JP2008056910A - Polymer compound and polymer light emitting device using the same - Google Patents

Abstract

〔式中、Ａｒ₁及びＡｒ₂は、それぞれ独立に、置換基を有していてもよいアリーレン基、置換基を有していてもよい２価の複素環基、又は置換基を有していてもよい２価の芳香族アミン基を表す。Ａｒ₁及びＡｒ₂が複数存在する場合には、それらは同一であっても異なっていてもよい。Ｚ₁は、−ＣＲ₁＝ＣＲ₂−又は−Ｃ≡Ｃ−を表す。ここで、Ｒ₁及びＲ₂は、それぞれ独立に、水素原子、アルキル基、アリール基、１価の複素環基又はシアノ基を表す。ｍ及びｎは、それぞれ独立に、１又は２である。Ｒ^s及びＲ^tは、それぞれ独立に、水素原子、アルキル基又はアルコキシ基を表す。〕
で表される繰り返し単位を含み、ポリスチレン換算の数平均分子量が１×１０³〜１×１０⁸である高分子化合物。
【選択図】なしThe present invention provides a novel polymer compound that is excellent in deep color and useful as a light emitting material in a red region, and a polymer light-emitting device using the polymer compound.
The following formula (1):

[In the formula, Ar ₁ and Ar ₂ each independently have an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or a substituent. The divalent aromatic amine group which may be sufficient is represented. When a plurality of Ar ₁ and Ar ₂ are present, they may be the same or different. Z ₁ represents —CR ₁ ═CR ₂ — or —C≡C—. Here, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. m and n are each independently 1 or 2. R ^s and R ^t each independently represents a hydrogen atom, an alkyl group or an alkoxy group. ]
A high molecular compound having a polystyrene-reduced number average molecular weight of 1 × 10 ³ to 1 × 10 ⁸ .
[Selection figure] None

Description

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

  High-molecular-weight light-emitting materials are variously studied because they are useful as materials used for the light-emitting layer of light-emitting elements. Specifically, a polyarylene composed of a benzothiadiazole derivative and spirofluorene (Patent Document 1) and a polyarylene composed of a benzothiadiazole derivative and fluorene (Patent Documents 2 and 3) have been proposed.

WO03 / 020790 pamphlet International Publication No. 00/046321 Pamphlet WO 02/059121 pamphlet

However, these compounds are not sufficiently deep-colored as light emitting materials in the red region.
Accordingly, an object of the present invention is to provide a novel polymer compound that is excellent in deep color and is useful as a light emitting material in the red region, and a polymer light emitting device using the polymer compound.

〔式中、Ａｒ₁及びＡｒ₂は、それぞれ独立に、置換基を有していてもよいアリーレン基、置換基を有していてもよい２価の複素環基、又は置換基を有していてもよい２価の芳香族アミン基を表す。Ａｒ₁及びＡｒ₂が複数存在する場合には、それらは同一であっても異なっていてもよい。Ｚ₁は、−ＣＲ₁＝ＣＲ₂−又は−Ｃ≡Ｃ−を表す。ここで、Ｒ₁及びＲ₂は、それぞれ独立に、水素原子、アルキル基、アリール基、１価の複素環基又はシアノ基を表す。ｍ及びｎは、それぞれ独立に、１又は２である。Ｒ^s及びＲ^tは、それぞれ独立に、水素原子、アルキル基又はアルコキシ基を表す。〕
で表される繰り返し単位を含み、ポリスチレン換算の数平均分子量が１×１０³〜１×１０⁸である高分子化合物を提供する。 The present invention provides the following formula (1):

[In the formula, Ar ₁ and Ar ₂ each independently have an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or a substituent. The divalent aromatic amine group which may be sufficient is represented. When a plurality of Ar ₁ and Ar ₂ are present, they may be the same or different. Z ₁ represents —CR ₁ ═CR ₂ — or —C≡C—. Here, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. m and n are each independently 1 or 2. R ^s and R ^t each independently represents a hydrogen atom, an alkyl group or an alkoxy group. ]
A high molecular compound having a polystyrene-reduced number average molecular weight of 1 × 10 ³ to 1 × 10 ⁸ is provided.

  Since the polymer compound of the present invention has the peak wavelength of the fluorescence spectrum on the long wavelength side, it is excellent in deep color and useful as a light emitting material in the red region. Moreover, since the polymer compound of the present invention has an absorption edge wavelength on the long wavelength side, it is also useful for thin films, organic transistors, solar cells and the like. Since a polymer light emitting device using the polymer compound has high performance, it is useful for a planar light source, a display device and the like.

The present invention will be described below. In the present specification, when a vinylene moiety is present in the structure, the moiety may have either a cis or trans structure.
<Polymer compound>
The polymer compound of the present invention contains a repeating unit represented by the formula (1) and has a polystyrene-equivalent number average molecular weight of 1 × 10 ³ to 1 × 10 ⁸ , preferably 2 × 10 ³ to 10 ⁷ . Is. One type of repeating unit may be included, or two or more types of repeating units may be included.

-Repeating unit represented by Formula (1) In said Formula (1), the group represented by Ar < ₁ >, Ar < ₂ > may have a substituent. Examples of the substituent include alkyl groups, alkoxy groups, alkylthio groups, alkylsilyl groups, alkylamino groups, aryl groups, aryloxy groups, arylalkyl groups, arylalkoxy groups, arylalkenyl groups, arylalkynyl groups, arylamino groups. Group, monovalent heterocyclic group, acyl group, acyloxy group, substituted carboxyl group, cyano group and the like. These substituents are the same as those described and exemplified for the group represented by R described later. When Ar ₁ and Ar ₂ have a plurality of substituents, they may be the same or different from each other. Ar ₁ and Ar ₂ are preferably an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent from the viewpoint of increasing the emission wavelength. In the formula (1), it is preferable that at least one of the groups represented by Ar ₁ and Ar ₂ has a substituent from the viewpoint of increasing the solubility of the polymer compound of the present invention in a solvent.

  In said Formula (1), an arylene group is the remaining atomic group remove | excluding two hydrogen atoms from aromatic hydrocarbon, and carbon number is about 6-60 normally. The carbon number does not include the carbon number of the substituent. 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 arylene group may have a substituent.

  Examples of the arylene group include a phenylene group (for example, the following formulas 1 to 3), a naphthalenediyl group (the following formulas 4 to 13), an anthracenylene group (the following formulas 14 to 19), a biphenylene group (the following formulas 20 to 25), and triphenylene. Group (following formulas 26 to 28), condensed ring compound group (following formulas 29 to 38), stilbene-diyl group (following formulas AD), distilbene-diyl group (following formulas E and F), benzofluorene-diyl group (Formulas G, H, I, K) and the like are exemplified. Among these, a phenylene group (the following formulas 1 to 3), a naphthalenediyl group (the following formulas 4 to 13), a biphenylene group (the following formulas 20 to 25), a fluorene-diyl group (the following formulas 36 to 38), and stilbene-diyl. A group (the following formulas A to D), a distilbene-diyl group (the following formulas E and F), and a benzofluorene-diyl group (the following formulas G, H, I, and K) are preferable.

  In the above formulas 1 to 38, A to I, and K, each R independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, or an arylalkyl group. , Arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group, monovalent heterocyclic group, acyl group, acyloxy group, substituted carboxyl group or cyano group. In the above formula, one structural formula has a plurality of Rs, but they may be the same or different. Next, the group represented by R will be described. A plurality of R may be the same or different. Two Rs may be bonded to each other to form a ring.

The alkyl group may be linear, branched or cyclic, or a combination thereof, and usually has about 1 to 20 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group. , 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, etc., and pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, 3,7-dimethyloctyl. Groups are preferred. Examples of non-linear groups include isoamyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, cyclohexyl group, 4-C ₁ -C ₁₂ alkylcyclohexyl group (“C ₁ -C ₁₂ alkyl” is alkyl The carbon number of the portion is 1 to 12. The same applies to the following.

  The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specific examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, Examples include heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, pentyloxy group, hexyloxy group, octyloxy group, 2 -An ethylhexyloxy group, a decyloxy group, and a 3,7- dimethyloctyloxy group are preferable.

  The alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, i-propylthio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group. Group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, etc., and pentylthio group, hexylthio group, octylthio group, 2-ethylhexylthio group, decylthio group, 3, A 7-dimethyloctylthio group is preferred.

  The alkylsilyl group may be linear, branched or cyclic, and usually has about 1 to 60 carbon atoms. Specific examples of the alkylsilyl group include methylsilyl group, ethylsilyl group, propylsilyl group, i-propylsilyl group, butylsilyl group, i-butylsilyl group, t-butylsilyl group, pentylsilyl group, hexylsilyl group, and cyclohexylsilyl group. , Heptylsilyl group, octylsilyl group, 2-ethylhexylsilyl group, nonylsilyl group, decylsilyl group, 3,7-dimethyloctylsilyl group, laurylsilyl group, trimethylsilyl group, ethyldimethylsilyl group, propyldimethylsilyl group, i-propyl Dimethylsilyl group, butyldimethylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, Nyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, etc. are mentioned, pentylsilyl group, hexylsilyl group, octylsilyl group, 2-ethylhexylsilyl group, decylsilyl group 3,7-dimethyloctylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group are preferred. .

  The alkylamino group may be linear, branched or cyclic, and may be a monoalkylamino group or a dialkylamino group, and usually has about 1 to 40 carbon atoms. Specific examples of the alkylamino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, i-propylamino group, butylamino group, i-butylamino group, and 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, etc. A pentylamino group, a hexylamino group, an octylamino group, a 2-ethylhexylamino group, a decylamino group, and a 3,7-dimethyloctylamino group are preferred.

  The aryl group usually has about 6 to 60 carbon atoms. Specific examples of the aryl group include a phenyl group which may have a substituent, a 1-naphthyl group which may have a substituent, a 2-naphthyl group which may have a substituent, and the like. Can be mentioned. Examples of the substituent of the phenyl group which may have the substituent include an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, Examples thereof include an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group, an acyl group, an acyloxy group, a substituted carboxyl group, and a cyano group. When a plurality of substituents are present, they may be the same or different. When the phenyl group which may have a substituent has a substituent, the number of the substituent is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.

When the phenyl group which may have the substituent has a substituent, and the substituent is an alkyl group, the phenyl group having the substituent has a carbon number of 1 to 1 as a substituent on the phenyl ring. A phenyl group into which 12 alkyl groups have been introduced (hereinafter referred to as “C ₁ -C ₁₂ alkylphenyl group”. “C ₁ -C ₁₂ alkyl” indicates that the alkyl moiety has 1 to 12 carbon atoms. The same applies hereinafter).
Examples of the C _{1 to} C ₁₂ alkylphenyl group include a methyl substituted phenyl group, an ethyl substituted phenyl group, a propyl substituted phenyl group, an i-propyl substituted phenyl group, a butyl substituted phenyl group, an i-butyl substituted phenyl group, and a t-butyl. Substituted phenyl group, pentyl substituted phenyl group, hexyl substituted phenyl group, cyclohexyl substituted phenyl group, heptyl substituted phenyl group, octyl substituted phenyl group, 2-ethylhexyl substituted phenyl group, nonyl substituted phenyl group, decyl substituted phenyl group, 3,7- Examples include dimethyloctyl substituted phenyl group, lauryl substituted phenyl group, trifluoromethyl substituted phenyl group, pentafluoroethyl substituted phenyl group, perfluorobutyl substituted phenyl group, perfluorohexyl substituted phenyl group, perfluorooctyl substituted phenyl group, etc. Among them, from the viewpoint of solubility of the polymer compound in the solvent, butyl-substituted phenyl group, i-butyl-substituted phenyl group, t-butyl-substituted phenyl group, hexyl-substituted phenyl group, heptyl-substituted phenyl group, octyl-substituted phenyl Group, 2-ethylhexyl substituted phenyl group, nonyl substituted phenyl group, decyl substituted phenyl group, 3,7-dimethyloctyl substituted phenyl group are preferable. These C _{1 to} C ₁₂ alkylphenyl groups may further have a substituent.

