ₁ , Y _2, Y _3, Y _4, Y _5, Y _6, Y _7, Y _8, Y _9, and Y ₁₀ are each independently a halogen atom, an alkyl sulfonate group, It is an aryl sulfonate group or an arylalkyl sulfonate group, and a production method in which condensation polymerization is performed in the presence of a nickel zero-valent complex is preferable.
As raw material compounds, dihalogenated compounds, bis (alkyl sulfonate) compounds, bis (aryl sulfonate) compounds, bis (aryl alkyl sulfonate) compounds or halogen-alkyl sulfonate compounds, halogen-aryl sulfonate compounds, halogen-aryl alkyl sulfonate compounds, Examples include alkyl sulfonate-aryl sulfonate compounds, alkyl sulfonate-aryl alkyl sulfonate compounds, and aryl sulfonate-aryl alkyl sulfonate compounds.

In the production method of the present invention, Y ₁ , Y _2, Y _3, Y _4, Y _5, Y _6, Y _7, Y _8, Y _9, and Y ₁₀ are each independently a halogen atom, alkyl sulfonate. Group, aryl sulfonate group, aryl alkyl sulfonate group, boric acid group, or boric acid ester group, the total number of moles of halogen atom, alkyl sulfonate group, aryl sulfonate group and aryl alkyl sulfonate group (J), and boric acid The ratio of the total number of moles of groups and borate groups (K) is substantially 1 (usually K / J is in the range of 0.7 to 1.2), and condensation polymerization is performed using a nickel catalyst or a palladium catalyst. The manufacturing method is preferred.
Specific combinations of raw material compounds include a combination of a dihalogenated compound, a bis (alkyl sulfonate) compound, a bis (aryl sulfonate) compound or a bis (aryl alkyl sulfonate) compound and a diboric acid compound or a diboric acid ester compound. .
Also, halogen-boric acid compounds, halogen-boric acid ester compounds, alkyl sulfonate-boric acid compounds, alkyl sulfonate-boric acid ester compounds, aryl sulfonate-boric acid compounds, aryl sulfonate-boric acid ester compounds, arylalkyl sulfonate-borates Examples include acid compounds, arylalkyl sulfonate-boric acid compounds, and arylalkyl sulfonate-boric acid ester compounds.

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

In order to make it react, an alkali and a suitable catalyst are added suitably. These may be selected according to the reaction used. The alkali or catalyst is preferably one that is sufficiently dissolved in the solvent used in the reaction. As a method of mixing the alkali or catalyst, slowly add the alkali or catalyst solution while stirring the reaction solution under an inert atmosphere such as argon or nitrogen, or conversely, slowly add the reaction solution to the alkali or catalyst solution. And the method of adding.
The polymerization time is usually about 5 minutes to 200 hours depending on the kind of polymerization, but is preferably within 10 hours from the viewpoint of production cost.
Although superposition | polymerization temperature is based also on the kind of superposition | polymerization, although it is about -50-160 degreeC normally, 20-100 degreeC is preferable from the point of a high yield and a fall heat.

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

Next, the use of the polymer compound of the present invention will be described.
The polymer compound of the present invention usually has fluorescence or phosphorescence in a solid state, and can be used as a polymer light emitter (high molecular weight light emitting material). The polymer LED using the polymer light emitter is a high-performance polymer LED that can be driven with low voltage and high efficiency. Therefore, the polymer LED can be preferably used for a backlight of a liquid crystal display, or a device such as a curved or flat light source for illumination, a segment type display element, a dot matrix flat panel display.
The polymer compound of the present invention can also be used as a material for conductive thin films such as laser dyes, organic solar cell materials, organic semiconductors for organic transistors, conductive thin films, and organic semiconductor thin films.
Furthermore, it can also be used as a light-emitting thin film material that emits fluorescence or phosphorescence.

Next, the polymer LED of the present invention will be described.
The polymer LED of the present invention has a layer containing the polymer compound of the present invention between electrodes composed of an anode and a cathode.
The layer containing the polymer compound of the present invention may be any of a light emitting layer, a hole transport layer, an electron transport layer and the like, but is preferably a light emitting layer.

Here, the light emitting layer refers to a layer having a function of emitting light, the hole transporting layer refers to a layer having a function of transporting holes, and the electron transporting layer is a layer having a function of transporting electrons. Say. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. Two or more light emitting layers, hole transport layers, and electron transport layers may be used independently.

  When the layer containing the polymer compound of the present invention is a light emitting layer, the light emitting layer may further contain a hole transport material, an electron transport material or a light emitting material. Here, the light emitting material refers to a material exhibiting fluorescence and / or phosphorescence.

When the polymer compound of the present invention and the hole transport material are mixed, the mixing ratio of the hole transport material is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt% with respect to the entire mixture. is there. When the polymer material of the present invention and the electron transporting material are mixed, the mixing ratio of the electron transporting material is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt% with respect to the entire mixture. Further, when the polymer compound of the present invention and the light emitting material are mixed, the mixing ratio of the light emitting material is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt% with respect to the entire mixture. When the polymer compound of the present invention is mixed with a light emitting material, a hole transporting material and / or an electron transporting material, the mixing ratio of the light emitting material with respect to the whole mixture is 1 wt% to 50 wt%, preferably The total amount of the hole transporting material and the electron transporting material is 1 wt% to 50 wt%, preferably 5 wt% to 40 wt%, and the content of the polymer compound of the present invention is 5 wt% to 40 wt% Is 99 wt% to 20 wt%.

As the hole transport material, electron transport material, and light-emitting material to be mixed, known low molecular compounds and high molecular compounds can be used, but it is preferable to use high molecular compounds. As the hole transport material, electron transport material and light-emitting material of the polymer compound, WO99 / 13692, WO99 / 48160, GB2340304A, WO00 / 53656, WO01 / 19834, WO00 / 55927, GB23448316, WO00 / 46321, WO00 / 06665, WO99 / 54943, WO99 / 54385, US5777070, WO98 / 06773, WO97 / 05184, WO00 / 35987, WO00 / 53655, WO01 / 34722, WO99 / 24526, WO00 / 22027, WO00 / 22026, WO98 / 27136, US573636, WO98 / 21262, US5741921, WO97 / 09394, WO96 / 29356, WO96 / 10617, EP07070720 WO95 / 07955, JP 2001-181618, JP 2001-123156, JP 2001-3045, JP 2000-351967, JP 2000-303066, JP 2000-299189, JP 2000-252065, JP 2000-200065 136,379, JP-A 2000-104057, JP-A 2000-80167, JP-A 10-324870, JP-A 10-114891, JP-A 9-111233, JP-A 9-45478, etc. Examples include polymers, polyarylenes, derivatives and copolymers thereof, polyarylene vinylenes, derivatives and copolymers thereof, and (co) polymers of aromatic amines and derivatives thereof.
Examples of low molecular weight fluorescent materials include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine-based, xanthene-based, coumarin-based, cyanine-based pigments, 8-hydroxyquinoline or its derivatives of metals. A complex, an aromatic amine, tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used.
Specifically, for example, known ones such as those described in JP-A-57-51781 and 59-194393 can be used.

Examples of phosphorescent materials for low molecular weight compounds include Ir (ppy) 3, Btp ₂ Ir (acac) with iridium as the central metal, PtOEP with platinum as the central metal, Eu (TTA) 3phen with europium as the central metal, etc. And a triplet light-emitting complex.

三重項発光錯体として具体的には、例えばNature, (1998), 395, 151、Appl. Phys. Lett. (1999), 75(1), 4、Proc. SPIE-Int. Soc. Opt. Eng. (2001), 4105(Organic Light-Emitting Materials and DevicesＩＶ), 119、J. Am. Chem. Soc., (2001), 123, 4304、Appl. Phys. Lett., (1997), 71(18), 2596、Syn. Met., (1998), 94(1), 103、Syn. Met., (1999), 99(2), 1361、Adv. Mater., (1999), 11(10), 852 、Jpn.J.Appl.Phys.,34, 1883 (1995)などに記載されている。

Specific examples of triplet light emitting complexes include Nature, (1998), 395, 151, Appl. Phys. Lett. (1999), 75 (1), 4, Proc. SPIE-Int. Soc. Opt. Eng. (2001), 4105 (Organic Light-Emitting Materials and Devices IV), 119, J. Am. Chem. Soc., (2001), 123, 4304, Appl. Phys. Lett., (1997), 71 (18), 2596, Syn. Met., (1998), 94 (1), 103, Syn. Met., (1999), 99 (2), 1361, Adv. Mater., (1999), 11 (10), 852, Jpn. J. Appl. Phys., 34, 1883 (1995).

