JP2007224282A - Polymer compound and polymer light emitting device using the same - Google Patents

Abstract

〔式中、Ａｒ₂は、アリーレン基等を表し、Ａｒ₅は、直接結合、アリーレン基等を表し、Ｒ³、Ｒ⁴は、直接結合、置換基等を表し、Ａｒ₃、Ａｒ₄は、アリール基等を表し、Ｙは、ホスフィン、又はホスフィンオキシドを表す。但し、Ａｒ₅が直接結合の場合、Ｒ³は直接結合である。〕
【選択図】なしA novel polymer compound that is particularly useful as a light-emitting material and has a practical level of heat resistance and fluorescence intensity, and a polymer light-emitting device using the polymer compound.
A polymer compound containing a repeating unit represented by the formula (1). -[Ar _1- (X ₁ ) _n ]-(1) [wherein Ar ₁ represents an arylene group having a group represented by the formula (2), etc., and X ₁ represents —CR ¹ ═CR ² — ( R ¹ and R ² represent a hydrogen atom or a substituent) or —C≡C—, and n represents 0 or 1. ]

[In the formula, Ar ₂ represents an arylene group, Ar ₅ represents a direct bond, an arylene group, etc., R ³ and R ⁴ represent a direct bond, a substituent, etc., and Ar ₃ and Ar ₄ represent Represents an aryl group or the like, and Y represents phosphine or phosphine oxide. However, when Ar ₅ is a direct bond, R ³ is a direct bond. ]
[Selection figure] None

Description

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

  Various light-emitting materials soluble in a solvent have been studied because a layer in a light-emitting element can be formed by a coating method. Specific examples of the light-emitting material include polyarylene vinylene having a triarylamine group in the side chain (Patent Document 1), polyarylene having an aromatic heterocyclic group in the side chain (Patent Document 2), and a quinoline group in the side chain. Have been proposed, such as polyfluorene having a triarylamine group in the side chain (Non-patent document 2).

US Pat. No. 6,414,104 JP 2004-277568 A J. of Polymer Science, Part A, Polymer Chemistry, Vol.43, 859-869 (2005) Advanced Materials, 14, No.11, 809-811 (2002)

  The present invention is particularly useful as a light-emitting material, and an object thereof is to provide a novel polymer compound having practical levels of heat resistance and fluorescence intensity, and a polymer light-emitting device using the polymer compound.

As a result of intensive studies, the present inventors have made the present invention. That is, this invention provides the high molecular compound containing the repeating unit shown by following formula (1).
-[Ar _1- (X ₁ ) _n ]-(1)
[In the formula, Ar ₁ represents an arylene group having a group represented by the following formula (2), a divalent heterocyclic group having a group represented by the following formula (2), or a group represented by the following formula (2). X ₁ represents —CR ¹ ═CR ² — (wherein R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic group) Or represents a cyano group) or —C≡C—, and n represents 0 or 1. ]

〔式中、Ａｒ₂は、アリーレン基、２価の複素環基または２価の芳香族アミン基を表し、Ａｒ₅は、直接結合、アリーレン基、２価の複素環基または２価の芳香族アミン基を表し、Ｒ³およびＲ⁴はそれぞれ独立に、直接結合、−Ｒ⁵−、−Ｏ−Ｒ⁵−、−Ｒ⁵−Ｏ−、−Ｒ⁵−Ｃ（Ｏ）Ｏ−、−Ｒ⁵−ＯＣ（Ｏ）−、−Ｒ⁵−Ｎ（Ｒ⁶）−、−Ｏ−、−Ｓ−、−Ｃ（Ｏ）Ｏ−、−Ｃ（Ｏ）−、−ＣＲ⁷＝ＣＲ⁸−または−Ｃ≡Ｃ−（ここで、Ｒ⁵は、アルキレン基またはアルケニレン基を表し、Ｒ⁶、Ｒ⁷およびＲ⁸はそれぞれ独立に、水素原子、アルキル基、アリール基、１価の複素環基またはシアノ基を示す。）を表し、Ａｒ₃およびＡｒ₄はそれぞれ独立に、アリール基、１価の複素環基または１価の芳香族アミン基を表し、Ｙは、下記式：

[In the formula, Ar ₂ represents an arylene group, divalent heterocyclic group or divalent aromatic amine group, and Ar ₅ represents a direct bond, an arylene group, a divalent heterocyclic group or a divalent aromatic group. Represents an amine group, and R ³ and R ⁴ are each independently a direct bond, —R ⁵ —, —O—R ⁵ —, —R ⁵ —O—, —R ⁵ —C (O) O—, —R. ⁵ —OC (O) —, —R ⁵ —N (R ⁶ ) —, —O—, —S—, —C (O) O—, —C (O) —, —CR ⁷ ═CR ⁸ — or —C≡C— (wherein R ⁵ represents an alkylene group or an alkenylene group, and R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or represents.) of a cyano group, Ar ₃ and Ar ₄ each independently represent an aryl group, a monovalent heterocyclic group or monovalent aromatic amine group, Y is represented by the following formula

、または

Or

を表す。但し、Ａｒ₅が直接結合の場合には、Ｒ³は直接結合である。〕

Represents. However, when Ar ₅ is a direct bond, R ³ is a direct bond. ]

  The polymer compound of the present invention is particularly useful as a light emitting material, and has excellent heat resistance and fluorescence intensity. A polymer light emitting device using this polymer compound has high performance (for example, high luminance and high luminous efficiency), and is particularly useful for a planar light source, a display device and the like. Moreover, this high molecular compound can be used also for an organic transistor and a solar cell.