When the phenyl group which may have the substituent has a substituent, and the substituent is an alkoxy group, the phenyl group having the substituent may have 1 to 1 carbon atoms as a substituent on the phenyl ring. A phenyl group into which 12 alkoxy groups have been introduced (hereinafter referred to as “C ₁ -C ₁₂ alkoxyphenyl group”. “C ₁ -C ₁₂ alkoxy” indicates that the alkoxy moiety has 1 to 12 carbon atoms. The same applies hereinafter).
The C ₁ -C ₁₂ alkoxyphenyl group include a methoxy-substituted phenyl group, an ethoxy-substituted phenyl group, propyloxy-substituted phenyl group, i- propyloxy-substituted phenyl group, butoxy-substituted phenyl group, i- butoxy-substituted phenyl group, t -Butoxy substituted phenyl group, pentyloxy substituted phenyl group, hexyloxy substituted phenyl group, cyclohexyloxy substituted phenyl group, heptyloxy substituted phenyl group, octyloxy substituted phenyl group, 2-ethylhexyloxy substituted phenyl group, nonyloxy substituted phenyl group, decyloxy Substituted phenyl group, 3,7-dimethyloctyloxy substituted phenyl group, lauryloxy substituted phenyl group, trifluoromethoxy substituted phenyl group, pentafluoroethoxy substituted phenyl group, perfluorobutoxy substitution Examples include a phenyl group, a perfluorohexyloxy-substituted phenyl group, a perfluorooctyloxy-substituted phenyl group, a methoxymethyloxy-substituted phenyl group, and a 2-methoxyethyloxy-substituted phenyl group. From the viewpoint of, butoxy-substituted phenyl group, i-butoxy-substituted phenyl group, t-butoxy-substituted phenyl group, pentyloxy-substituted phenyl group, hexyloxy-substituted phenyl group, heptyloxy-substituted phenyl group, octyloxy-substituted phenyl group, 2- An ethylhexyloxy substituted phenyl group, a nonyloxy substituted phenyl group, a decyloxy substituted phenyl group, a 3,7-dimethyloctyloxy substituted phenyl group, and a lauryloxy substituted phenyl group are preferred. These C _{1 to} C ₁₂ alkoxyphenyl groups may further have a substituent.

  When the phenyl group which may have the substituent has a substituent and the substituent is an acyl group, the phenyl group having the substituent has 2 to 30 carbon atoms, preferably 2 to 2 carbon atoms. And a phenyl group substituted with 15 acyl groups, specifically, an acetyl substituted phenyl group, a propionyl substituted phenyl group, a butyryl substituted phenyl group, an isobutyryl substituted phenyl group, a pivaloyl substituted phenyl group, a trifluoroacetyl substituted phenyl group. Etc.

  When the phenyl group which may have the substituent has a substituent and the substituent is an acyloxy group, the phenyl group having the substituent has 2 to 30 carbon atoms, preferably 2 to 2 carbon atoms. 15 acyloxy groups, specifically, acetoxy-substituted phenyl group, propionyloxy-substituted phenyl group, butyryloxy-substituted phenyl group, isobutyryloxy-substituted phenyl group, pivaloyloxy-substituted phenyl group, trifluoroacetyloxy-substituted phenyl group, etc. Is mentioned.

  When the phenyl group which may have the substituent has a substituent, and the substituent is a substituted carboxyl group, the phenyl group having the substituent includes an alkyl group, an aryl group, an arylalkyl group or Examples thereof include a phenyl group having a carboxyl group substituted with a monovalent heterocyclic group (the number of carbon atoms is usually about 2 to 30, preferably about 2 to 15) as a substituent. From the viewpoint, a phenyl group having a carboxyl group substituted with an alkyl group as a substituent is preferable. Specific examples of the phenyl group having the substituent include a methoxycarbonyl substituted phenyl group, an ethoxycarbonyl substituted phenyl group, a propoxycarbonyl substituted phenyl group, an i-propoxycarbonyl substituted phenyl group, a butoxycarbonyl substituted phenyl group, and an i-butoxycarbonyl substituted. Phenyl group, t-butoxycarbonyl substituted phenyl group, pentyloxycarbonyl substituted phenyl group, hexyloxycarbonyl substituted phenyl group, cyclohexyloxycarbonyl substituted phenyl group, heptyloxycarbonyl substituted phenyl group, octyloxycarbonyl substituted phenyl group, 2-ethylhexyl Siloxycarbonyl substituted phenyl group, nonyloxycarbonyl substituted phenyl group, decyloxycarbonyl substituted phenyl group, 3,7-dimethyloctyloxycarbonyl substituted Phenyl group, dodecyloxycarbonyl substituted phenyl group, trifluoromethoxycarbonyl substituted phenyl group, pentafluoroethoxycarbonyl substituted phenyl group, perfluorobutoxycarbonyl substituted phenyl group, perfluorohexyloxycarbonyl substituted phenyl group, perfluorooctyloxycarbonyl substituted phenyl Group, a phenoxycarbonyl-substituted phenyl group, and the like.

The aryloxy group usually has about 6 to 60 carbon atoms. Specific examples of the aryloxy group include a phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group and the like exemplified is, C ₁ -C ₁₂ alkoxy phenoxy group, a C ₁ -C ₁₂ alkylphenoxy group are preferable.

The arylalkyl group usually has about 7 to 60 carbon atoms. Specific examples of the arylalkyl group, a phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl Group, 1-naphthyl-C ₁ -C ₁₂ alkyl group, 2-naphthyl-C ₁ -C ₁₂ alkyl group and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group, C ₁ -C _{A 12} alkylphenyl-C ₁ -C ₁₂ alkyl group is preferred.

The arylalkoxy group usually has about 7 to 60 carbon atoms. Specific examples of the arylalkoxy group include a phenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy Group, 1-naphthyl-C ₁ -C ₁₂ alkoxy group, 2-naphthyl-C ₁ -C ₁₂ alkoxy group and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxy group, C ₁ -C preferably ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy group.

The arylalkenyl group usually has about 8 to 60 carbon atoms. Specific examples of the arylalkenyl group include a phenyl -C ₂ -C ₁₂ alkenyl group ( "C ₂ -C ₁₂ alkenyl", also similar to that. Hereinafter indicating that the number of carbon atoms of the alkenyl moiety is 2 to 12 ), C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl-C ₂ -C ₁₂ alkenyl group, 1-naphthyl-C ₂ -C ₁₂ alkenyl group, 2-naphthyl -C ₂ -C ₁₂ alkenyl group, etc. are exemplified, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, a C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl group are preferred.

The arylalkynyl group usually has about 8 to 60 carbon atoms. Specific examples of the arylalkynyl group include a phenyl-C ₂ -C ₁₂ alkynyl group, a C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkynyl group, and 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 preferably ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group.

The arylamino group usually has about 6 to 60 carbon atoms. Specific examples of the arylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl ) amino group, 1-naphthylamino group, are exemplified 2-naphthylamino group and the like, C ₁ -C ₁₂ alkylphenyl group, di (C ₁ -C ₁₂ alkylphenyl) amino group are preferable.

  The acyl group usually has about 2 to 30 carbon atoms, preferably about 2 to 15 carbon atoms. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

  The acyloxy group usually has about 2 to 30 carbon atoms, preferably about 2 to 15 carbon atoms. Specific examples of the acyloxy group include an acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetyloxy group, pentafluorobenzoyloxy group and the like.

  Examples of the substituted carboxyl group include a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and usually has about 2 to 30 carbon atoms, preferably about 2 to 15 carbon atoms. It is. Specific examples of the substituted carboxyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, i-propoxycarbonyl group, butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyl group. Siloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl Group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooxy group Chill oxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group and the like. In addition, these groups may have a substituent. The carbon number of the substituted carboxyl group does not include the carbon number of the substituent.

The monovalent heterocyclic group refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound.
The monovalent heterocyclic group usually has about 4 to 60 carbon atoms. As the monovalent heterocyclic group, a monovalent aromatic heterocyclic group is preferable. Examples of the monovalent heterocyclic group include a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group are thienyl group , C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

（式中、Ｒ’は、水素原子、炭素数１〜２０のアルキル基、炭素数６〜６０のアリール基、又は炭素数４〜６０の１価の複素環基を表す。Ｒ’が複数存在する場合には、それらは同一であっても異なっていてもよい。） When the substituent is a group containing an alkyl chain, the alkyl chain may be interrupted by a hetero atom or a group containing a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the hetero atom or the group containing a hetero atom include the following groups.

(In the formula, R ′ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, or a monovalent heterocyclic group having 4 to 60 carbon atoms. They may be the same or different.)

  In the above formula, the alkyl group, aryl group, and monovalent heterocyclic group represented by R ′ are the same as those described and exemplified as the substituent represented by R.

  In said formula (1), a bivalent heterocyclic group means the remaining atomic groups remove | excluding two hydrogen atoms from the heterocyclic compound, and carbon number is about 4-60 normally. The carbon number does not include the carbon number of the substituent. The heterocyclic compound means an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus and boron in the ring. To do. As the divalent heterocyclic group, a divalent aromatic heterocyclic group is preferable. The divalent heterocyclic group may have a substituent.

Examples of the divalent heterocyclic group include the following.
A group containing nitrogen as a hetero atom; pyridine-diyl group (formula 39 to 44), diazaphenylene group (formula 45 to 48), quinoline diyl group (formula 49 to 63), quinoxaline diyl group (formula 64 -68), acridine diyl group (lower formulas 69-72), bipyridyldiyl group (lower formulas 73-75), phenanthroline diyl group (lower formulas 76-78), and the like.
Groups having a fluorene structure containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a hetero atom (the following formulas 79 to 93).
5-membered ring heterocyclic groups containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a hetero atom (the following formulas 94 to 98).
5-membered condensed heterocyclic groups containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a hetero atom (the following formulas 99 to 108).
A 5-membered heterocyclic group containing sulfur or the like as a heteroatom and bonded to the α-position of the heteroatom to form a dimer or oligomer (the following formulas 109 to 110).
A 5-membered heterocyclic group containing silicon, nitrogen, oxygen, sulfur, selenium or the like as a hetero atom, and a group bonded to the phenyl group at the α-position of the hetero atom (the following formulas 111 to 117).
Phenoxazine group (formula L), phenothiazine group (formula M).

  In the above formulas 39 to 117, L and M, R represents the same meaning as described above.

（式中、Ａｒ₅及びＡｒ₇はそれぞれ独立に、置換基を有していてもよいアリーレン基、一般式（４）で表される基、又は一般式（５）で表される基を表す。Ａｒ₆は、置換基を有していてもよいアリール基、一般式（６）で表される基又は一般式（７）で表される基を表す。また、Ａｒ₅とＡｒ₆の間、Ａｒ₅とＡｒ₇の間、又はＡｒ₆とＡｒ₇の間に環を形成していてもよい。

（式中、Ａｒ₈及びＡｒ₉は、それぞれ独立に、置換基を有していてもよいアリーレン基を表す。Ｒ₇及びＲ₈は、それぞれ独立に、水素原子、アルキル基、アリール基、１価の複素環基又はシアノ基を表す。ｌは、０又は１である。）

（式中、Ａｒ₁₀及びＡｒ₁₁は、それぞれ独立に、置換基を有していてもよいアリーレン基を表す。Ａｒ₁₂は、置換基を有していてもよいアリール基を表す。また、Ａｒ₁₀とＡｒ₁₂の間、Ａｒ₁₀とＡｒ₁₁の間、又はＡｒ₁₁とＡｒ₁₂の間に環を形成していてもよい。）

（式中、Ａｒ₁₃は、置換基を有していてもよいアリーレン基を表す。Ａｒ₁₆及びＡｒ₁₇は、それぞれ独立に、置換基を有していてもよいアリール基を表す。また、Ａｒ₁₃とＡｒ₁₆の間、Ａｒ₁₃とＡｒ₁₇の間、又はＡｒ₁₆とＡｒ₁₇の間に環を形成していてもよい。）

（式中、Ａｒ₁₄は、置換基を有していてもよいアリーレン基を示す。Ａｒ₁₅は、置換基を有していてもよいアリール基を表す。Ｒ₁₁及びＲ₁₂は、それぞれ独立に、水素原子、アルキル基、アリール基、１価の複素環基又はシアノ基を表す。ｒは０又は１である。） In said formula (1), a bivalent aromatic amine group means the remaining atomic groups remove | excluding two hydrogen atoms from aromatic amine, and carbon number is about 4-60 normally. The divalent aromatic amine group may have a substituent, but the carbon number does not include the carbon number of the substituent. Examples of the divalent aromatic amine group include a group represented by the following general formula (3).