The composition of the present invention contains at least one material selected from a hole transport material, an electron transport material and a light emitting material and the polymer compound of the present invention, and can be used as a light emitting material or a charge transport material. The composition of the present invention may contain two or more polymer compounds of the present invention.
The content ratio of the polymer compound of the present invention and at least one material selected from the hole transport material, electron transport material, and light emitting material may be determined according to the use. The same content ratio as in the light emitting layer is preferable.

  As the film thickness of the light emitting layer of the polymer LED of the present invention, the optimum value varies depending on the material to be used, and it may be selected so that the driving voltage and the light emission efficiency are appropriate values, for example, 1 nm to 1 μm, Preferably it is 2 nm-500 nm, More preferably, it is 5 nm-200 nm.

Examples of the method for forming the light emitting layer include a method by film formation from a solution.
As a film forming method 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, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, Application methods such as a flexographic printing method, an offset printing method, and an ink jet printing method can be used.

The ink composition used in the printing method or the like only needs to contain at least one polymer compound of the present invention. Besides the polymer compound of the present invention, a hole transport material, an electron transport material, a light emitting material, Additives such as solvents and stabilizers may be included.
The ratio of the polymer compound of the present invention in the ink composition is 20 wt% to 100 wt%, preferably 40 wt% to 100 wt%, based on the total weight of the composition excluding the solvent.
When the ink composition contains a solvent, the ratio of the solvent is 1 wt% to 99.9 wt%, preferably 60 wt% to 99.5 wt%, and more preferably 80 wt% with respect to the total weight of the composition. % To 99.0 wt%.
The viscosity of the ink composition varies depending on the printing method. However, when the ink composition passes through a discharge device such as an ink jet printing method, the viscosity is 1 at 25 ° C. in order to prevent clogging at the time of discharge and flight bending. It is preferably in the range of ˜20 mPa · s.
Although there is no restriction | limiting in particular as a solvent used as an ink composition, The thing which can melt | dissolve or disperse | distribute materials other than the solvent which comprises this ink composition is preferable. When the material constituting the ink composition is soluble in a nonpolar solvent, the solvent is a chlorinated solvent such as chloroform, methylene chloride or dichloroethane, an ether solvent such as tetrahydrofuran, or an aromatic such as toluene or xylene. Examples include aromatic hydrocarbon solvents, ketone solvents such as acetone and methyl ethyl ketone, and ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate.

  In addition, as the polymer LED of the present invention, a polymer LED having an electron transport layer provided between the cathode and the light emitting layer, a polymer LED having a hole transport layer provided between the anode and the light emitting layer, Examples include a polymer LED in which an electron transport layer is provided between the cathode and the light emitting layer, and a hole transport layer is provided between the anode and the light emitting layer.

For example, the following structures a) to d) are specifically exemplified.
a) Anode / light emitting layer / cathode b) Anode / hole transport layer / light emitting layer / cathode c) Anode / light emitting layer / electron transport layer / cathode d) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (Here, / indicates that each layer is laminated adjacently. The same shall apply hereinafter.)

  When the polymer LED of the present invention has a hole transport layer, the hole transport material used is polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, polysiloxane having an aromatic amine in a side chain or a main chain. Derivatives, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or 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 a 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, a polyaniline or a derivative thereof , Polythiophene or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, or a polymer hole transporting material such as poly (2,5-thienylene vinylene) or a derivative thereof is preferable, and polyvinyl carbazole or a derivative thereof is more preferable Derivatives, polysilanes or derivatives thereof, and polysiloxane derivatives having an aromatic amine in the side chain or main chain.

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

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those showing no strong absorption against visible light are suitably used. As the polymer binder, poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, poly (2,5-thienylenevinylene) or a derivative thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

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

  Examples of polysilane or derivatives thereof include compounds described in Chem. Rev. 89, 1359 (1989) and GB 2300196 published specification. 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 hole transporting material in the side chain or main chain are preferably used. Particularly, those having a hole transporting aromatic amine in the side chain or main chain are exemplified.

  Although there is no restriction | limiting in the film-forming method of a positive hole transport layer, The method by the film-forming from a mixed solution with a polymer binder is illustrated with a low molecular hole transport material. In the case of a polymer hole transporting material, a method by film formation from a solution is exemplified.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transporting material. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

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

  The film thickness of the hole transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. 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 film 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.

  When the polymer LED of the present invention has an electron transport layer, known materials can be used as the electron transport material used, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or Derivatives thereof, anthraquinone 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 Alternatively, derivatives thereof, polyfluorene or derivatives thereof, and the like are exemplified.

  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.

  Of these, oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinones 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 preferred, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

  There are no particular restrictions on the method of forming the electron transport layer, but for low molecular weight electron transport materials, vacuum deposition from powder, or by film formation from a solution or molten state, solution for polymer electron transport materials is possible. Or the method by the film-forming from a molten state is illustrated, respectively. When forming a film from a solution or a molten state, the above polymer binder may be used in combination.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve an electron transport material and / or a polymer binder. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

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

  The film thickness of the electron transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the 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.

  Further, among the charge transport layers provided adjacent to the electrodes, those having a function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element are particularly charge injection layers (hole injection layers). , An electron injection layer).

Further, in order to improve adhesion with the electrode and charge injection from the electrode, the charge injection layer or an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode, and the adhesion at the interface may be improved. In order to prevent mixing, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.
The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

In the present invention, a polymer LED provided with a charge injection layer (electron injection layer, hole injection layer) includes a polymer LED provided with a charge injection layer adjacent to the cathode, and a charge injection layer adjacent to the anode. The provided polymer LED is mentioned.
For example, the following structures e) to p) are specifically mentioned.
e) Anode / charge injection layer / light emitting layer / cathode f) Anode / light emitting layer / charge injection layer / cathode g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode h) Anode / charge injection layer / hole Transport layer / light emitting layer / cathode i) anode / hole transport layer / light emitting layer / charge injection layer / cathode j) anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode k) anode / charge Injection layer / light emitting layer / electron transport layer / cathode l) anode / light emitting layer / electron transport layer / charge injection layer / cathode m) anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode n) anode / Charge injection layer / hole transport layer / light emitting layer / electron transport layer / cathode o) anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode p) anode / charge injection layer / hole transport Layer / light emitting layer / electron transport layer / charge injection layer / cathode

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

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ or less, and the leakage current between the light emitting pixels is reduced. In order to achieve this, 10 ⁻⁵ S / cm to 10 ² is more preferable, and 10 ⁻⁵ S / cm to 10 ¹ is more preferable.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less. in order to reduce the current, 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 or less, the conductive polymer is doped with an appropriate amount of ions.

The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and examples of cations include lithium ions, sodium ions, potassium ions, tetrabutylammonium ions, and the like.
The thickness of the charge injection layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.

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

  An insulating layer having a thickness of 2 nm or less has a function of facilitating charge injection. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. As the polymer LED provided with the insulating layer having a thickness of 2 nm or less, the polymer LED provided with the insulating layer having a thickness of 2 nm or less adjacent to the cathode, or the insulating layer having a thickness of 2 nm or less provided adjacent to the anode. Polymer LED is mentioned.

Specific examples include the following structures q) to ab).
q) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / cathode r) Anode / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode s) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / film thickness 2 nm Insulating layer / cathode t) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / cathode u) Anode / hole transporting layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode v) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode w) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / cathode x) anode / Light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode y) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode z) anode / film Insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / cathode aa) anode / hole transport layer / light emitting layer / electron transport Layer / thickness 2nm or less of the insulating layer / cathode ab) anode / thickness 2nm or less of the insulating layer / hole transport layer / light emitting layer / electron transporting layer / thickness 2nm or less of the insulating layer / cathode

  The substrate on which the polymer LED of the present invention is formed may be any substrate that does not change when the electrode is formed and the organic layer is formed, and examples thereof include glass, plastic, polymer film, and silicon substrate. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

Usually, at least one of the anode and the cathode of the polymer LED of the present invention is transparent or translucent. 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 film made of conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. 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 electric conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. is there.
Further, in order to facilitate charge injection on the anode, a layer made of a phthalocyanine derivative, a conductive polymer, carbon or the like, or an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like. A layer may be provided.