(In the formula, Ar ₅ and Ar ₇ each independently represent an arylene group which may have a substituent, a group represented by the general formula (4), or a group represented by the general formula (5). Ar ₆ represents an aryl group which may have a substituent, a group represented by the general formula (6), or a group represented by the general formula (7), and between Ar ₅ and Ar ₆ . , Ar ₅ and Ar ₇ , or Ar ₆ and Ar ₇ may form a ring.

(In the formula, Ar ₈ and Ar ₉ each independently represent an arylene group which may have a substituent. R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, 1 Represents a valent heterocyclic group or a cyano group, and l is 0 or 1.)

(Wherein, Ar ₁₀ and Ar ₁₁ are each independently, .Ar ₁₂ which represents an arylene group optionally having a substituent, represents an aryl group which may have a substituent. In addition, Ar _A ring may be formed between ₁₀ and Ar ₁₂ , between Ar ₁₀ and Ar ₁₁ , or between Ar ₁₁ and Ar _12. )

(In the formula, Ar ₁₃ represents an arylene group which may have a substituent. Ar ₁₆ and Ar ₁₇ each independently represents an aryl group which may have a substituent. Ar _A ring may be formed between ₁₃ and Ar ₁₆ , between Ar ₁₃ and Ar ₁₇ , or between Ar ₁₆ and Ar _17. )

(In the formula, Ar ₁₄ represents an arylene group which may have a substituent. Ar ₁₅ represents an aryl group which may have a substituent. R ₁₁ and R ₁₂ are each independently Represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group, and r is 0 or 1.)

In the above formula, the arylene group represented by Ar ₅ , Ar ₇ , Ar ₈ , Ar ₉ , Ar ₁₀ , Ar ₁₁ , Ar ₁₃ , Ar ₁₄ has usually 6 to 60 carbon atoms, Specific examples include phenylene group, naphthalenediyl group, anthracene-diyl group, biphenylene group, triphenylene group, fluorene-diyl group, stilbenediyl group and the like. From the viewpoint of ease of synthesis of the polymer compound, a phenylene group is preferable.

In the above formula, the aryl group represented by Ar ₆ , Ar ₁₂ , Ar ₁₅ , Ar ₁₆ , Ar ₁₇ has usually 6 to 60 carbon atoms. Specific examples thereof include a phenyl group, C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl, 2-naphthyl and the like. From the viewpoint of ease of synthesis of the polymer compound is preferably a phenyl-group.

In the above formula, the alkyl group, aryl group, and monovalent heterocyclic group represented by R ₇ , R ₈ , R ₁₁ , and R ₁₂ are the same as those described and exemplified as the substituent represented by R. is there.

Ar _{5 to} Ar ₁₇ in the above formula are alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group , Arylamino group, monovalent heterocyclic group, acyl group, acyloxy group, substituted carboxyl group, cyano group and the like.

（上記式１１８〜１２２中、Ｒは、前記と同じ意味を表す。） Specific examples of the divalent aromatic amine group include the following groups.

(In the above formulas 118 to 122, R represents the same meaning as described above.)

In the above formula _(1), Z 1 is, -CR ₁ = CR ₂ - or an -C≡C-, -CR ₁ = CR ₂ - is preferable from the viewpoint of oxidation stability. Here, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. From the viewpoint of ease of synthesis of the polymer compound, An atom, an alkyl group, or an aryl group is preferable.

The alkyl group represented by R ₁ and R ₂ has the same meaning as described for R.

The aryl group represented by R ₁ and R ₂ usually has about 6 to 60 carbon atoms. Specific examples thereof include a phenyl group, C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl, 2-naphthyl, anthracenyl group, biphenyl group, triphenyl group, pyrenyl group, etc. and the like, from the viewpoint of easiness of synthesis of a polymer compound, a phenyl group, C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ alkylphenyl group, naphthyl group, biphenyl group are preferable, and more is a phenyl group preferable.

The monovalent heterocyclic group represented by R ₁ and R ₂ is the remaining atomic group obtained by removing one hydrogen atom from the heterocyclic compound, and usually has about 2 to 60 carbon atoms. Specific examples thereof include the following.
Monovalent heterocyclic group containing nitrogen as a hetero atom; pyridinyl group, diazaphenyl group, quinolinyl group, quinoxalinyl group, acridinyl group, bipyridinyl group, phenanthroline-yl group and the like.
A group containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a heteroatom and having a fluorene structure (in the formulas 79 to 93, one of the bonds is a substituent R).
5-membered heterocyclic group containing silicon, nitrogen, oxygen, sulfur, selenium, etc. as a hetero atom (in the above formulas 94 to 98, one of the bonds becomes a substituent R)
A 5-membered condensed heterocyclic group containing silicon, nitrogen, oxygen, sulfur, selenium or the like as a heteroatom (in the above formulas 99 to 108, one of the bonds becomes a substituent R).
A 5-membered ring heterocyclic group containing sulfur or the like as a heteroatom, a group bonded in the α-position of the heteroatom to form a two-body or oligomer (in the above formulas 109 to 110, one of the bonds is a substituent R).
A 5-membered heterocyclic group containing silicon, nitrogen, oxygen, sulfur, selenium, etc. as a hetero atom, and a group bonded to the phenyl group at the α-position of the hetero atom (in the formulas 111 to 117, One of the substituents R).

  In the formula (1), m and n are each independently 1 or 2. m and n are preferably the same from the standpoint of ease of monomer synthesis.

In the formula (1), the alkyl group and alkoxy group represented by R ^s and R ^t are the same as those described and exemplified as the group represented by R. R ^s and R ^t are preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom, from the viewpoint of ease of monomer synthesis.

〔式中、Ｒ^a、Ｒ^b、Ｒ^c及びＲ^dは、それぞれ独立に、水素原子、アルキル基、アルコキシ基又はアリール基を表す。Ｒ^e及びＲ^fは、それぞれ独立に、水素原子、アルキル基又はアリール基を表す。ｍ’及びｎ’は、それぞれ独立に、１又は２である。Ｒ^a〜Ｒ^dが複数存在する場合には、それらは同一であっても異なっていてもよい。〕
で表されるものであることが、高分子化合物の溶解性や蛍光波長の長波長化の観点から好ましい。 The repeating unit represented by the formula (1) is represented by the following formula (1a):

[Wherein, R ^a , R ^b , R ^c and R ^d each independently represents a hydrogen atom, an alkyl group, an alkoxy group or an aryl group. R ^e and R ^f each independently represents a hydrogen atom, an alkyl group or an aryl group. m ′ and n ′ are each independently 1 or 2. When ^a plurality of R ^{a to} R ^d are present, they may be the same or different. ]
It is preferable from the viewpoint of the solubility of the polymer compound and the increase in the fluorescence wavelength.

In the above formula (1a), the alkyl group and aryl group represented by R ^a , R ^b , R ^c , R ^d , R ^e and R ^f , and R ^a , R ^b , R ^c and R ^d are represented. The alkoxy group is the same as described and exemplified as R.

In the above formula (1a), R ^a , R ^b , R ^c and R ^d are preferably a hydrogen atom, an alkyl group or an aryl group, and one or more of them are an alkyl group. From the viewpoint of solubility of the polymer compound. Moreover, it is preferable from a soluble viewpoint of a high molecular compound that at least one of ^Re and ^Rf is an alkyl group or an aryl group.

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

  In the above formula, each R independently has the same meaning as described above. Moreover, although it has several R in one structural formula, they may be the same and may differ.

〔式中、Ａｒ₅は、置換基を有していてもよいアリーレン基、置換基を有していてもよい２価の複素環基、又は置換基を有していてもよい２価の芳香族アミン基を表す。Ｚ₂は、−ＣＲ₃＝ＣＲ₄−又は−Ｃ≡Ｃ−を表す。Ｒ₃及びＲ₄は、それぞれ独立に、水素原子、アルキル基、アリール基、１価の複素環基又はシアノ基を表す。〕
で表される繰り返し単位を含むものが、高分子化合物の溶解性や成膜性の観点から好ましい。 -Repeating unit represented by formula (2) In addition to the repeating unit represented by the formula (1), the polymer compound of the present invention further comprises the following formula (2):

[In the formula, Ar ₅ represents an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or a divalent aromatic which may have a substituent. Represents a group amine group. Z ₂ represents —CR ₃ ═CR ₄ — or —C≡C—. R ₃ and R ₄ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. ]
In view of the solubility of the polymer compound and the film formability, those containing a repeating unit represented by

In the formula (2), the group represented by Ar ₅ is an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent from the viewpoint of fluorescence intensity. It is preferable that The group represented by Ar ₅ is the same as described and exemplified as the group represented by Ar ₁ and Ar ₂ .

〔式中、Ａ環及びＢ環は、それぞれ独立に、置換基を有していてもよい芳香族炭化水素環を表す。２つの結合手はそれぞれＡ環又はＢ環上に存在する。Ｒｗ及びＲｘ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、アルキルシリル基、アルキルアミノ基、アリール基、アリールオキシ基、アリールアルキル基、アリールアルコキシ基、アリールアルケニル基、アリールアルキニル基、アリールアミノ基、１価の複素環基、アシル基、置換カルボキシル基又はシアノ基を表し、Ｒｗ及びＲｘは、それぞれ互いに結合して環を形成していてもよい。〕
で表されるものであることが、高分子化合物の溶解性や蛍光強度の観点から好ましい。 In the formula (2), the arylene group which may have a substituent represented by Ar ₅ is represented by the following formula (60):

[In formula, A ring and B ring represent the aromatic-hydrocarbon ring which may have a substituent each independently. Two bonds exist on the A ring or the B ring, respectively. Rw and Rx are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl Represents a group, an arylamino group, a monovalent heterocyclic group, an acyl group, a substituted carboxyl group or a cyano group, and Rw and Rx may be bonded to each other to form a ring. ]
It is preferable from the viewpoint of the solubility of the polymer compound and the fluorescence intensity.

  In the formula (60), an alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group The monovalent heterocyclic group, acyl group, and substituted carboxyl group are the same as those described and exemplified as R in Formulas 1 to 38, A to I, and K.

In Formula (60), R _w and R _x are preferably the same group from the viewpoint of ease of monomer synthesis.

  In the arylene group which may have a substituent represented by the formula (60), from the viewpoint of ease of synthesis of the monomer, one of two bonds is present on the A ring, and the other Are preferably present on the B ring. From the viewpoint of heat resistance, it is preferable that at least one of the A ring and the B ring is an aromatic hydrocarbon ring in which a plurality of benzene rings are condensed.

  The aromatic hydrocarbon ring is preferably a benzene ring alone or a condensed benzene ring, specifically, for example, a benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, An aromatic hydrocarbon ring such as a phenanthrene ring is mentioned, and from the viewpoint of ease of monomer synthesis, a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring are preferable, and a benzene ring and a naphthalene ring are more preferable. is there.

  The combination of A ring and B ring is preferably a benzene ring and a benzene ring, a benzene ring and a naphthalene ring, a benzene ring and an anthracene ring, a benzene ring and a phenanthrene ring, naphthalene from the viewpoint of ease of monomer synthesis. And an anthracene ring, a naphthalene ring and a phenanthrene ring, an anthracene ring and a phenanthrene ring, and the like. A benzene ring and a benzene ring, and a benzene ring and a naphthalene ring are more preferable.

〔式中、Ｒ^gは、水素原子、アルキル基又はアリール基を表す。２個存在するＲ^gは、同一であっても異なっていてもよい。２個存在するＲ^gは、互いに結合して環を形成していてもよい。〕
のいずれかで表されるものであることが、単量体の合成の容易さや高分子化合物の蛍光強度の観点から好ましい。 The arylene group which may have a substituent represented by the formula (60) is represented by the following formulas (2A) to (2D):

[Wherein, R ^g represents a hydrogen atom, an alkyl group or an aryl group. Two R ^{g s} may be the same or different. Two R ^{g s} may be bonded to each other to form a ring. ]
It is preferable from the viewpoint of ease of monomer synthesis and fluorescence intensity of the polymer compound.

In the above formulas (2A) to (2D), R ^g is preferably an alkyl group from the viewpoint of the solubility of the polymer compound. The alkyl group and aryl group represented by R ^g are the same as those described and exemplified as the groups represented by R ^{a to} R ^f .