As a material of the cathode used in the polymer LED of the present invention, 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 an alloy of one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite intercalation compound, etc. Is used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, and the like. The cathode may have a laminated structure of two or more layers.
The thickness of the cathode can be appropriately 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. Further, a layer made of a conductive polymer or a layer made of a metal oxide, a metal fluoride, an organic insulating material or the like having an average film thickness of 2 nm or less may be provided between the cathode and the organic material layer. A protective layer for protecting the polymer LED may be attached. In order to use the polymer LED stably for a long period of time, it is preferable to attach a protective layer and / or protective cover in order to protect the element from the outside.

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

The polymer LED of the present invention can be used as a backlight for a planar light source, a segment display device, a dot matrix display device, and a liquid crystal display device.
In order to obtain planar light emission using the polymer LED of the present invention, the planar anode and cathode may be arranged so as to overlap each other. In addition, 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 material layer of a non-light-emitting portion is formed extremely thick and substantially non- There are a method of emitting light and a method of forming either one of the anode or the cathode or both electrodes in a pattern. By forming a pattern by any of these methods and arranging some electrodes so that they can be turned on / off independently, a segment type display element capable of displaying numbers, letters, simple symbols and the like can be obtained. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multi-color display are possible by a method of separately coating a plurality of types of 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.

化合物Ａ
不活性雰囲気下１ｌの四つ口フラスコに２，８−ジブロモジベンゾチオフェン ７ｇとＴＨＦ ２８０ｍｌを入れ、室温で撹拌、溶かした後、−７８℃まで冷却した。ｎ−ブチルリチウム ２９ｍｌ（１．６モルヘキサン溶液）を滴下した。滴下終了後、温度を保持したまま２時間撹拌し、トリメトキシボロン酸 １３ｇを滴下した。滴下終了後、ゆっくり室温まで戻した。３時間室温で撹拌後、ＴＬＣで原料の消失を確認した。５％硫酸 １００ｍｌを加えて反応を終了させ、室温で１２時間撹拌した。水を加えて洗浄し、有機層を抽出した。溶媒を酢酸エチルに置換した後、３０％過酸化水素水 ５ｍｌを加え、４０℃で５時間撹拌した。その後有機層を抽出し、１０％硫酸アンモニウム鉄（II）水溶液で洗浄後乾燥、溶媒を除去することにより、茶色の固体 ４．４３ｇを得た。ＬＣ−ＭＳ測定からは二量体などの副生成物も生成しており、化合物Ａの純度は７７％であった（ＬＣ面百）。
ＭＳ（ＡＰＣＩ（−））：（Ｍ−Ｈ）^- ２１５ Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
Here, for the number average molecular weight, the number average molecular weight in terms of polystyrene was determined by gel permeation chromatography (GPC) using chloroform as a solvent.

Synthesis Example 1 (Synthesis of Compound A)

Compound A
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 and dissolved at room temperature, and then cooled to -78 ° C. 29 ml of n-butyllithium (1.6 molar 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 returned to room temperature. After stirring at room temperature for 3 hours, disappearance of the raw material was confirmed by TLC. The reaction was terminated by adding 100 ml of 5% 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% aqueous hydrogen peroxide was added and stirred at 40 ° C. for 5 hours. Thereafter, the organic layer was extracted, washed with a 10% 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 A was 77% (LC area percentage).
MS (APCI (-)) :( M-H) - 215

化合物Ｂ
不活性雰囲気下で２００ｍｌの三つ口フラスコに化合物Ａ ４．４３ｇと臭化ｎ−オクチル ２５．１ｇ、および炭酸カリウム １２．５ｇ（２３．５ｍｍｏｌ）を入れ、溶媒としてメチルイソブチルケトン ５０ｍｌを加えて１２５℃で６時間加熱還流した。反応終了後、溶媒を除き、クロロホルムと水で分離、有機層を抽出し、さらに水で２回洗浄した。無水硫酸ナトリウムで乾燥後、シリカゲルカラム（展開溶媒：トルエン／シクロヘキサン＝１／１０）で精製することにより、８．４９ｇ（ＬＣ面百９７％、収率９４％）の化合物Ｂを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９１（ｔ、６Ｈ）、１．３１〜１．９０（ｍ、２４Ｈ）、４．０８（ｔ、４Ｈ）、７．０７（ｄｄ、２Ｈ）、７．５５（ｄ、２Ｈ）、７．６８（ｄ、２Ｈ） Synthesis Example 2 (Synthesis of Compound B)

Compound B
Under an inert atmosphere, 4.43 g of compound A, 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 to reflux at 125 ° C. for 6 hours. After completion of the reaction, the solvent was removed, the organic layer was extracted with chloroform and water, and 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 B.
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)

化合物Ｃ Synthesis Example 3 (Synthesis of Compound C)

Compound C

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

化合物Ｄ
不活性雰囲気下２００ｍｌ四つ口フラスコに化合物Ｃ ３．９６ｇと酢酸／クロロホルム＝１：１混合液 １５ｍｌを加え、７０℃で撹拌し、溶解させた。続いて、臭素 ６．０２ｇを上記の溶媒 ３ｍｌに溶かして加え、３時間撹拌した。チオ硫酸ナトリウム水溶液を加えて未反応の臭素を除き、クロロホルムと水で分離、有機層を抽出、乾燥した。溶媒を除去し、シリカゲルカラム（展開溶媒：クロロホルム／ヘキサン＝１／４）で精製することにより、４．４６ｇ（ＬＣ面百９８％、収率８４％）の化合物Ｄを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９５（ｔ、６Ｈ）、１．３０〜１．９９（ｍ、２４Ｈ）、４．１９（ｔ、４Ｈ）、７．０４（ｓ、２Ｈ）、７．８９（ｓ、２Ｈ）

ＭＳ（ＦＤ^＋）Ｍ^＋ ６３０

合成例５（化合物Ｅの合成）

化合物Ｅ
不活性雰囲気下２００ｍｌ三つ口フラスコに化合物Ｄ ３．９ｇとジエチルエーテル ５０ｍｌを入れ、４０℃まで昇温、撹拌した。水素化アルミニウムリチウム １．１７ｇを少量ずつ加え、５時間反応させた。水を少量ずつ加えることによって過剰な水素化アルミニウムリチウムを分解し、３６％塩酸 ５．７ｍｌで洗浄した。クロロホルム、水で分離、有機層を抽出後乾燥した。シリカゲルカラム（展開溶媒：クロロホルム／ヘキサン＝１／５）で精製することにより、１．８ｇ（ＬＣ面百９９％、収率４９％）の化合物Ｅを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９０（ｔ、６Ｈ）、１．２６〜１．９７（ｍ、２４Ｈ）、４．１５（ｔ、４Ｈ）、７．４５（ｓ、２Ｈ）、７．９４（ｓ、２Ｈ）
ＭＳ（ＦＤ⁺）Ｍ⁺ ５９８
Synthesis Example 4 (Synthesis of Compound D)

Compound D
Under an inert atmosphere, 3.96 g of Compound C and 15 ml of a 1: 1 mixture of acetic acid / chloroform were added to a 200 ml four-necked flask, and the mixture was stirred at 70 ° C. to dissolve. Subsequently, 6.02 g of bromine was dissolved in 3 ml of the above solvent, and the mixture was stirred for 3 hours. An aqueous sodium thiosulfate solution was added to remove unreacted bromine, and the mixture was separated with chloroform and water, and the organic layer was extracted and dried. The solvent was removed and the residue was purified by a silica gel column (developing solvent: chloroform / hexane = 1/4) to obtain 4.46 g (LC area percentage 98%, yield 84%) of Compound D.
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

Synthesis Example 5 (Synthesis of Compound E)

Compound E
Under an inert atmosphere, 3.9 g of Compound D and 50 ml of diethyl ether were placed in a 200 ml three-necked flask, heated to 40 ° C. and stirred. Lithium aluminum hydride 1.17 g 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% hydrochloric acid. Separated with chloroform and water, the organic layer was extracted and dried. Purification by a silica gel column (developing solvent: chloroform / hexane = 1/5) gave 1.8 g (LC area percentage 99%, yield 49%) of Compound E.
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.

Synthesis Example 6
<Synthesis of Polymer Compound 1>
2,7-dibromo-9,9-dioctylfluorene (26 g, 0.047 mol), 2,7-dibromo-9,9-diisopentylfluorene (5.6 g, 0.012 mol) and 2,2′-bipyridyl (22 g, 0.141 mol) was dissolved in 1600 mL of dehydrated tetrahydrofuran, and the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (40 g, 0.15 mol) was added to this solution, and the temperature was raised to 60 ° C. and allowed to react for 8 hours. It was. After the reaction, this reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 200 mL / methanol 1200 mL / ion-exchanged water 1200 mL and stirred for 30 minutes, and then the deposited precipitate was filtered. Air dried. Then, it melt | dissolved in 1100 mL of toluene, it filtered, and the filtrate was dripped at 3300 mL of methanol, and was stirred for 30 minutes. The deposited precipitate was filtered, washed with 1000 mL of methanol, and dried under reduced pressure for 5 hours. The yield of the obtained copolymer was 20 g (hereinafter referred to as polymer compound 1). The average molecular weight and weight average molecular weight in terms of polystyrene of the polymer compound 1 were Mn = 4.6 × 10 ⁴ and Mw = 1.1 × 10 ⁵ , respectively.

Synthesis example 7
<Synthesis of Polymer Compound 2>
2,7-dibromo-9,9-dioctylfluorene (5.8 g, 0.0105 mol), N, N′-bis (4-bromophenyl) -N, N′-bis (4-n-butylphenyl)- 1,4-phenylenediamine (3.1 g, 0.0045 mmol) and 2,2′-bipyridyl (6.6 g) were dissolved in 20 mL of dehydrated tetrahydrofuran, and the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (12.0 g) was added to this solution, the temperature was raised to 60 ° C., and the reaction was continued for 3 hours with stirring. I let you. After the reaction, this reaction solution is cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% aqueous ammonia 50 mL / methanol about 200 mL / ion exchanged water about 300 mL, and stirred for 1 hour, and then the deposited precipitate is filtered. And dried under reduced pressure for 2 hours, and dissolved in about 350 mL of toluene. Thereafter, about 200 mL of 1N hydrochloric acid was added and stirred for 1 hour. The aqueous layer was removed, and about 200 mL of 4% aqueous ammonia was added to the organic layer. After stirring for 1 hour, the aqueous layer was removed. About 200 mL of ion exchange water was added to the organic layer and stirred, and then the aqueous layer was removed. The organic layer was dropped into about 700 mL of methanol and stirred for 1 hour, the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in about 350 mL of toluene. Thereafter, purification was performed through an alumina column, the recovered toluene solution was added dropwise to about 700 ml of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained copolymer (hereinafter referred to as polymer compound 2) was 3.5 g. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 3.4 × 10 ⁴ and Mw = 5.4 × 10 ⁴ , respectively.

化合物F

不活性雰囲気下、１Ｌ三つ口フラスコにトリス（ジベンジリデンアセトン）ジパラジウム１．６８ｇ（１．８３ｍｍｏｌ）、ジフェニルホスフィノフェロセン１．５２ｇ（２．７４ｍｍｏｌ）、ナトリウムターシャルブトキシド１７．６ｇ（１８３ｍｍｏｌ）およびトルエン４３０ｍＬを入れ、室温で１０分間撹拌した。続いて、アニリンを加えてさらに１０分間撹拌した。その後、８０℃に昇温し、１−ブロモ−４‐ブチルベンゼン１３ｇ（６１ｍｍｏｌ）をトルエン５０ｍＬに溶かして滴下し、滴下終了後、１２５℃まで昇温した。２時間後、室温まで冷却し、１Ｎの塩酸で洗浄、有機層を抽出し、硫酸ナトリウムで乾燥させた。硫酸ナトリウムおよび溶媒を除去後、トルエン：シクロヘキサン＝１：５混合溶媒を展開溶媒とするシリカゲルカラムで精製することにより、目的とする化合物Ｆを５．３９ｇ（収率２５％）得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９４（ｔ、６Ｈ）、１．３１〜１．４３（ｍ、４Ｈ）、１．５１〜１．６４（ｍ、４Ｈ）、２．５６（ｔ、４Ｈ）、６．９０〜７．０６（ｍ、７Ｈ）、７．１６〜７．２４（ｍ、６Ｈ）
ＭＳ（ＡＰＣＩ（＋））（Ｍ＋Ｈ）⁺ ３５８ Example 1
<Synthesis of Compound F>

Compound F

Under an inert atmosphere, in a 1 L three-necked flask, 1.68 g (1.83 mmol) of tris (dibenzylideneacetone) dipalladium, 1.52 g (2.74 mmol) of diphenylphosphinoferrocene, 17.6 g (183 mmol) of sodium tertiary butoxide ) And toluene (430 mL) were added, and the mixture was stirred at room temperature for 10 minutes. Subsequently, aniline was added and stirred for another 10 minutes. Thereafter, the temperature was raised to 80 ° C., 13 g (61 mmol) of 1-bromo-4-butylbenzene was dissolved in 50 mL of toluene and dropped, and the temperature was raised to 125 ° C. after completion of the dropping. After 2 hours, the mixture was cooled to room temperature, washed with 1N hydrochloric acid, and the organic layer was extracted and dried over sodium sulfate. After removing sodium sulfate and the solvent, 5.39 g (yield 25%) of the target compound F was obtained by purification with a silica gel column using a toluene: cyclohexane = 1: 5 mixed solvent as a developing solvent.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.94 (t, 6H), 1.31-1.43 (m, 4H), 1.51-1.64 (m, 4H), 2.56 (t, 4H), 6.90-7. 06 (m, 7H), 7.16-7.24 (m, 6H)
MS (APCI (+)) (M + H) ^<+> 358

化合物Ｇ

化合物Ｆ５．３９ｇ（１５ｍｍｏｌ）をＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）１３０ｍＬに溶解させた。その後、Ｎ−ブロモコハク酸イミド（ＮＢＳ）２．６３ｇ（１４．８ｍｍｏｌ）をＤＭＦ６５ｍＬに溶かし、室温で滴下した。滴下終了後、２４時間撹拌し、チオ硫酸ナトリウム水溶液を加えることによって反応を終了させた。トルエンと水で分離、有機層を抽出後、硫酸ナトリウムで乾燥させた。硫酸ナトリウムと溶媒を除去することによって、目的とする化合物Gを６．０５ｇ（収率９２％）得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９３（ｔ、６Ｈ）、１．３０〜１．４３（ｍ、４Ｈ）、１．５３〜１．６４（ｍ、４Ｈ）、２．５６（ｔ、４Ｈ）、６．９１（ｄ、４Ｈ）、６．９５（ｄ、２Ｈ）、７．０１（ｄ、４Ｈ）、７．２７（ｄ、２Ｈ） <Synthesis of Compound G>

Compound G

5.39 g (15 mmol) of Compound F was dissolved in 130 mL of N, N-dimethylformamide (DMF). Thereafter, 2.63 g (14.8 mmol) of N-bromosuccinimide (NBS) was dissolved in 65 mL of DMF and added dropwise at room temperature. After completion of the dropwise addition, the reaction was terminated by stirring for 24 hours and adding an aqueous sodium thiosulfate solution. After separating with toluene and water, the organic layer was extracted and dried over sodium sulfate. By removing sodium sulfate and the solvent, 6.05 g (yield 92%) of the target compound G was obtained.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.93 (t, 6H), 1.30 to 1.43 (m, 4H), 1.53 to 1.64 (m, 4H), 2.56 (t, 4H), 6.91 (d, 4H), 6.95 (d, 2H), 7.01 (d, 4H), 7.27 (d, 2H)

化合物Ｈ

不活性雰囲気下、５００ｍＬ三つ口フラスコにトリス（ジベンジリデンアセトン）ジパラジウム０．６９ｇ（０．７６ｍｍｏｌ）、ジフェニルホスフィノフェロセン０．６３ｇ（１．１３ｍｍｏｌ）、およびトルエン１８０ｍＬを入れ、室温で１０分間撹拌した。続いて、化合物Ｇ １１ｇ（２５．２ｍｍｏｌ）を入れ、さらに室温で１０分間撹拌した。
その後、Ｎ，Ｎ−ジフェニルフェニレンジアミン１３．１ｇ（５０．４ｍｍｏｌ）及びナトリウムターシャルブトキシド１４．５ｇ（１５１ｍｍｏｌ）を入れ、１２５℃まで昇温、８時間還流させた。反応終了後、１Ｎの塩酸で洗浄、有機層を抽出し、硫酸ナトリウムで乾燥させた。硫酸ナトリウムおよび溶媒を除去後、トルエン：ヘキサン＝５：１混合溶媒を展開溶媒とするシリカゲルカラムで精製することにより、目的とする化合物Ｈを８．８４ｇ（収率５７％）得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９３（ｔ、６Ｈ）、１．３０〜１．４２（ｍ、４Ｈ）、１．５１〜１．６４（ｍ、４Ｈ）、２．５５（ｔ、４Ｈ）、６．９８〜７．３４（ｂｒ、２７Ｈ） <Synthesis of Compound H>