  Examples of the arylene group which may have the substituent include a phenylene group (the above formulas 1 to 3) and naphthalene, including those represented by the formula (60) and the formulas (2A) to (2D). Diyl group (formula 4 to 13), biphenylene group (formula 20 to 25), fluorene-diyl group (formula 36 to 38), stilbene-diyl (formula AD), distilbene-diyl (formula E F), benzofluorene-diyl (formulas G, H, I, K) and the like are preferable from the viewpoint of ease of monomer synthesis and fluorescence intensity of the polymer compound.

〔式中、Ｃ環及びＤ環は、それぞれ独立に、芳香環を表す。Ｃ環及びＤ環は、アルキル基、アルコキシ基、アルキルチオ基、アルキルシリル基、アルキルアミノ基、アリール基、アリールオキシ基、アリールアルキル基、アリールアルコキシ基、アリールアルケニル基、アリールアルキニル基、アリールアミノ基、１価の複素環基、アシル基、アシルオキシ基、置換カルボキシル基及びシアノ基からなる群から選ばれる置換基を有していてもよい。置換基が複数ある場合には、それらは同一であっても異なっていてもよい。Ｅは、Ｏ又はＳである。〕
で表されるものであることが、単量体の合成の容易さや高分子化合物の蛍光強度の観点から好ましい。 In the formula (2), the divalent heterocyclic group optionally having a substituent represented by Ar ₅ is represented by the following formula (70):

[In formula, C ring and D ring represent an aromatic ring each independently. C ring and D ring are alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group It may have a substituent selected from the group consisting of a monovalent heterocyclic group, an acyl group, an acyloxy group, a substituted carboxyl group and a cyano group. When there are a plurality of substituents, they may be the same or different. E is O or S. ]
It is preferable from the viewpoint of the ease of monomer synthesis and the fluorescence intensity of the polymer compound.

  In the formula (70), examples of the aromatic ring represented by C ring and D ring include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, phenanthrene ring; pyridine Heteroaromatic ring such as ring, bipyridine ring, phenanthroline ring, quinoline ring, isoquinoline ring, thiophene ring, furan ring, pyrrole ring, etc., from the viewpoint of ease of monomer synthesis, aromatic hydrocarbon ring Is preferable, and a benzene ring is more preferable.

  When the C ring and the D ring have the substituent, an alkyl group and an alkoxy group are preferable from the viewpoint of ease of monomer synthesis and solubility of the polymer compound. Furthermore, when there are a plurality of substituents, they may be the same or different. The group which becomes the substituent is the same as that described and exemplified as R in the formulas 1 to 38, A to I and K.

〔式中、Ｙは、Ｏ又はＳを表す。Ｒ^j及びＲ^kは、それぞれ独立に、アルキル基、アルコキシ基又はアリール基を表す。ａ及びｂは、それぞれ独立に、０又は１である。〕
で表されるものであることが、単量体の合成の容易さや高分子化合物の蛍光強度の観点から好ましい。 The divalent heterocyclic group optionally having a substituent represented by the formula (70) is represented by the following formula (2E):

[Wherein Y represents O or S. R ^j and R ^k each independently represents an alkyl group, an alkoxy group or an aryl group. a and b are each independently 0 or 1. ]
It is preferable from the viewpoint of the ease of monomer synthesis and the fluorescence intensity of the polymer compound.

In the formula (2E), R ^j and R ^k are the same from the viewpoint of ease of monomer synthesis (that is, both are a hydrogen atom, an alkyl group, an alkoxy group, or an aryl group). It is preferable that it is an alkoxy group. The alkyl group and aryl group represented by R ^j and R ^k are the same as those described and exemplified as the groups represented by R ^{a to} R ^f . Examples of the alkoxy group represented by R ^j and R ^k include a butoxy group, an i-butoxy group, a t-butoxy group, a pentyloxy group, a hexyloxy group, from the viewpoint of the solubility and fluorescence intensity of the polymer compound. Heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group are preferred, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyl An oxy group, a decyloxy group, and a 3,7-dimethyloctyloxy group are more preferable.

  Examples of the divalent heterocyclic group that may have the substituent include those represented by the above formula (70) and the above formula (2E), etc., as heteroatoms such as silicon, nitrogen, oxygen, A group containing sulfur, selenium and the like and having a fluorene structure (the above formulas 79 to 93), a 5-membered heterocyclic group containing sulfur or the like as a heteroatom, and bonding to the α-position of the heteroatom becomes a dimer or oligomer. Groups (formulas 109 to 110), a 5-membered heterocyclic group containing silicon, nitrogen, oxygen, sulfur, selenium, etc. as a hetero atom, and a group bonded to the phenyl group at the α-position of the hetero atom (The above formulas 111 to 117) are preferable from the viewpoint of ease of monomer synthesis and fluorescence intensity of the polymer compound.

In the formula (2), Z ₂ is preferably —CR ₃ ═CR ₄ — from the viewpoint of oxidation stability in the atmosphere. The alkyl groups represented by R ₃ and R ₄ have the same meaning as described and exemplified as R.

In the formula (2), the aryl group and monovalent heterocyclic group represented by R ₃ and R ₄ are explained and exemplified as the aryl group and monovalent heterocyclic group represented by R ₁ and R _2. Has the same meaning as

Specific examples of the repeating unit represented by the formula (2) include those represented by the following formula.

  In the above formula, each R independently has the same meaning as described above. Moreover, although it has several R in one structural formula, they may be the same and may differ.

-Repeating unit represented by Formula (1) / Repeating unit represented by Formula (2) In the polymer compound of the present invention, the total of repeating units represented by Formula (1) is usually the polymer. Although it is 0.5-100 mol% of all the repeating units which a compound has, from a viewpoint of red deep color improvement, it is preferable that it is 2-80 mol% of all the repeating units which this high molecular compound has. Further, from the viewpoint of solubility of the polymer compound, it is preferably 2 to 50 mol% of all repeating units of the polymer compound.

  When the polymer compound of the present invention contains the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2), the repeating unit represented by the formula (1) And the sum total of the repeating unit represented by said Formula (2) is 50 mol% or more of all the repeating units which this high molecular compound has, and the repeating unit represented by said Formula (1), and said Formula (2) ) In which the repeating unit represented by the formula (1) is 2 to 80 mol% with respect to the total number of repeating units represented by () is more preferable from the viewpoint of increasing the wavelength of the fluorescence spectrum.

で表されるものの１種類以上と、前記式（２）で表される繰り返し単位として、下記式：

（式中、Ｒは前記と同じ意味を有する。）
で表されるものの１種類以上との共重合体が挙げられる。 When the polymer compound of the present invention contains the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2), specific examples thereof include the formula (1). As a repeating unit represented by the following formula:

As the repeating unit represented by one or more types of those represented by the formula (2), the following formula:

(In the formula, R has the same meaning as described above.)
The copolymer with one or more types of what is represented by these is mentioned.

-Other parts The terminal of the polymer compound of the present invention is protected with a stable group, because if the polymerization active group is left as it is, there is a possibility that the light emission characteristics and lifetime when the device is made will be reduced. Also good. Those having a conjugated bond continuous with the conjugated structure of the main chain are preferable, and for example, a structure bonded to an aryl group or a heterocyclic group via a vinylene group may be used. Specifically, substituents described in Chemical formula 10 of JP-A-9-45478 are exemplified.

（式中、Ｒは前記と同じ意味を有し、Ａｒは炭素数６〜６０個の炭化水素基を表す。） The polymer compound of the present invention contains a repeating unit other than the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) within a range not impairing the fluorescence property and the charge transport property. May be. Moreover, the repeating unit may be connected with vinylene or a non-conjugated part, or the vinylene or non-conjugated part may be contained in the repeating unit. Examples of the bonding structure including the non-conjugated moiety include those shown below, those shown below in combination with vinylene groups, and those shown below in which two or more are combined.

(In the formula, R has the same meaning 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 copolymer, a block copolymer, a graft copolymer or an alternating copolymer, or a polymer having an intermediate structure thereof, for example, a block property. It may be a random random copolymer. From the viewpoint of obtaining a polymer compound having a high fluorescence quantum yield, a random copolymer having a block property and a block or graft copolymer are preferable to a complete random copolymer. A case in which the main chain is branched and there are three or more terminal portions and dendrimers are also included.

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

-Manufacturing method Next, the manufacturing method of the high molecular compound of this invention is demonstrated.

  Examples of the method for producing the polymer compound of the present invention include the method described in JP-A-5-220355. That is, polymerization by a Wittig reaction of a compound having an aldehyde group and a compound having a phosphonium base, or a compound having an aldehyde group and a phosphonium base, a compound having a vinyl group and a compound having a halogen group, or a vinyl group Polymerization by Heck reaction of a compound having a halogen group, polymerization by a Horner-Wadsworth-Emmons method of a compound having an aldehyde group and a compound having an alkylphosphonate group, or a compound having an aldehyde group and an alkylphosphonate group, halogenation Polycondensation of a compound having two or more methyl groups by a dehydrohalogenation method, polycondensation of a compound having two or more sulfonium bases by a sulfonium salt decomposition method, a compound having an aldehyde group and an acetonitrile group With compound or with aldehyde group and aceto The method of polymerization by the Knoevenagel reaction of a compound having a tolyl group, a method such as polymerization by the McMurry reaction of a compound having an aldehyde group two or more are exemplified. Moreover, the method of superposing | polymerizing by a Suzuki coupling reaction from the relevant monomer is illustrated.

  Among these, polymerization by Wittig reaction, polymerization by Heck reaction, polymerization by Horner-Wadsworth-Emmons method, polymerization by Knoevenagel reaction, and polymerization by Suzuki coupling reaction are preferable because the structure can be easily controlled.

  Although the organic solvent varies depending on the compound and reaction to be used, it is generally preferable that the solvent to be used is sufficiently deoxygenated and the reaction is allowed to proceed under 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 reaction in a two-phase system with water such as a Suzuki coupling reaction).

  In order to advance the reaction, an alkali or a suitable catalyst is added as appropriate. These may be selected according to the reaction used. The alkali and the catalyst are preferably those sufficiently dissolved in the solvent used for the reaction. As a method of mixing the alkali and catalyst, the reaction solution is slowly added while stirring the reaction solution in an inert atmosphere such as argon or nitrogen, and the reaction solution is slowly added to the alkali or catalyst solution. The method of doing is illustrated.

  The reaction conditions will be described more specifically. In the case of Wittig reaction, Horner reaction, etc., the reaction is carried out using an alkali equivalent to the functional group of the monomer, preferably 1 to 3 equivalents. Although it does not specifically limit as alkali, For example, metal alcoholates, such as potassium tert-butoxide, sodium tert-butoxide, sodium ethylate, lithium methylate, 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 as long as the polymerization proceeds sufficiently, and it is not necessary to leave for a long time after completion of the reaction, so it is preferably 10 minutes to 24 hours. The concentration at the time of the reaction is poor if the reaction is too dilute, and if it is too thick, it becomes difficult to control the reaction, so it may be appropriately selected within the range of about 0.01% by weight to the maximum concentration at which it is dissolved. It is in the range of 0.1 to 20% by weight. In the case of the Heck reaction, a monomer is reacted with 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.

  In the case of Suzuki coupling reaction, for example, palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (triphenylphosphine) palladium (II), etc. are used as the catalyst, and potassium carbonate, sodium carbonate, barium hydroxide. Inorganic bases such as triethylamine, and inorganic salts such as cesium fluoride are added in an equivalent amount or more, preferably 1 to 20 equivalents, relative to the monomer. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. The base may be added as an aqueous solution and reacted in a two-phase system (in the case of reacting in a two-phase system, a phase transfer catalyst such as a quaternary ammonium salt may be added if necessary). 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 0.5 to 200 hours. The reaction is carried out under an inert atmosphere such as argon gas or nitrogen gas under conditions that do not deactivate the catalyst.

-Use of polymer compound The polymer compound of the present invention is useful, for example, as a light emitting material. When the polymer compound of the present invention is used as a light-emitting material for a polymer light-emitting device, the purity affects the light-emitting characteristics. Therefore, after the monomer before polymerization is purified by a method such as distillation, sublimation purification, or recrystallization. Polymerization is preferred, and after the synthesis, purification treatment such as reprecipitation purification and fractionation by chromatography is preferred. The polymer compound of the present invention is also useful for thin films, organic transistors, solar cells and the like.