Compound H

Under an inert atmosphere, a 500 mL three-necked flask was charged with 0.69 g (0.76 mmol) of tris (dibenzylideneacetone) dipalladium, 0.63 g (1.13 mmol) of diphenylphosphinoferrocene, and 180 mL of toluene, and 10 mL at room temperature. Stir for minutes. Subsequently, 11 g (25.2 mmol) of Compound G was added, and the mixture was further stirred at room temperature for 10 minutes.
Thereafter, 13.1 g (50.4 mmol) of N, N-diphenylphenylenediamine and 14.5 g (151 mmol) of sodium tertiary butoxide were added, heated to 125 ° C. and refluxed for 8 hours. After completion of the reaction, the mixture was washed with 1N hydrochloric acid, and the organic layer was extracted and dried over sodium sulfate. After removing sodium sulfate and the solvent, 8.84 g (yield 57%) of the target compound H was obtained by purification with a silica gel column using a mixed solvent of toluene: hexane = 5: 1.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.93 (t, 6H), 1.30 to 1.42 (m, 4H), 1.51 to 1.64 (m, 4H), 2.55 (t, 4H), 6.98 to 7. 34 (br, 27H)

化合物Ｊ

不活性雰囲気下、２００ｍＬ三つ口フラスコにトリス（ジベンジリデンアセトン）ジパラジウム０．１１ｇ（０．１２ｍｍｏｌ）、ジフェニルホスフィノフェロセン０．１０ｇ（０．１８ｍｍｏｌ）、ナトリウムターシャルブトキシド２．３４ｇ（２４．４ｍｍｏｌ）、およびトルエン６０ｍＬを入れ、室温で１０分間撹拌した。続いて、化合物Ｈ ５ｇ（８．１２ｍｍｏｌ）を入れ、さらに室温で１０分間撹拌した。その後、１−ブロモ−４‐ブチルベンゼン１．７３ｇ（８．１２ｍｍｏｌ）を入れ、１２５℃まで昇温、１１．５時間還流させた。反応終了後、１Ｎの塩酸で洗浄、有機層を抽出し、硫酸ナトリウムで乾燥させた。硫酸ナトリウムおよび溶媒を除去後、トルエン：シクロヘキサン＝１：５混合溶媒を展開溶媒とするシリカゲルカラムで精製することにより、目的とする化合物Ｊを４．５０ｇ（収率７４％）得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９３（ｔ、９Ｈ）、１．３０〜１．４３（ｍ、６Ｈ）、１．５２〜１．６４（ｍ、６Ｈ）、２．５６（ｂｒ、６Ｈ）、６．９５〜７．２８（ｂｒ、３０Ｈ） <Synthesis of Compound J>

Compound J

Under an inert atmosphere, 0.13 g (0.12 mmol) of tris (dibenzylideneacetone) dipalladium, 0.10 g (0.18 mmol) of diphenylphosphinoferrocene, 2.34 g of sodium tertiary butoxide (24 .4 mmol) and 60 mL of toluene were added, and the mixture was stirred at room temperature for 10 minutes. Subsequently, 5 g (8.12 mmol) of Compound H was added, and the mixture was further stirred at room temperature for 10 minutes. Thereafter, 1.73 g (8.12 mmol) of 1-bromo-4-butylbenzene was added, and the temperature was raised to 125 ° C. and refluxed for 11.5 hours. After completion of the reaction, the mixture was washed with 1N hydrochloric acid, and the organic layer was extracted and dried over sodium sulfate. After removing sodium sulfate and the solvent, 4.50 g (yield 74%) of the target compound J was obtained by purification on a silica gel column using a toluene: cyclohexane = 1: 5 mixed solvent as a developing solvent.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.93 (t, 9H), 1.30 to 1.43 (m, 6H), 1.52 to 1.64 (m, 6H), 2.56 (br, 6H), 6.95 to 7. 28 (br, 30H)

化合物Ｋ

化合物Ｊ４．５ｇ（６．０２ｍｍｏｌ）をＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）５０ｍＬに溶解させた。その後、Ｎ−ブロモコハク酸イミド（ＮＢＳ）２．１０ｇ（１１．８ｍｍｏｌ）をＤＭＦ５０ｍＬに溶かし、室温で滴下した。滴下終了後、２４時間撹拌し、チオ硫酸ナトリウム水溶液を加えることによって反応を終了させた。５００ｍＬの水に注いで洗浄し、ろ過することによって目的とする化合物Ｋを５．１０ｇ（収率９４％）得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９４（ｔ、９Ｈ）、１．３４〜１．４１（ｂｒ、６Ｈ）、１．５２〜１．６４（ｂｒ、６Ｈ）、２．５６（ｂｒ、６Ｈ）、６．４２（ｄ、４Ｈ）、６．８７〜７．４１（ｂｒ、２４Ｈ）
ＭＳ（ＡＰＣＩ（＋））（Ｍ＋Ｈ）⁺ ９０６ <Synthesis of Compound K>

Compound K

Compound J4.5 g (6.02 mmol) was dissolved in 50 mL of N, N-dimethylformamide (DMF). Thereafter, 2.10 g (11.8 mmol) of N-bromosuccinimide (NBS) was dissolved in 50 mL of DMF and added dropwise at room temperature. After completion of the dropwise addition, the reaction was terminated by stirring for 24 hours and adding an aqueous sodium thiosulfate solution. It was poured into 500 mL of water, washed, and filtered to obtain 5.10 g (yield 94%) of the target compound K.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.94 (t, 9H), 1.34 to 1.41 (br, 6H), 1.52 to 1.64 (br, 6H), 2.56 (br, 6H), 6.42 (d, 4H), 6.87-7.41 (br, 24H)
MS (APCI (+)) (M + H) ^<+> 906

<Synthesis of Polymer Compound 3>
0.63 g (1.05 mmol) of the above compound E 0.41 g (0.45 mmol) of the above compound K and 0.55 g of 2,2′-bipyridyl were dissolved in 45 mL of dehydrated tetrahydrofuran, and then bubbled with nitrogen to evacuate the system. Replaced with nitrogen. Under a nitrogen atmosphere, 1.0 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } is added to this solution, the temperature is raised to 60 ° C., and the mixture is reacted for 3 hours with stirring. It was. After the reaction, this reaction solution is cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 10 mL / methanol about 100 mL / ion-exchanged water about 200 mL, and stirred for 1 hour, and then the deposited precipitate is filtered. And dried under reduced pressure for 2 hours, and dissolved in about 350 mL of toluene. Thereafter, about 200 mL of 1N hydrochloric acid was added and stirred for 1 hour. The aqueous layer was removed, and about 200 mL of 2% aqueous ammonia was added to the organic layer. After stirring for 1 hour, the aqueous layer was removed. About 200 mL of ion exchange water was added to the organic layer and stirred, and then the aqueous layer was removed. Thereafter, purification was performed through an alumina column, the recovered toluene solution was added dropwise to about 700 ml of methanol and stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained copolymer (hereinafter referred to as polymer compound 3) was 0.4 g. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 2.3 × 10 ⁴ and Mw = 8.8 × 10 ⁴ , respectively.