<Composition (Liquid composition)>
The composition of this invention contains the said high molecular compound and the compound whose number average molecular weights of polystyrene other than this high molecular compound are 10 < ³ > -10 < ⁸ >. The compounds having a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ other than the polymer compound include poly (phenylene) and derivatives thereof, poly (fluorene) and derivatives thereof, poly (benzofluorene) and derivatives thereof, poly (Dibenzofuran) and derivatives thereof, poly (dibenzothiophene) and derivatives thereof, poly (carbazole) and derivatives thereof, poly (thiophene) and derivatives thereof, poly (phenylene vinylene) and derivatives thereof, poly (fluorene vinylene) and derivatives thereof, Examples include poly (benzofluorene vinylene) and derivatives thereof, poly (dibenzofuranvinylene) and derivatives thereof, and the like. However, these derivatives are other than the repeating unit represented by the formula (1).

In the composition of the present invention, a compound having a number average molecular weight in terms of polystyrene other than the polymer compound of 10 ³ to 10 ⁸ relative to the polymer compound (referred to as “polymer compound A” in this paragraph) (this paragraph) In the polymer compound B, the ratio of all repeating units of the polymer compound B is preferably the same as all repeating units of the polymer compound A and all repeating units of the polymer compound B. The ratio is 0.5 to 99.5 mol% of the total of the units, and more preferably the ratio is 10 to 95 mol%.

  The liquid composition of the present invention is useful for production of light-emitting elements such as polymer light-emitting elements and organic transistors. The liquid composition comprises the polymer compound and a solvent. In the present specification, the “liquid composition” means a liquid that is liquid at the time of device fabrication, and typically means a liquid at normal pressure (ie, 1 atm) and 25 ° C. The liquid composition is generally called an ink, an ink composition, a solution or the like.

  In addition to the polymer compound, the liquid composition of the present invention includes a low molecular light emitting material, a hole transport material, an electron transport material, a stabilizer, an additive for adjusting viscosity and / or surface tension, an antioxidant, and the like. May be included. Each of these optional components may be used alone or in combination of two or more.

  Examples of the low-molecular light-emitting material that may be contained in the liquid composition of the present invention include naphthalene derivatives, anthracene, anthracene derivatives, perylene, perylene derivatives, polymethine dyes, xanthene dyes, coumarin dyes, cyanine dyes, Metal complexes having a metal complex of 8-hydroxyquinoline as a ligand, metal complexes having an 8-hydroxyquinoline derivative as a ligand, other fluorescent metal complexes, aromatic amines, tetraphenylcyclopentadiene, tetraphenylcyclopentadiene Derivative, tetraphenylcyclobutadiene, tetraphenylcyclobutadiene derivative, stilbene, silicon-containing aromatic, oxazole, furoxan, thiazole, tetraarylmethane, thiadiazole, pyrazole, metacyclophane, Fluorescent material of low molecular weight compounds of acetylene-based, and the like. Specific examples include those described in JP-A-57-51781, JP-A-59-194393, and the like.

  Examples of the hole transport material that the liquid composition of the present invention may contain include, for example, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, Arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof Derivatives and the like.

  Examples of the electron transport material that may be contained in the liquid composition of the present invention include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyano Anthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives, etc. Can be mentioned.

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

  As an additive for adjusting the viscosity and / or surface tension which the liquid composition of the present invention may contain, for example, a high molecular weight compound (thickener) for increasing the viscosity, a poor solvent, a viscosity A low molecular weight compound for lowering, a surfactant for lowering surface tension, and the like may be used in appropriate combination.

  The high molecular weight compound is not particularly limited as long as it does not inhibit light emission or charge transport, and is usually soluble in the solvent of the liquid composition. As the high molecular weight compound, for example, high molecular weight polystyrene, high molecular weight polymethyl methacrylate, or the like can be used. The high molecular weight compound preferably has a polystyrene equivalent weight average molecular weight of 500,000 or more, more preferably 1,000,000 or more. A poor solvent can also be used as a thickener.

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

  When the liquid composition of the present invention contains a hole transport material, the ratio of the hole transport material in the liquid composition is usually 1 wt% to 80 wt%, preferably 5 wt% to 60% by weight. When the liquid composition of the present invention contains an electron transport material, the ratio of the electron transport material in the liquid composition is usually 1% by weight to 80% by weight, preferably 5% by weight to 60% by weight. %.

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

  For film formation using a liquid composition, spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, nozzle coating Methods such as a method, a capillary coating method, a screen printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  The ratio of the solvent in the liquid composition is usually 1% by weight to 99.9% by weight, preferably 60% by weight to 99.9% by weight, and more preferably 90% by weight with respect to the total weight of the liquid composition. % By weight to 99.8% by weight. The viscosity of the liquid composition varies depending on the printing method, but it is preferably in the range of 0.5 to 500 mPa · s at 25 ° C. In the case of the liquid composition passing through the discharge device, such as an ink jet printing method, In order to prevent flight bending, the viscosity is preferably in the range of 0.5 to 20 mPa · s at 25 ° C.

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

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

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

  When two kinds of solvents are contained in the liquid composition, one of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, it is preferable that one type of solvent has a boiling point of 180 ° C. or higher, and the other one type of solvent preferably has a boiling point of less than 180 ° C. One type of solvent has a boiling point of 200 ° C. More preferably, the solvent has a boiling point of less than 180 ° C. Further, from the viewpoint of viscosity, at 60 ° C., it is preferable that 0.2% by weight or more of the component excluding the solvent from the liquid composition is dissolved in the solvent, and one of the two solvents has 25 ° C. In this case, it is preferable that 0.2% by weight or more of the component excluding the solvent from the liquid composition is dissolved.

  When the liquid composition contains three kinds of solvents, one or two kinds of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, at least one of the three solvents is preferably a solvent having a boiling point of 180 ° C. or higher, and at least one solvent is preferably a solvent having a boiling point of 180 ° C. or lower. At least one of the types of solvents is a solvent having a boiling point of 200 ° C. or more and 300 ° C. or less, and at least one of the solvents is more preferably a solvent having a boiling point of 180 ° C. or less. Further, from the viewpoint of viscosity, it is preferable that two of the three types of solvents have 0.2% by weight or more of the component obtained by removing the solvent from the liquid composition dissolved at 60 ° C. in the solvent. Of these solvents, it is preferable that 0.2% by weight or more of the component obtained by removing the solvent from the liquid composition is dissolved in the solvent at 25 ° C.

  When two or more kinds of solvents are contained in the liquid composition, the solvent having the highest boiling point is 40 to 90% by weight of the total solvent contained in the liquid composition from the viewpoint of viscosity and film formability. Preferably, it is 50 to 90% by weight, more preferably 65 to 85% by weight.

-Thin film-
The thin film of the present invention will be described. This thin film is formed using the polymer compound. Examples of the thin film include a light-emitting thin film, a conductive thin film, and an organic semiconductor thin film.

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

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

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

-Organic transistors (polymer field effect transistors)-
Next, a polymer field effect transistor which is an embodiment of the organic transistor will be described.

  The polymer compound of the present invention can be suitably used as a material for a polymer field effect transistor, especially as an active layer. As a structure of a polymer field effect transistor, a source electrode and a drain electrode are usually provided in contact with an active layer made of a polymer, and a gate electrode is provided with an insulating layer in contact with the active layer interposed therebetween. Just do it.

  The polymer field effect transistor is usually formed on a supporting substrate. The material of the support substrate is not particularly limited as long as the characteristics as a field effect transistor are not hindered, but a glass substrate, a flexible film substrate, or a plastic substrate can also be used.

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

  In forming the active layer, it is very advantageous and preferable to use an organic solvent-soluble polymer compound. For film formation from a solution in which an organic solvent-soluble polymer compound is dissolved in a solvent, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method Methods such as a dip coating method, a spray coating method, a nozzle coating method, a capillary coating method, a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method can be used.

  A sealed polymer field effect transistor obtained by sealing after producing a polymer field effect transistor is preferred. Thereby, the polymer field effect transistor is shielded from the atmosphere, and deterioration of the characteristics of the polymer field effect transistor can be suppressed.

  Examples of the sealing method include a method of covering with an ultraviolet (UV) curable resin, a thermosetting resin, an inorganic SiONx film, or the like, and a method of bonding a glass plate or film with a UV curable resin, a thermosetting resin, or the like. In order to effectively cut off from the atmosphere, it is preferable to carry out the steps from the preparation of the polymer field effect transistor to the sealing without exposure to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).

-Organic solar cells-
Next, an organic solar cell will be described. A solid photoelectric conversion element utilizing the photovoltaic effect as an organic photoelectric conversion element which is one embodiment of an organic solar battery will be described.

  The polymer compound of the present invention is used as a material of an organic photoelectric conversion element, particularly as an organic semiconductor layer of a Schottky barrier type element utilizing an interface between an organic semiconductor and a metal, and between an organic semiconductor and an inorganic semiconductor or between organic semiconductors. It can be suitably used as an organic semiconductor layer of a pn heterojunction element utilizing an interface.

  Furthermore, as an electron-donating polymer and an electron-accepting polymer in a bulk heterojunction device with an increased donor-acceptor contact area, an organic photoelectric conversion device using a polymer / low-molecular composite system, for example, electron accepting It can be suitably used as an electron donating conjugated polymer (dispersion support) of a bulk heterojunction organic photoelectric conversion element in which a fullerene derivative is dispersed as a body.

  As the structure of the organic photoelectric conversion element, for example, in a pn heterojunction type element, a p-type semiconductor layer is formed on an ohmic electrode, for example, ITO, and an n-type semiconductor layer is further stacked thereon. It is sufficient that an ohmic electrode is provided.

  The organic photoelectric conversion element is usually formed on a support substrate. The material of the support substrate is not particularly limited as long as the characteristics as the organic photoelectric conversion element are not impaired, but a glass substrate, a flexible film substrate, or a plastic substrate can also be used.

  The organic photoelectric conversion element can be produced by a known method, for example, the method described in Synth. Met., 102, 982 (1999) or the method described in Science, 270, 1789 (1995).

<Light emitting material>
The polymer compound of the present invention can be used for a light emitting material. This light-emitting material contains the polymer compound of the present invention.

  This luminescent material may contain a known luminescent material. Examples of the luminescent material include naphthalene derivatives, anthracene and derivatives thereof, perylene and derivatives thereof, dyes such as polymethine, xanthene, coumarin, and cyanine, metal complexes of 8-hydroxyquinoline and derivatives thereof, aromatics, and the like. Group amine, tetraphenylcyclopentadiene and derivatives thereof, tetraphenylbutadiene and derivatives thereof, and the like. Examples of such a light emitting material include those described in JP-A-57-51781 and JP-A-59-194393. In addition, examples of the light-emitting material include metal complexes that emit light from a triplet excited state (triplet light-emitting complexes: for example, phosphorescence emission, and complexes in which fluorescence emission is observed in addition to the phosphorescence emission. ), For example, conventionally known low-molecular EL light-emitting materials.

<Polymer light emitting device>
Next, the polymer light emitting device of the present invention will be described.

  The polymer light emitting device of the present invention has an electrode composed of an anode and a cathode, and a light emitting layer provided between the electrodes and containing the polymer compound.

  Further, as the polymer light-emitting device of the present invention, (1) a polymer light-emitting device in which an electron transport layer is provided between the cathode and the light-emitting layer, and (2) a hole transport layer is provided between the anode and the light-emitting layer. Examples thereof include a polymer light emitting device provided, and (3) a polymer light emitting device in which an electron transport layer is provided between the cathode and the light emitting layer and a hole transport layer is provided between the anode and the light emitting layer.

More specifically, the following structures a) to d) are 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.)

  Here, the light emitting layer is a layer having a function of emitting light, the hole transporting layer is a layer having a function of transporting holes, and the electron transporting layer is a layer having a function of transporting electrons. It is. 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.

  Although there is no restriction | limiting in the film-forming method of a light emitting layer, The method by the film-forming from a solution is illustrated.

  For film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, nozzle coating method, capillary Methods such as a coating method, a screen printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  When forming a film from a solution by using the polymer compound of the present invention at the time of preparing a polymer light emitting device, it is only necessary to remove the solvent by drying after coating this solution, and charge transport materials and light emitting materials can be used. Even in the case of mixing, the same technique can be applied, which is very advantageous in production.

  The film thickness of the light emitting layer varies depending on the material used and may be selected so that the drive voltage and the light emission efficiency are appropriate. For example, the film thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm. More preferably, it is 5 nm to 200 nm.

  In the polymer light emitting device of the present invention, a light emitting material other than the polymer compound may be mixed and used in the light emitting layer. In the polymer light emitting device of the present invention, a light emitting layer containing a light emitting material other than the polymer compound may be laminated with a light emitting layer containing the polymer compound.

  As the light emitting material other than the polymer compound, known materials can be used. Examples of the low molecular weight compound include naphthalene derivatives, anthracene and derivatives thereof, perylene and derivatives thereof, polymethine-type, xanthene-type, coumarin-type and cyanine-type pigments, 8-hydroxyquinoline and metal complexes of its derivatives, aromatic amines, and the like. , Tetraphenylcyclopentadiene and derivatives thereof, tetraphenylbutadiene and derivatives thereof, and the like can be used. Specifically, for example, known ones such as those described in JP-A-57-51781 and 59-194393 can be used.

  When the polymer light-emitting device of the present invention has a hole transport layer, the hole transport material used includes polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, and polysiloxane having an aromatic amine in the side chain or main chain. Derivatives, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thieni Lembinylene) and its derivatives are exemplified. Specifically, as the hole transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209988, Examples described in JP-A-3-7992 and JP-A-3-152184 are exemplified.

  Among these, as the hole transport material used for the hole transport layer, polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine compound group in the side chain or main chain, polyaniline and derivatives thereof A polymer hole transport material such as polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, more preferably polyvinyl carbazole and derivatives thereof, Polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.

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

  Examples of the polysilane and derivatives thereof include compounds described in Chemical Review, Vol. 89, page 1359 (1989), GB 2300196 published specification, and the like. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.

  Since the polysiloxane derivative 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, In the low molecular hole transport material, the method by the film-forming from a mixed solution with a polymer binder is illustrated. In the case of a polymer hole transport material, a method of 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 transport 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.

  For film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, nozzle coating method, capillary Methods such as a coating method, a screen printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  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. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  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 light-emitting device of the present invention has an electron transport layer, known electron transport materials can be used, such as oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and Derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and Examples thereof include polyfluorene and derivatives thereof. Specifically, JP-A 63-70257, 63-175860, JP 2-135359, 2-135361, 2-209988, 3-37992, Examples described in JP-A-3-152184 are exemplified.

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

  There are no particular restrictions on the method for forming the electron transport layer, but for low molecular weight electron transport materials, the vacuum evaporation method from powder, or the method by film formation from a solution or molten state, the polymer electron transport material is a solution or melt. Each method is exemplified by film formation from the state. When forming a film from a solution or a molten state, a 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.

  For film formation from solution or molten state, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, nozzle coating Methods such as a method, a capillary coating method, a screen printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those not strongly absorbing visible light are suitably used. Examples of the polymer binder include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, Examples include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

  The film thickness of the electron transport layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are moderate values, but at least a thickness that does not cause pinholes is required. If the thickness is too thick, the drive 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 the function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element are particularly the 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 the insulating layer may be provided adjacent to the electrode, and the adhesion at the interface is improved or mixing is prevented. For this purpose, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.

  The order and number of layers to be stacked, and the thickness of each layer may be appropriately selected in consideration of light emission efficiency and element lifetime.

  In the present invention, a polymer light emitting device provided with a charge injection layer (electron injection layer, hole injection layer) is a polymer light emitting device provided with a charge injection layer adjacent to the cathode, or a charge injection adjacent to the anode. Examples thereof include a polymer light emitting device provided with a layer.

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 / charge 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 / charge 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 anode and a hole transport layer provided between the anode material and the hole transport material included in the hole transport layer. A layer containing a material having a value ionization potential, a layer provided between a cathode and an electron transport layer, and a layer containing a material having an intermediate value of electron affinity between the cathode material and the electron transport material contained in the electron transport layer, etc. Is exemplified.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, and leakage between light emitting pixels 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 make the electric conductivity of the conductive polymer 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, the conductive polymer is doped with an appropriate amount of ions.

  The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of the anion include polystyrene sulfonate ion, alkylbenzene sulfonate ion, camphor sulfonate ion, and the like, and examples of the cation include lithium ion, sodium ion, potassium ion, tetrabutylammonium ion, 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 derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene And derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanine (copper phthalocyanine, etc.), carbon, etc. .

  The insulating layer has a function of facilitating charge injection. The average thickness of this insulating layer is usually 0.1 to 20 nm, preferably 0.5 to 10 nm, more preferably 1 to 5 nm. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. Examples of the polymer light emitting device provided with the insulating layer include a polymer light emitting device provided with an insulating layer adjacent to the cathode and a polymer light emitting device provided with an insulating layer adjacent to the anode.

Specific examples include the following structures q) to ab).
q) anode / insulating layer / light emitting layer / cathode r) anode / light emitting layer / insulating layer / cathode s) anode / insulating layer / light emitting layer / insulating layer / cathode t) anode / insulating layer / hole transport layer / light emitting layer / Cathode u) anode / hole transport layer / light emitting layer / insulating layer / cathode v) anode / insulating layer / hole transport layer / light emitting layer / insulating layer / cathode w) anode / insulating layer / light emitting layer / electron transport layer / Cathode x) anode / light emitting layer / electron transport layer / insulating layer / cathode y) anode / insulating layer / light emitting layer / electron transport layer / insulating layer / cathode z) anode / insulating layer / hole transport layer / light emitting layer / Electron transport layer / cathode
aa) Anode / hole transport layer / light emitting layer / electron transport layer / insulating layer / cathode
ab) Anode / insulating layer / hole transporting layer / light emitting layer / electron transporting layer / insulating layer / cathode

  The substrate on which the polymer light-emitting device of the present invention is formed may be any substrate that does not change when an electrode is formed and an organic layer is formed. Examples thereof include substrates such as glass, plastic, polymer film, and silicon. Is done. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

  In the present invention, it is usually preferred that at least one of the anode and cathode electrodes is transparent or translucent, and the anode side is transparent or translucent.

  As the material for the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and their composite films 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. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as this anode.

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

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

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

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

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

  As the protective layer, resins, metal oxides, metal fluorides, metal borides 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 thermosetting resin or a photocurable 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 light-emitting device of the present invention can be used in a display device such as a planar light source, a segment display device, a dot matrix display device, a liquid crystal display device (for example, a backlight).

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

  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.

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples. In this example, the weight average molecular weight and number average molecular weight were determined in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

で表されるジブロム化合物単量体（２）４．８６ｇとを反応容器に仕込んだ後、直ちに、反応系内を窒素ガス置換した。次に、この容器に、予めアルゴンガスをバブリングして脱気したトルエン８０ｇを加えた。このトルエン溶液に、テトラ−ｎ−ブチルアンモニウムブロミド１．６ｇを加えた。次に、予めアルゴンガスをバブリングして脱気した１６．７重量％炭酸ナトリウム水溶液５０ｍｌを加えた。この溶液をアルゴンガスでバブリングして完全に脱気した後、テトラキス（トリフェニルホスフィン）パラジウム（０）１．２ｇを加え、昇温し、２０時間還流した。なお、反応は窒素ガス雰囲気下で行った。 <Synthesis Example 1> (Synthesis of Monomer (1))
3.3 g of 4-formylphenylboric acid and the following structural formula:

Then, 4.86 g of the dibromo compound monomer (2) represented by the formula (1) was charged into the reaction vessel, and immediately, the inside of the reaction system was replaced with nitrogen gas. Next, 80 g of toluene deaerated by bubbling argon gas in advance was added to the container. To this toluene solution, 1.6 g of tetra-n-butylammonium bromide was added. Next, 50 ml of a 16.7 wt% aqueous sodium carbonate solution deaerated by bubbling argon gas in advance was added. The solution was completely deaerated by bubbling with argon gas, and then added with 1.2 g of tetrakis (triphenylphosphine) palladium (0), heated up and refluxed for 20 hours. The reaction was performed in a nitrogen gas atmosphere.

で表される単量体（１）０．７ｇを得た。 The reaction solution was cooled to near room temperature, and 100 g of toluene was added. This solution was allowed to stand, and a lower layer containing a liquid separation and a precipitate was collected. Next, this solution containing the precipitate was filtered to collect the precipitate. This precipitate was washed with a mixed solvent of methanol / ion-exchanged water = 1/1 (volume ratio) and then dried under reduced pressure to obtain a crude product. Next, this crude product was dissolved in 800 ml of chloroform. The solution was filtered to remove insolubles, and then the solvent was distilled off from the solution under reduced pressure. The resulting product was dried under reduced pressure to obtain the following structural formula:

The monomer (1) represented by this was obtained 0.7g.

で表される単量体（２）０．６１ｇと、下記構造式：

で表される単量体（３） ０．２９３ｇとを、脱水トルエン５０ｇに溶解した。この溶液にアルゴンガスを吹き込み、バブリングして反応系内をアルゴンガスで置換した。次に、この溶液に、第三ブトキシカリウム ０．４５ｇを加え、９５℃で２時間反応した。なお、反応は窒素ガス雰囲気下で行った。 <Example 1> (Synthesis of polymer compound 1)
0.107 g of the monomer (1) and the following structural formula:

0.61 g of the monomer (2) represented by the following structural formula:

The monomer (3) represented by the formula (0.23 g) was dissolved in dehydrated toluene 50 g. Argon gas was blown into this solution and bubbled to replace the reaction system with argon gas. Next, 0.45 g of tert-butoxy potassium was added to this solution and reacted at 95 ° C. for 2 hours. The reaction was performed in a nitrogen gas atmosphere.

  After the reaction, this reaction solution was cooled to near room temperature, and then acetic acid was added to the reaction solution to neutralize it. After adding 50 g of toluene to this solution, this solution was slowly poured into methanol and reprecipitated. The produced precipitate was collected by filtration and dried under reduced pressure to obtain a polymer. Subsequently, after dissolving this polymer in toluene, the obtained toluene solution was filtered to remove insoluble matters. This toluene solution was purified by passing through an alumina column. The obtained toluene solution was concentrated under reduced pressure and then reprecipitated by pouring into methanol. The produced precipitate was collected by filtration and dried under reduced pressure to obtain 0.06 g of a polymer. Hereinafter, this polymer is referred to as “polymer compound 1”.

The polymer compound 1 had a polystyrene equivalent weight average molecular weight of 1.4 × 10 ⁴ and a polystyrene equivalent number average molecular weight of 7.1 × 10 ³ .

  The structure of the repeating unit contained in the polymer compound 1 estimated from the charging is as follows, and the molar ratio estimated from the charging is repeating unit J: repeating unit K = 9: 1.

・繰り返し単位Ｋ

・ Repeat unit J

・ Repeat unit K

で表される単量体（４）０．４４１ｇと、下記構造式：

で表される単量体（５）０．１２７ｇと、下記構造式：

で表される単量体（１００）｛[1-cis-1,2-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)heptene]和光純薬工業（株）製｝０．３５２ｇと、メチルトリオクチルアンモニウムクロライド（商品名：aliquat336、Aldrich製、CH₃N[(CH₂)₇CH₃]₃Cl、density 0.884g/ml,25℃、trademark of Henkel Corporation）０．１３ｇと、ジクロロビス（トリフェニルホスフィン）パラジウム（II） １．６ｍｇとを反応容器に仕込み、反応容器内をアルゴンガスで十分置換した。この反応容器に、予めアルゴンガスでバブリングして脱気したトルエン １５ｍｌを加えた。次に、この溶液に、予めアルゴンガスでバブリングして脱気した１６．７重量％Ｎａ₂ＣＯ₃水溶液 ５ｍｌを数分間で滴下した後、昇温し、１１時間還流した。なお、反応は、アルゴンガス雰囲気下で行った。 <Example 2> (Synthesis of polymer compound 2)
The following structural formula:

0.441 g of the monomer (4) represented by the following structural formula:

0.127 g of the monomer (5) represented by the following structural formula:

Monomer (100) {[1-cis-1,2-Bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) heptene] Wako Pure Chemical Industries Co., Ltd.} 0.352 g, methyl trioctyl ammonium chloride (trade name: aliquat336, manufactured by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / ml, 25 ° C., trademark of Henkel Corporation) 0.13 g and dichlorobis (triphenylphosphine) palladium (II) 1.6 mg were charged into a reaction vessel, and the inside of the reaction vessel was sufficiently replaced with argon gas. To this reaction vessel, 15 ml of toluene previously deaerated by bubbling with argon gas was added. Next, 5 ml of a 16.7 wt% Na ₂ CO ₃ aqueous solution previously deaerated by bubbling with an argon gas was dropped into this solution in several minutes, and then the temperature was raised and refluxed for 11 hours. The reaction was performed in an argon gas atmosphere.