化合物Ｌ

三つ口フラスコに４−ｎ−ブチルアニリン６３．４ｇ（０．４２５ｍｏｌ）、ブロモベンゼン６３．４ｇ（０．４０４ｍｏｌ）をトルエン４２５ｍｌに溶解した。これにナトリウムブトキシド１０２．１ｇ（１．０６ｍｏｌ）を加え、窒素置換した。そこにトリスジベンジリデンアセトン０．９２ｇ、トリ-ｔｅｒｔ-ブチルフェニルホスフィン０．８２ｇを仕込み、還流条件下５時間反応させた。 放冷後、トルエン１２００ｍｌを加え、２分割してそれぞれ水９００ｍｌで４回洗浄し、有機層を併せて、硫酸ナトリウムで乾燥後、溶媒を留去し黒色油状物を得た。これをシリカゲルカラムクロマトグラフィー（ヘキサン／クロロホルム＝７／３）で分離精製し、目的物を得た（収量６８．２ｇ、収率７３．８％）。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ０．９１（ｔ、３Ｈ）、１．３５（ｍ、４Ｈ）、１．５６（ｍ、４Ｈ）、２．５３（ｔ、２Ｈ）、５．４０（ｓ、１Ｈ）、６．８３〜７．２１（ｍ、９Ｈ）。
ＬＣ／ＥＳＩ（＋） ｍ／ｚ＝２２６ Example 2
<Synthesis of Compound L>

Compound L

In a three-necked flask, 63.4 g (0.425 mol) of 4-n-butylaniline and 63.4 g (0.404 mol) of bromobenzene were dissolved in 425 ml of toluene. To this, 102.1 g (1.06 mol) of sodium butoxide was added, and the atmosphere was replaced with nitrogen. Thereto, 0.92 g of trisdibenzylideneacetone and 0.82 g of tri-tert-butylphenylphosphine were charged and reacted for 5 hours under reflux conditions. After allowing to cool, 1200 ml of toluene was added, and the mixture was divided into two and washed 4 times with 900 ml of water. The organic layers were combined, dried over sodium sulfate, and the solvent was distilled off to obtain a black oil. This was separated and purified by silica gel column chromatography (hexane / chloroform = 7/3) to obtain the desired product (yield 68.2 g, yield 73.8%).
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 0.91 (t, 3H), 1.35 (m, 4H), 1.56 (m, 4H), 2.53 (t, 2H), 5.40 (s, 1H), 6.83-7 .21 (m, 9H).
LC / ESI (+) m / z = 226

化合物Ｍ

三つ口フラスコに化合物Ｌ６．７６ｇ（３０．０ｍｍｏｌ）、ＴＰＡ６．２０ｇ（１３．５ｍｍｏｌ）ををトルエン３０ｍｌに溶解した。これにナトリウムブトキシド７．２１ｇ水（７５．０ｍｍｏｌ）を加え、窒素置換した。そこにトリスジベンジリデンアセトン０．０６ｇ、トリ-ｔｅｒｔ-ブチルフェニルホスフィン０．０５ｇを仕込み、還流条件下５時間反応させた。

ＴＰＡ

放冷後、トルエン２００ｍｌを加え、水１００ｍｌで３回洗浄し、硫酸ナトリウムで乾燥後、溶媒を留去し褐色結晶を得た。これをヘキサンで再結晶して目的物を得た（収量８．００ｇ、収率７５．６％）。
ＦＤ ＭＳ ｍ／ｚ＝７４８
<Synthesis of Compound M>

Compound M

Compound L 6.76 g (30.0 mmol) and TPA 6.20 g (13.5 mmol) were dissolved in 30 ml of toluene in a three-necked flask. Sodium butoxide 7.21 g water (75.0 mmol) was added thereto, and the atmosphere was replaced with nitrogen. Thereto, 0.06 g of trisdibenzylideneacetone and 0.05 g of tri-tert-butylphenylphosphine were charged and reacted for 5 hours under reflux conditions.

TPA

After allowing to cool, 200 ml of toluene was added, washed with 100 ml of water three times, dried over sodium sulfate, and then the solvent was distilled off to obtain brown crystals. This was recrystallized from hexane to obtain the desired product (yield 8.00 g, yield 75.6%).
FD MS m / z = 748

化合物Ｎ
三つ口フラスコに化合物Ｍ３．７４ｇ（５．０ｍｍｏｌ）をＮ，Ｎ−ジメチルホルムアミド４００ｍｌに分散させ、クロロホルム１０ｍｌを加えた。そのスラリーを３０℃に保温しながら、Ｎ−ブロモスクシンイミド１．８７ｇ（１０．５ｍｍｏｌ）をＮ，Ｎ−ジメチルホルムアミド８ｍｌに溶解した溶液を遮光しながら１時間かけて滴下した。その後自然冷却しながら１９時間反応させた。反応後、析出した結晶を濾別し、得られた結晶をＮ，Ｎ−ジメチルホルムアミド２００ｍｌで２回洗浄した。乾燥後目的物を得た。
（収量２．５０ｇ、収率５５．２％）。
ＦＤ ＭＳ ｍ／ｚ＝９０５ Synthesis of Compound N

Compound N
In a three-necked flask, 3.74 g (5.0 mmol) of Compound M was dispersed in 400 ml of N, N-dimethylformamide, and 10 ml of chloroform was added. While keeping the slurry at 30 ° C., a solution prepared by dissolving 1.87 g (10.5 mmol) of N-bromosuccinimide in 8 ml of N, N-dimethylformamide was added dropwise over 1 hour while shielding light. Thereafter, the mixture was allowed to react for 19 hours with natural cooling. After the reaction, the precipitated crystals were separated by filtration, and the obtained crystals were washed twice with 200 ml of N, N-dimethylformamide. The desired product was obtained after drying.
(Yield 2.50 g, Yield 55.2%).
FD MS m / z = 905

<Synthesis of Polymer Compound 4>
0.42 g (0.7 mmol) of the compound E, 0.27 g (0.3 mmol) of the compound N and 0.39 g of 2,2′-bipyridyl were dissolved in 28 mL of dehydrated tetrahydrofuran, and then bubbled with nitrogen. Was replaced with nitrogen. Under a nitrogen atmosphere, 0.69 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } is added to this solution, heated to 60 ° C., and allowed to react for 3 hours with stirring. It was. After the reaction, this reaction solution is cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% aqueous ammonia 14 mL / methanol about 170 mL / ion exchanged water about 70 mL, and stirred for 1 hour, and then the deposited precipitate is filtered. The solution was dried under reduced pressure for 2 hours and dissolved in about 40 mL of toluene. Thereafter, about 40 mL of 1N hydrochloric acid was added and stirred for 1 hour, the aqueous layer was removed, about 40 mL of 2% aqueous ammonia was added to the organic layer, and the aqueous layer was removed after stirring for 1 hour. About 40 mL of ion exchange water was added to the organic layer and stirred, and then the aqueous layer was removed. About 200 mL of methanol was added dropwise, and the precipitate was collected and dried under reduced pressure.
Then, it melt | dissolved in 40 mL of toluene, it refine | purified through an alumina column, the collect | recovered toluene solution was dripped at about 280 mL of methanol, it stirred for 1 hour, the depositing precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained copolymer (hereinafter referred to as polymer compound 4) was 0.4 g. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 1.9 × 10 ⁴ and Mw = 6.4 × 10 ⁴ , respectively.

アルゴン雰囲気下、１−ブロモ−４−ｔ−ブチル−２，６−ジメチルベンゼン １９．５ｇ （８０．９ｍｍｏｌ）にｔ−ブトキシナトリウム９．３ｇ （９７．０ｍｍｏｌ）、Ｐｄ２（ｄｂａ）３ ０．７ｇ （０．８ｍｍｏｌ）、トリ−ｔ−ブチルホスフィン０．７ｇ（３．２ｍｍｏｌ）、アニリン ７．８ｇ （８０．９ｍｍｏｌ）、トルエン８７．８ｇを加え室温で５分攪拌した後、１００℃に昇温し５時間攪拌した。攪拌が終了した後室温に冷却し、トルエン１００ｍＬ加え室温で１時間攪拌し析出した固体を濾別した。得られた濾液をシリカゲルカラムクロマトグラフィーにかけた後、減圧濃縮し粗生成物１９．７ｇを得た。粗生成物にメタノール４５ｍＬを加え７０℃まで昇温し攪拌した後、氷浴で冷却して得られた沈殿を濾取、減圧乾燥し目的物であるＮ−４−ｔ−ブチル−２，６−ジメチルフェニル−Ｎ−フェニルアミンを白色固体として得た（収量１５．７ｇ、収率７６．４％）。 Example 3
<Synthesis of Compound O>

Under an argon atmosphere, 19.5 g (80.9 mmol) of 1-bromo-4-t-butyl-2,6-dimethylbenzene, 9.3 g (97.0 mmol) of sodium t-butoxy, and 0.7 g of Pd2 (dba) 3 (0.8 mmol), tri-t-butylphosphine 0.7 g (3.2 mmol), aniline 7.8 g (80.9 mmol) and toluene 87.8 g were added and stirred at room temperature for 5 minutes, and then the temperature was raised to 100 ° C. And stirred for 5 hours. After completion of the stirring, the mixture was cooled to room temperature, 100 mL of toluene was added, and the mixture was stirred at room temperature for 1 hour, and the precipitated solid was separated by filtration. The obtained filtrate was subjected to silica gel column chromatography and then concentrated under reduced pressure to obtain 19.7 g of a crude product. 45 mL of methanol was added to the crude product, and the mixture was heated to 70 ° C. and stirred, and then the precipitate obtained by cooling in an ice bath was collected by filtration, dried under reduced pressure, and the target product, N-4-t-butyl-2,6. -Dimethylphenyl-N-phenylamine was obtained as a white solid (yield 15.7 g, yield 76.4%).