After completion of the reaction, the reaction solution was cooled to near room temperature, and then 40 g of toluene was added to the reaction solution. The reaction solution was allowed to stand, and the separated toluene solution was recovered. Next, this toluene solution was filtered to remove insoluble matters, and then this toluene solution was passed through an alumina column for purification. Next, this toluene solution was concentrated under reduced pressure, poured into methanol, purified by reprecipitation, and the generated precipitate was recovered. This precipitate was washed with methanol and then dried under reduced pressure to obtain 0.3 g of a polymer. Hereinafter, this polymer is referred to as “polymer compound 2”. The polymer compound 2 had a polystyrene equivalent weight average molecular weight of 1.1 × 10 ⁴ and a polystyrene equivalent number average molecular weight of 6.0 × 10 ³ .

  The structure of the repeating unit contained in the polymer compound 2 estimated from the preparation is as follows, and the molar ratio estimated from the preparation is (repeating unit A + repeating unit A ′) :( repeating unit B + repeating unit B) ') = 4: 1.

・繰り返し単位Ｂ ・繰り返し単位Ｂ'

-Repeating unit A-Repeating unit A '

-Repeating unit B-Repeating unit B '

で表される単量体（２００）｛[cis-1,2-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)styrene] Aldrich製｝０．３５７ｇと、メチルトリオクチルアンモニウムクロライド（商品名：aliquat336、Aldrich製、CH₃N[(CH₂)₇CH₃]₃Cl、density 0.884g/ml,25℃、trademark of Henkel Corporation）０．１３ｇとジクロロビス（トリフェニルホスフィン）パラジウム（II） １．６ｍｇとを反応容器に仕込み、反応容器内をアルゴンガスで十分置換した。この反応容器に、予めアルゴンガスでバブリングして脱気したトルエン １５ｍｌを加えた。次に、この溶液に、予めアルゴンガスでバブリングして脱気した１６．７重量％Ｎａ₂ＣＯ₃水溶液５ｍｌを数分間で滴下した後、昇温し、１１時間還流した。なお、反応は、アルゴンガス雰囲気下で行った。 <Example 3> (Synthesis of polymer compound 3)
0.440 g of the monomer (4), 0.126 g of the monomer (5), and the following structural formula:

(200) {[cis-1,2-Bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) styrene] Aldrich} 0.357 g And 0.13 g of methyltrioctylammonium chloride (trade name: aliquat336, manufactured by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / ml, 25 ° C., trademark of Henkel Corporation) and dichlorobis 1.6 mg of (triphenylphosphine) palladium (II) was charged into a reaction vessel, and the inside of the reaction vessel was sufficiently replaced with argon gas. To this reaction vessel, 15 ml of toluene previously deaerated by bubbling with argon gas was added. Next, 5 ml of a 16.7 wt% Na ₂ CO ₃ aqueous solution previously deaerated by bubbling with an argon gas was dropped into this solution in several minutes, and then the temperature was raised and the mixture was refluxed for 11 hours. The reaction was performed in an argon gas atmosphere.

After completion of the reaction, the reaction solution was cooled to near room temperature, and then 40 g of toluene was added to the reaction solution. The reaction solution was allowed to stand, and the separated toluene solution was recovered. Next, this toluene solution was filtered to remove insoluble matters, and then this toluene solution was passed through an alumina column for purification. Next, this toluene solution was concentrated under reduced pressure, poured into methanol, purified by reprecipitation, and the generated precipitate was recovered. This precipitate was washed with methanol and then dried under reduced pressure to obtain 0.3 g of a polymer. Hereinafter, this polymer is referred to as “polymer compound 3”. The polymer compound 3 had a polystyrene-equivalent weight average molecular weight of 8.7 × 10 ³ and a polystyrene-equivalent number average molecular weight of 4.8 × 10 ³ .

  The structure of the repeating unit contained in the polymer compound 3 estimated from the preparation is as follows, and the molar ratio estimated from the preparation is (repeating unit C + repeating unit C ′) :( repeating unit D + repeating unit D) ') = 4: 1.

・繰り返し単位Ｄ ・繰り返し単位Ｄ'

-Repeating unit C-Repeating unit C '

・ Repeating unit D ・ Repeating unit D ′

<Example 4> (Synthesis of polymer compound 4)
0.277 g of the monomer (4), 0.313 g of the monomer (5), 0.356 g of the monomer (100) and methyltrioctylammonium chloride (trade name: aliquat336, manufactured by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / ml, 25 ° C., trademark of Henkel Corporation) 0.10 g and dichlorobis (triphenylphosphine) palladium (II) 1.2 mg were charged in a reaction vessel, The inside of the reaction vessel was sufficiently replaced with argon gas. To this reaction vessel, 15 ml of toluene previously deaerated by bubbling with argon gas was added. Next, 5 ml of a 16.7 wt% Na ₂ CO ₃ aqueous solution previously deaerated by bubbling with an argon gas was dropped into this solution in several minutes, and then the temperature was raised and the mixture was refluxed for 10 hours. The reaction was performed in an argon gas atmosphere.

After completion of the reaction, the reaction solution was cooled to near room temperature, and then 40 g of toluene was added to the reaction solution. The reaction solution was allowed to stand, and the separated toluene solution was recovered. Next, this toluene solution was filtered to remove insoluble matters, and then this toluene solution was passed through an alumina column for purification. Next, this toluene solution was concentrated under reduced pressure, poured into methanol, purified by reprecipitation, and the generated precipitate was recovered. This precipitate was washed with methanol and then dried under reduced pressure to obtain 0.3 g of a polymer. This polymer is referred to as “polymer compound 4”. The polymer compound 4 had a polystyrene equivalent weight average molecular weight of 8.5 × 10 ³ and a polystyrene equivalent number average molecular weight of 4.7 × 10 ³ .

  The structure of the repeating unit contained in the polymer compound 4 estimated from the preparation is as follows, and the molar ratio estimated from the preparation is (repeating unit E + repeating unit E ′) :( repeating unit F + repeating unit F) ') = 1: 1.

・繰り返し単位Ｆ ・繰り返し単位Ｆ’

-Repeating unit E-Repeating unit E '

・ Repeating unit F ・ Repeating unit F ′

で表される単量体（６）０．４１４ｇと前記単量体（５）０．１２５ｇと前記単量体（２００）０．３５６ｇとメチルトリオクチルアンモニウムクロライド（商品名：aliquat336、Aldrich製、CH₃N[(CH₂)₇CH₃]₃Cl、density 0.884g/ml,25℃、trademark of Henkel Corporation）０．１５ｇとジクロロビス（トリフェニルホスフィン）パラジウム（II） １．８ｍｇとを反応容器に仕込み、反応容器内をアルゴンガスで十分置換した。この反応容器に、予めアルゴンガスでバブリングして脱気したトルエン１５ｍｌを加えた。次に、この溶液に、予めアルゴンガスでバブリングして脱気した１６．７重量％Ｎａ₂ＣＯ₃水溶液 ６ｍｌを数分間で滴下した後、昇温し、１０時間還流した。なお、反応は、アルゴンガス雰囲気下で行った。 <Example 5> (Synthesis of polymer compound 5)
The following structural formula:

0.414 g of the monomer (6), 0.125 g of the monomer (5), 0.356 g of the monomer (200), and methyltrioctylammonium chloride (trade name: aliquat336, manufactured by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884g / ml, 25 ° C, trademark of Henkel Corporation) 0.15g and dichlorobis (triphenylphosphine) palladium (II) 1.8mg The inside of the reaction vessel was sufficiently replaced with argon gas. To this reaction vessel, 15 ml of toluene previously deaerated by bubbling with argon gas was added. Next, 6 ml of a 16.7 wt% Na ₂ CO ₃ aqueous solution previously deaerated by bubbling with an argon gas was dropped into this solution in several minutes, and then the temperature was raised and refluxed for 10 hours. The reaction was performed in an argon gas atmosphere.

After completion of the reaction, the reaction solution was cooled to near room temperature, and 30 ml of toluene was added to the reaction solution. The reaction solution was allowed to stand, and the separated toluene solution was recovered. Next, the obtained toluene solution was slowly poured into methanol and reprecipitated, and the generated precipitate was recovered. The precipitate was dried under reduced pressure, and the resulting precipitate was dissolved in toluene. The obtained toluene solution was filtered and then passed through an alumina column for purification. Next, the obtained toluene solution was slowly poured into methanol and reprecipitated, and the generated precipitate was collected. This precipitate was washed with methanol and then dried under reduced pressure to obtain 0.1 g of a polymer. This polymer is referred to as “polymer compound 5”. The polymer compound 5 had a polystyrene equivalent weight average molecular weight of 5.7 × 10 ³ and a polystyrene equivalent number average molecular weight of 3.2 × 10 ³ .

  The structure of the repeating unit contained in the polymer compound 5 estimated from the preparation is as follows, and the molar ratio estimated from the preparation is (repeating unit AA + repeating unit AA ′) :( repeating unit BB + repeating unit BB) ') = 8: 2.

繰り返し単位ＢＢ 繰り返し単位ＢＢ’

Repeating unit AA Repeating unit AA '

Repeating unit BB Repeating unit BB '

で表される単量体（７）０．７９７ｇと下記構造式：

で表される単量体（８）０．１８４ｇと前記単量体（５）０．２５１ｇと前記単量体（２００）０．７１２ｇとメチルトリオクチルアンモニウムクロライド（商品名：aliquat336、Aldrich製、CH₃N[(CH₂)₇CH₃]₃Cl、density 0.884g/ml,25℃、trademark of Henkel Corporation）０．３０ｇとジクロロビス（トリフェニルホスフィン）パラジウム（II） ３．７ｍｇとを反応容器に仕込み、反応容器内をアルゴンガスで十分置換した。この反応容器に、予めアルゴンガスでバブリングして脱気したトルエン３０ｍｌを加えた。次に、得られたトルエン溶液に、予めアルゴンガスでバブリングして脱気した１６．７重量％Ｎａ₂ＣＯ₃水溶液 １０ｍｌを数分間で滴下した後、昇温し、１０時間還流した。なお、反応は、アルゴンガス雰囲気下で行った。 <Example 6> (Synthesis of polymer compound 6)
The following structural formula:

0.797 g of the monomer (7) represented by the following structural formula:

0.184 g of the monomer (8), 0.251 g of the monomer (5), 0.712 g of the monomer (200) and methyl trioctyl ammonium chloride (trade name: aliquat336, manufactured by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / ml, 25 ° C., trademark of Henkel Corporation) 0.30 g and dichlorobis (triphenylphosphine) palladium (II) 3.7 mg The inside of the reaction vessel was sufficiently replaced with argon gas. To this reaction vessel, 30 ml of toluene previously deaerated by bubbling with argon gas was added. Next, 10 ml of a 16.7 wt% Na ₂ CO ₃ aqueous solution previously deaerated by bubbling with an argon gas was dropped into the obtained toluene solution in several minutes, and then the temperature was raised and refluxed for 10 hours. The reaction was performed in an argon gas atmosphere.

After completion of the reaction, the reaction solution was cooled to near room temperature, and 30 ml of toluene was added to the reaction solution. The reaction solution was allowed to stand, and the separated toluene solution was recovered. Next, this toluene solution was filtered to remove insoluble matters, and then the obtained toluene solution was slowly poured into methanol and re-precipitated, and the generated precipitate was recovered. The precipitate was dried under reduced pressure, and the resulting precipitate was dissolved in toluene. The obtained toluene solution was filtered and then passed through an alumina column for purification. Next, the obtained toluene solution was slowly poured into methanol and reprecipitated, and the generated precipitate was collected. This precipitate was washed with methanol and then dried under reduced pressure to obtain 0.15 g of a polymer. This polymer is referred to as “polymer compound 6”. The polymer compound 6 had a polystyrene equivalent weight average molecular weight of 4.4 × 10 ³ and a polystyrene equivalent number average molecular weight of 2.9 × 10 ³ .

  The structure of the repeating unit contained in the polymer compound 6 estimated from the preparation is as follows, and the molar ratio estimated from the preparation is (repeating unit CC + repeating unit CC ′) :( repeating unit DD + repeating unit DD) '): (Repeating unit EE + Repeating unit EE') = 6: 2: 2.

繰り返し単位ＤＤ 繰り返し単位ＤＤ’

繰り返し単位ＥＥ 繰り返し単位ＥＥ‘

Repeating unit CC Repeating unit CC '

Repeating unit DD Repeating unit DD '

Repeating unit EE Repeating unit EE '

で表される単量体（９）１．０４０ｇと下記構造式：

で表される単量体（１０）０．１８９ｇと前記単量体（５）０．２５１ｇと前記単量体（１００）０．７２８ｇとメチルトリオクチルアンモニウムクロライド（商品名：aliquat336、Aldrich製、CH₃N[(CH₂)₇CH₃]₃Cl、density 0.884g/ml,25℃、trademark of Henkel Corporation）０．３０ｇとジクロロビス（トリフェニルホスフィン）パラジウム（II） ３．６ｍｇとを反応容器に仕込み、反応容器内をアルゴンガスで十分置換した。この反応容器に、予めアルゴンガスでバブリングして脱気したトルエン３０ｍｌを加えた。次に、得られたトルエン溶液に、予めアルゴンガスでバブリングして脱気した１６．７重量％Ｎａ₂ＣＯ₃水溶液 １０ｍｌを数分間で滴下した後、昇温し、１０時間還流した。なお、反応は、アルゴンガス雰囲気下で行った。 <Example 7> (Synthesis of polymer compound 7)
The following structural formula:

1.040 g of monomer (9) represented by the following structural formula:

0.189 g of the monomer (10), 0.251 g of the monomer (5), 0.728 g of the monomer (100) and methyltrioctylammonium chloride (trade name: aliquat336, manufactured by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / ml, 25 ° C., trademark of Henkel Corporation) 0.30 g and dichlorobis (triphenylphosphine) palladium (II) 3.6 mg The inside of the reaction vessel was sufficiently replaced with argon gas. To this reaction vessel, 30 ml of toluene previously deaerated by bubbling with argon gas was added. Next, 10 ml of a 16.7 wt% Na ₂ CO ₃ aqueous solution previously deaerated by bubbling with an argon gas was dropped into the obtained toluene solution in several minutes, and then the temperature was raised and refluxed for 10 hours. The reaction was performed in an argon gas atmosphere.

After completion of the reaction, the reaction solution was cooled to near room temperature, and 30 ml of toluene was added to the reaction solution. The obtained reaction solution was allowed to stand, and the separated toluene solution was recovered. Next, this toluene solution was filtered to remove insoluble matters, and then the obtained toluene solution was slowly poured into methanol and re-precipitated, and the generated precipitate was recovered. The precipitate was dried under reduced pressure, and the resulting precipitate was dissolved in toluene. The obtained toluene solution was filtered and then passed through an alumina column for purification. Next, the obtained toluene solution was slowly poured into methanol and reprecipitated, and the generated precipitate was collected. This precipitate was washed with methanol and then dried under reduced pressure to obtain 0.12 g of a polymer. This polymer is referred to as “polymer compound 7”. The polymer compound 7 had a polystyrene-equivalent weight average molecular weight of 5.1 × 10 ³ and a polystyrene-equivalent number average molecular weight of 3.1 × 10 ³ .

  The structure of the repeating unit contained in the polymer compound 7 estimated from the preparation is as follows, and the molar ratio estimated from the preparation is (repeating unit FF + repeating unit FF ′): (repeating unit GG + repeating unit GG). '): (Repeating unit HH + Repeating unit HH') = 6: 2: 2.

繰り返し単位ＧＧ 繰り返し単位ＧＧ’

繰り返し単位ＨＨ 繰り返し単位ＨＨ’

Repeat unit FF Repeat unit FF '

Repeating unit GG Repeating unit GG '

Repeating unit HH Repeating unit HH '

<Example 8> (Synthesis of polymer compound 8)
0.987 g of the monomer (4), 0.250 g of the monomer (5), 0.712 g of the monomer (200), and methyl trioctyl ammonium chloride (trade name: aliquat336, manufactured by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / ml, 25 ° C., trademark of Henkel Corporation) 0.36 g and dichlorobis (triphenylphosphine) palladium (II) 3.6 mg are charged in a reaction vessel, The inside of the reaction vessel was sufficiently replaced with argon gas. To this reaction vessel, 30 ml of toluene previously deaerated by bubbling with argon gas was added. Next, 10 ml of a 16.7 wt% Na ₂ CO ₃ aqueous solution previously deaerated by bubbling with an argon gas was dropped into the obtained toluene solution in several minutes, and then the temperature was raised and refluxed for 10 hours. The reaction was performed in an argon gas atmosphere.

After completion of the reaction, the reaction solution was cooled to near room temperature, and 15 ml of toluene was added to the reaction solution. The obtained reaction solution was allowed to stand, and the separated toluene solution was recovered. Next, this toluene solution was filtered to remove insoluble matters, and then the obtained toluene solution was slowly poured into methanol and re-precipitated, and the generated precipitate was recovered. The precipitate was dried under reduced pressure, and the resulting precipitate was dissolved in toluene. The obtained toluene solution was filtered and then passed through an alumina column for purification. Next, the obtained toluene solution was slowly poured into methanol and reprecipitated, and the generated precipitate was collected. This precipitate was washed with methanol and then dried under reduced pressure to obtain 0.48 g of a polymer. This polymer is referred to as “polymer compound 8”. The polymer compound 8 had a polystyrene-equivalent weight average molecular weight of 4.9 × 10 ³ and a polystyrene-equivalent number average molecular weight of 3.3 × 10 ³ .

  The structure of the repeating unit contained in the polymer compound 8 estimated from the preparation is as follows, and the molar ratio estimated from the preparation is (repeating unit II + repeating unit II ′): (repeating unit JJ + repeating unit JJ ') = 9: 1.

・繰り返し単位ＪＪ ・繰り返し単位ＪＪ’

-Repeating unit II-Repeating unit II '

・ Repeating unit JJ ・ Repeating unit JJ '

<Example 9> (Fluorescence characteristic evaluation)
Thin films of polymer compounds 1-8 were prepared by spin-coating 0.8 wt% toluene solutions of polymer compounds 1-8 on a quartz plate. Using this thin film, the fluorescence spectra of the polymer compounds 1 to 8 are obtained by measuring with a fluorescence spectrophotometer (manufactured by JOBINYVON-SPEX, trade name: Fluorolog) at an excitation wavelength of 350 nm, and the absorption spectrum is obtained with a spectrophotometer ( Varian's product name: Cary5E).

  Table 1 shows the measurement results of the absorption peak wavelength and the fluorescence peak wavelength of the polymer compounds 1 to 8 thus obtained. Polymer compounds 1 to 8 of the present invention exhibited red fluorescence.

[Table 1] Absorption peak wavelength and fluorescence peak wavelength of polymer compound

<Example 10> (Creation and evaluation of device)
About 50 nm thick by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (trade name: Baytron) on a glass substrate on which an ITO film is applied with a thickness of about 150 nm by sputtering. And then dried on a hot plate at 120 ° C. for about 5 minutes. Next, a film having a thickness of about 70 nm is formed by spin coating using about 1.5 wt% toluene solution of polymer compound 1. Further, this was dried at 80 ° C. under reduced pressure for about 1 hour, and then lithium fluoride was deposited by about 4 nm, then, as a cathode, calcium was deposited by about 20 nm, and then aluminum was deposited by about 50 nm to produce a polymer light emitting device. To do. By applying a voltage to the obtained device, EL light emission (deep red) from the polymer compound 1 can be obtained.
Similarly, for the polymer compounds 2 to 8, a polymer light-emitting device is produced. By applying a voltage to the obtained elements 2 to 8, EL light emission (deep red) from the polymer compound is obtained.

Claims (16)

Following formula (1):

[In the formula, Ar ₁ and Ar ₂ each independently have an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or a substituent. The divalent aromatic amine group which may be sufficient is represented. When a plurality of Ar ₁ and Ar ₂ are present, they may be the same or different. Z ₁ represents —CR ₁ ═CR ₂ — or —C≡C—. Here, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. m and n are each independently 1 or 2. R ^s and R ^t each independently represents a hydrogen atom, an alkyl group or an alkoxy group. ]
A high molecular compound having a polystyrene-reduced number average molecular weight of 1 × 10 ³ to 1 × 10 ⁸ . The repeating unit represented by the formula (1) is represented by the following formula (1a):

[Wherein, R ^a , R ^b , R ^c and R ^d each independently represents a hydrogen atom, an alkyl group, an alkoxy group or an aryl group. R ^e and R ^f each independently represents a hydrogen atom, an alkyl group or an aryl group. m ′ and n ′ are each independently 1 or 2. When ^a plurality of R ^{a to} R ^d are present, they may be the same or different. ]
The polymer compound according to claim 1, which is represented by: Furthermore, the following formula (2):

[In the formula, Ar ₅ represents an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or a divalent aromatic which may have a substituent. Represents a group amine group. Z ₂ represents —CR ₃ ═CR ₄ — or —C≡C—. R ₃ and R ₄ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. ]
The high molecular compound of Claim 1 or 2 containing the repeating unit represented by these. In the formula (2), an arylene group optionally having a substituent represented by Ar ₅ is represented by the following formula (60):

[In formula, A ring and B ring represent the aromatic-hydrocarbon ring which may have a substituent each independently. Two bonds exist on the A ring or the B ring, respectively. Rw and Rx are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl Represents a group, an arylamino group, a monovalent heterocyclic group, an acyl group, a substituted carboxyl group or a cyano group, and Rw and Rx may be bonded to each other to form a ring. ]
The polymer compound according to claim 3, which is represented by: The arylene group which may have a substituent represented by the formula (60) is represented by the following formulas (2A) to (2D):

[Wherein, R ^g represents a hydrogen atom, an alkyl group or an aryl group. Two R ^{g s} may be the same or different. Two R ^{g s} may be bonded to each other to form a ring. ]
The polymer compound according to claim 4, which is represented by any one of: In the formula (2), a divalent heterocyclic group optionally having a substituent represented by Ar ₅ is represented by the following formula (70):

[In formula, C ring and D ring represent an aromatic ring each independently. C ring and D ring are alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group It may have a substituent selected from the group consisting of a monovalent heterocyclic group, an acyl group, an acyloxy group, a substituted carboxyl group and a cyano group. When there are a plurality of substituents, they may be the same or different. E is O or S. ]
The polymer compound according to claim 3, which is represented by: The divalent heterocyclic group optionally having a substituent represented by the formula (70) is represented by the following formula (2E):

[Wherein Y represents O or S. R ^j and R ^k each independently represents an alkyl group, an alkoxy group or an aryl group. a and b are each independently 0 or 1. ]
The polymer compound according to claim 6, which is represented by: The group represented by said Z < ₂ > is -CR < ₃ > = CR < ₄ >-, The high molecular compound as described in any one of Claims 3-7. The composition containing the high molecular compound as described in any one of Claims 1-8, and the compound whose number average molecular weights of polystyrene other than this high molecular compound are 10 < ³ > -10 < ⁸ >.   The polymer light emitting element which has an electrode which consists of an anode and a cathode, and the light emitting layer which is provided between this electrode and contains the polymer compound as described in any one of Claims 1-8.   A planar light source comprising the polymer light emitting device according to claim 10.   A display device comprising the polymer light emitting device according to claim 10.   A liquid composition comprising the polymer compound according to any one of claims 1 to 8 and a solvent.   The thin film containing the high molecular compound as described in any one of Claims 1-8.   The organic transistor containing the high molecular compound as described in any one of Claims 1-8.   The solar cell containing the high molecular compound as described in any one of Claims 1-8.