化合物Ｐ

アルゴン雰囲気下、１-ブロモ-２，４，６-トリメチルベンゼン ２３．６ｇ(１１８．２ｍｍｏｌ)にｔ-ブトキシナトリウム １３．６ｇ (１４１．８ｍｍｏｌ)、Ｐｄ_２(ｄｂａ)_３ ０．５ｇ (０．６ｍｍｏｌ)、トリ-ｔ-ブチルホスフィン０．５ｇ(２．４ｍｍｏｌ)、ジフェニルアミン ２０．０ｇ (１１８．２ｍｍｏｌ)、トルエン９０．０ｇを加え室温で５分攪拌した後、１００℃に昇温し４時間攪拌した。攪拌が終了した後、室温に冷却し、トルエン３００ｍＬ加え室温で１時間攪拌し析出した固体を濾別した。得られた濾液を減圧濃縮し粗生成物３２．７ｇを得た。粗生成物にシクロヘキサン１０５ｍＬを加え７０℃まで昇温し攪拌した後、氷浴で冷却して得られた沈殿を濾取、減圧乾燥し目的物であるＮ-２，４，６-トリメチルフェニル-Ｎ-フェニルアミンを白色固体として得た（収量２４．
８ｇ、収率７２．８％）。 <Synthesis of Compound P>

Compound P

Under an argon atmosphere, 23.6 g (118.2 mmol) of 1-bromo-2,4,6-trimethylbenzene, 13.6 g (141.8 mmol) of sodium t-butoxy, 0.5 g of Pd ₂ (dba) ₃ (0. 6 mmol), 0.5 g (2.4 mmol) of tri-t-butylphosphine, 20.0 g (118.2 mmol) of diphenylamine and 90.0 g of toluene, and the mixture was stirred at room temperature for 5 minutes, and then heated to 100 ° C. for 4 hours. Stir. After completion of the stirring, the mixture was cooled to room temperature, 300 mL of toluene was added, and the mixture was stirred at room temperature for 1 hour, and the precipitated solid was separated by filtration. The obtained filtrate was concentrated under reduced pressure to obtain 32.7 g of a crude product. After adding 105 mL of cyclohexane to the crude product and raising the temperature to 70 ° C. and stirring, the precipitate obtained by cooling in an ice bath was collected by filtration, dried under reduced pressure, and the target product N-2,4,6-trimethylphenyl- N-phenylamine was obtained as a white solid (yield 24.
8 g, yield 72.8%).

化合物Ｑ

アルゴン雰囲気下、化合物Ｐ ５．０ｇ（１７．４ｍｍｏｌ）、クロロホルム２５０．１ｇからなる溶液に、臭素５．５ｇ（３４．６ｍｍｏｌ）を５℃で１時間かけて滴下し、同温で２時間攪拌した。攪拌終了後、水１００ｍＬを加え２５℃で１５分攪拌した後、油層を水層と分液した。さらに、水層にクロロホルム２００ccを加え２５℃で１５分攪拌した後、油層を水層と分液した。上記２回の分液操作で得られた油層を合一し、無水硫酸ナトリウムを加え攪拌した。無水硫酸ナトリウムを濾別し、得られた濾液を減圧濃縮し粗生成物７．８ｇを得た。粗生成物に２-プロパノール５５ｍＬを加え８０℃まで昇温し攪拌した後、放冷して得られた沈殿を濾取、減圧乾燥し目的物であるＮ-２，４，６-トリメチルフェニル-Ｎ-フェニルアミンを白色固体として得た（収量６．７ｇ、収率８６．２％）。 <Synthesis of Compound Q>

Compound Q

In an argon atmosphere, 5.5 g (34.6 mmol) of bromine was added dropwise to a solution consisting of 5.0 g (17.4 mmol) of compound P and 250.1 g of chloroform over 1 hour at 5 ° C., and the mixture was stirred at the same temperature for 2 hours. did. After completion of stirring, 100 mL of water was added and stirred at 25 ° C. for 15 minutes, and then the oil layer was separated from the aqueous layer. Further, 200 cc of chloroform was added to the aqueous layer and stirred at 25 ° C. for 15 minutes, and then the oil layer was separated from the aqueous layer. The oil layers obtained by the above two liquid separation operations were combined, and anhydrous sodium sulfate was added and stirred. Anhydrous sodium sulfate was removed by filtration, and the resulting filtrate was concentrated under reduced pressure to obtain 7.8 g of a crude product. After adding 55 mL of 2-propanol to the crude product and raising the temperature to 80 ° C. and stirring, the precipitate obtained by allowing to cool was collected by filtration, dried under reduced pressure, and the target product N-2,4,6-trimethylphenyl- N-phenylamine was obtained as a white solid (yield 6.7 g, yield 86.2%).

化合物Ｒ

不活性雰囲気下で、１００ｍｌの３つ口フラスコに脱気した脱水トルエン４０ｍｌを入れ、トリ（ｔ−ブチル）ホスフィン０．２７ｇを加えた。続いてトリス（ジベンジリデンアセトン）ジパラジウム０．１８ｇ、化合物Ｏ ４．３ｇ、ｔ−ブトキシナトリウム２．２ｇ、化合物Ｑ ３．５ｇを加えた後、１００℃で３時間反応させた。
反応液を飽和食塩水３００ｍｌに加え、温めたクロロホルム３００ｍｌで抽出した。溶媒を留去した後、トルエン５０ｍｌを加えて、加熱、放冷した後、沈殿をろ過し、白色の固体５．２ｇを得た。 <Synthesis of Compound R>

Compound R

Under an inert atmosphere, 40 ml of degassed dehydrated toluene was placed in a 100 ml three-necked flask, and 0.27 g of tri (t-butyl) phosphine was added. Subsequently, tris (dibenzylideneacetone) dipalladium (0.18 g), compound O (4.3 g), t-butoxy sodium (2.2 g), and compound Q (3.5 g) were added, followed by reaction at 100 ° C. for 3 hours.
The reaction solution was added to 300 ml of saturated brine and extracted with 300 ml of warm chloroform. After the solvent was distilled off, 50 ml of toluene was added, and the mixture was heated and allowed to cool, and then the precipitate was filtered to obtain 5.2 g of a white solid.

化合物Ｓ

不活性雰囲気下で、１０００ｍｌの３つ口フラスコに脱水Ｎ，Ｎ−ジメチルホルムアミド３５０ｍｌを入れ、化合物Ｒ ５．０ｇを溶解した後、氷浴下でＮ−ブロモスクシンイミド２．４ｇ／Ｎ，Ｎ−ジメチルホルムアミド溶液を滴下し、一昼夜反応させた。
反応液に水１５０ｍｌを加え、析出した沈殿をろ過し、メタノール５０ｍｌで２回洗浄し白色の固体４．４ｇを得た。
１Ｈ−ＮＭＲ（３００ＭＨｚ／ＴＨＦ−ｄ８）：
δ１．３（ｓ，１８Ｈ）、１．９（ｓ，６Ｈ）、２．０（ｓ，１２Ｈ）、２．２（ｓ，３Ｈ）、６．６〜６．７（ｄ，４Ｈ）、６．７〜６．８（ｂｒ，８Ｈ）、６．９（ｓ，２Ｈ）、７．１（ｓ，４Ｈ）、７．１〜７．２（ｄ，４Ｈ）
ＭＳ（ＦＤ＋）Ｍ＋ ９４７ <Synthesis of Compound S>

Compound S

Under an inert atmosphere, 350 ml of dehydrated N, N-dimethylformamide was placed in a 1000 ml three-necked flask to dissolve 5.0 g of Compound R, and then 2.4 g / N, N-N-bromosuccinimide was dissolved in an ice bath. A dimethylformamide solution was added dropwise and allowed to react overnight.
150 ml of water was added to the reaction solution, and the deposited precipitate was filtered and washed twice with 50 ml of methanol to obtain 4.4 g of a white solid.
1H-NMR (300 MHz / THF-d8):
δ1.3 (s, 18H), 1.9 (s, 6H), 2.0 (s, 12H), 2.2 (s, 3H), 6.6 to 6.7 (d, 4H), 6 .7 to 6.8 (br, 8H), 6.9 (s, 2H), 7.1 (s, 4H), 7.1 to 7.2 (d, 4H)
MS (FD +) M + 947

<Synthesis of Polymer Compound 5>
0.48 g (0.8 mmol) of the compound E, 0.19 g (0.2 mmol) of the compound S and 0.33 g of 2,2′-bipyridyl were dissolved in 28 mL of dehydrated tetrahydrofuran, and then bubbled with nitrogen. Was replaced with nitrogen. Under a nitrogen atmosphere, 0.58 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } is added to this solution, heated to 60 ° C., and allowed to react for 3 hours with stirring. It was. After the reaction, this reaction solution is cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% aqueous ammonia 14 mL / methanol about 170 mL / ion exchanged water about 70 mL, and stirred for 1 hour, and then the deposited precipitate is filtered. The solution was dried under reduced pressure for 2 hours and dissolved in about 40 mL of toluene. Thereafter, about 40 mL of 1N hydrochloric acid was added and stirred for 1 hour. The aqueous layer was removed, and about 40 mL of 2% aqueous ammonia was added to the organic layer. After stirring for 1 hour, the aqueous layer was removed. About 40 mL of ion exchange water was added to the organic layer and stirred, and then the aqueous layer was removed. About 200 mL of methanol was added dropwise, and the precipitate was collected and dried under reduced pressure. Then, it melt | dissolved in 40 mL of toluene, it refine | purified through an alumina column, the collect | recovered toluene solution was dripped at about 280 mL of methanol, it stirred for 1 hour, the depositing precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained copolymer (hereinafter referred to as polymer compound 5) was 0.35 g. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 5.2 × 10 ⁴ and Mw = 2.4 × 10 ⁴ , respectively.

Example 4
A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is formed into a film having a thickness of 70 nm by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrenesulfonic acid (Bayer, BaytronP). Dry on a hot plate at 200 ° C. for 10 minutes. Next, a film was formed at a rotational speed of 1500 rpm by spin coating using a toluene solution prepared such that a 5: 5 (weight ratio) mixture of the polymer compound 3 and the polymer compound 1 was 1.5 wt%. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then about 4 nm of lithium fluoride was vapor-deposited, and about 5 nm of calcium and then about 50 nm of aluminum were vapor-deposited as a cathode to produce an EL device. After the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.
By applying voltage to the resulting device, EL light emission having a peak at 480 nm was obtained. When the initial luminance was set to 100 cd / m ² and the attenuation of the luminance was measured, the luminance after 300 hours was 71 cd / m ² .

Example 5
A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is formed into a film having a thickness of 70 nm by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrenesulfonic acid (Bayer, BaytronP). Dry on a hot plate at 200 ° C. for 10 minutes. Next, a film was formed at a rotational speed of 1500 rpm by spin coating using a toluene solution prepared such that a 3: 7 (weight ratio) mixture of polymer compound 4 and polymer compound 1 was 1.5 wt%. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then about 4 nm of lithium fluoride was vapor-deposited, and about 5 nm of calcium and then about 80 nm of aluminum were vapor-deposited as a cathode, thereby producing an EL device. After the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.
By applying a voltage to the obtained device, EL light emission having a peak at 472 nm was obtained. When the initial luminance was set to 100 cd / m ² and the attenuation of luminance was measured, the luminance after 300 hours was 65 cd / m ² .

Example 6
A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is formed into a film having a thickness of 70 nm by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrenesulfonic acid (Bayer, BaytronP). Dry on a hot plate at 200 ° C. for 10 minutes. Next, a film was formed at a rotational speed of 1500 rpm by spin coating using a toluene solution prepared such that a 5: 5 (weight ratio) mixture of the polymer compound 3 and the polymer compound 1 was 1.5 wt%. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then about 4 nm of lithium fluoride was vapor-deposited, and about 5 nm of calcium and then about 80 nm of aluminum were vapor-deposited as a cathode, thereby producing an EL device. After the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.
By applying voltage to the resulting device, EL light emission having a peak at 480 nm was obtained. When the initial luminance was set to 100 cd / m ² and the attenuation of the luminance was measured, the luminance after 300 hours was 68 cd / m ² .

Comparative Example 1
Using high molecular compound 2 instead of high molecular compound 3, a 1.5 wt% toluene solution of a 3: 7 (weight ratio) mixture of high molecular compound 2 and high molecular compound 1 was formed by spin coating at a rotation speed of 1200 rpm. A device was produced in the same manner as in Example 4 except that the film was formed.
By applying voltage to the resulting device, EL light emission having a peak at 464 nm was obtained. Further, when the initial luminance was set to 100 cd / m ² and the luminance attenuation was measured, the luminance attenuation was measured and the luminance after 300 hours was 53 cd / m ² .

Claims (18)

A polymer compound comprising a repeating unit represented by the following formula (1 ′ ) and having a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ .

_Wherein, Ar 1, the Ar ₂ Contact and Ar ₃ each independently represent an arylene group or a divalent heterocyclic group, _{E 5} and _{E 6} are each independently 4-position, 2-position and 6-position substituent Represents a phenyl group having an alkyl group or an alkoxy group . n represents 2 . ] _2. The polymer compound according to claim ₁ , wherein Ar ₁ , Ar ₂ and Ar ₃ are each independently a group represented by the following formula (2).

[In the formula, Ra, Rb, Rc and Rd are each independently a hydrogen atom, 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, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, Represents a monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group. q represents an integer of 1 to 3. When a plurality of Ra, Rb, Rc, and Rd are present, they may be the same or different. Ra and Rb, and Rc and Rd may each form an aromatic ring together with the carbon atom on the benzene ring to which they are bonded. ] Furthermore, the high molecular compound of Claim 1 or 2 containing the repeating unit shown by following formula (4), (5), (6) or (7).

-Ar ₁₃ - (4)

—Ar ₁₆ —X ₂ — (6)

-X _3- (7)

[Wherein, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ , and Ar ₁₆ each independently represent an arylene group, a divalent heterocyclic group, or a divalent group having a metal complex structure. X ₁ , X ₂ and X ₃ each independently represent —CR ₂ ═CR ₃ —, —C≡C—, —N (R ₄ ) —, or — (SiR ₅ R ₆ ) b—. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, or a cyano group. R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or an arylalkyl group. a shows the integer of 0-2. b shows the integer of 1-12. When a plurality of Ar ₁₄ , X ₁ , R ₅ and R ₆ are present, they may be the same or different. ] Furthermore, it has a repeating unit chosen from the repeating unit shown by following formula (4) or (5), The high molecular compound of Claim 1 or 2 characterized by the above-mentioned.
-Ar ₁₃ - (4)

[Wherein, Ar ₁₃ , Ar ₁₄ , and Ar ₁₅ each independently represent an arylene group, a divalent heterocyclic group, or a divalent group having a metal complex structure. X ₁ represents —N (R ₄ ) —. R ₄ represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or an arylalkyl group. a shows the integer of 0-2. When a plurality of Ar ₁₄ , X ₁ , and R ₄ are present, they may be the same or different. ] In the formula (4), Ar ₁₃ is a divalent heterocyclic group, The polymer compound according to claim 4 . A composition comprising at least one material selected from a hole transport material, an electron transport material, and a light-emitting material and at least one polymer compound according to any one of claims 1 to 5 . An ink composition comprising the polymer compound according to any one of claims 1 to 5 . The ink composition according to claim 7 , wherein the viscosity is 1 to 20 mPa · s at 25 ° C. Light-emitting thin film containing the polymer compound according to any one of claims 1-5. The electroconductive thin film containing the high molecular compound in any one of Claims 1-5 . The organic-semiconductor thin film containing the high molecular compound in any one of Claims 1-5 . A polymer light emitting device comprising a layer containing the polymer compound according to any one of claims 1 to 5 between electrodes composed of an anode and a cathode. The polymer light emitting device according to claim 12, wherein the layer containing the polymer compound according to any one of claims 1 to 5 is a light emitting layer. 14. The polymer light emitting device according to claim 13 , wherein the light emitting layer further contains a hole transport material, an electron transport material or a light emitting material. Planar light source characterized by using the polymer light-emitting device according to any one of claims 12-14. Segment display device characterized by using the polymer light-emitting device according to any one of claims 12-14. Dot matrix display device characterized by using the polymer light-emitting device according to any one of claims 12-14. The liquid crystal display device, characterized in that the backlight polymer light-emitting device according to any one of claims 12-14.