  Hereinafter, the present invention will be described in detail.

<Polymer compound>
The polymer compound of the present invention is a polymer compound containing a repeating unit represented by the formula (1). The polymer compound of the present invention may contain only one type of repeating unit represented by the formula (1) or two or more types.

In the formula (1), Ar ₁ represents an arylene group having a group represented by the formula (2), a divalent heterocyclic group having a group represented by the formula (2), or the formula (2). 2 having a group represented by formula (2), preferably an arylene group having a group represented by formula (2), or 2 having a group represented by formula (2). It is a valent heterocyclic group.

Ar ₁ represents 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 in addition to the group represented by the formula (2). , An arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group, a cyano group and the like. When Ar ₁ has a plurality of substituents, they may be the same or different. Details of these substituents are the same as those specifically described and exemplified as R in the examples of the arylene group described below (the following formulas 1 to 38, A to I, and K).

  In the formula (1), the arylene group means an atomic group remaining after removing two hydrogen atoms from an aromatic hydrocarbon. The number of carbon atoms of the arylene group is usually about 6 to 60. 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 a vinylene group.

  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 a triphenylene group. (Formula 26-28), condensed ring compound group (Formula 29-38), stilbene-diyl group (Formula A to D), distilbene-diyl group (Formula E, F), benzofluorene-diyl group ( The following formulas G, H, I, K) and the like are exemplified. Among these, a phenylene group, a naphthalenediyl group, a biphenylene group, a fluorene-diyl group (the following formulas 36 to 38), a stilbene-diyl group (the following formulas A to D), a distilbene-diyl group (the following formulas E and F), Benzofluorene-diyl groups (formulas G, H, I, K) are preferred.

  In these examples of arylene groups (the above formulas 1 to 38, A to I, and K), each R is independently a group represented by the formula (2), a hydrogen atom, 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, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group; In these examples of arylene groups, one structural formula has a plurality of Rs, but they may be the same or different. However, at least one of R is a group represented by the formula (2).

  The alkyl group may be linear, branched or cyclic, 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, Examples include 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, 3,7-dimethyloctyl group. Is preferred.

  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, heptyl. Examples include oxy 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. , 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, 3,7 -A 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, 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-propyldimethyl group Silyl group, butyldimethylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, Examples include dimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, 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, t-butylamino group, Examples include pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, etc. An amino group, hexylamino group, octylamino group, 2-ethylhexylamino group, decylamino group, and 3,7-dimethyloctylamino group are preferred.

The aryl group usually has about 6 to 60 carbon atoms. Specific examples of the aryl group, phenyl group, C ₁ -C ₁₂ alkoxyphenyl group ( "C ₁ -C ₁₂ alkoxy" means that the carbon number of the alkoxy moiety is 1 to 12, and so forth. ), C ₁ -C ₁₂ alkylphenyl group (“C ₁ -C ₁₂ alkyl” indicates that the alkyl moiety has 1 to 12 carbon atoms, the same shall apply hereinafter), 1-naphthyl group, 2- such as a naphthyl group, C ₁ -C ₁₂ alkoxyphenyl group, is C ₁ -C ₁₂ alkylphenyl group are preferable.

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, C ₁ -C ₁₂ alkoxyphenoxy group, C ₁ -C ₁₂ alkylphenoxy group are preferable.

The arylalkyl group usually has about 7 to 60 carbon atoms. Specific examples of the aryl alkyl group, a phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group 1-naphthyl-C ₁ -C ₁₂ alkyl group, 2-naphthyl-C ₁ -C ₁₂ alkyl group and the like, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group are preferable.

The arylalkoxy group usually has about 7 to 60 carbon atoms. 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, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ Alkylphenyl-C ₁ -C ₁₂ alkoxy groups are preferred.

The arylalkenyl group usually has about 8 to 60 carbon atoms. Specific examples of the arylalkenyl group include a phenyl-C ₂ -C ₁₂ alkenyl group (“C ₂ -C ₁₂ alkenyl” indicates that the alkenyl moiety has 2 to 12 carbon atoms, and the same shall apply hereinafter). , 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 etc. ₂ -C ₁₂ alkenyl group and the like, 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 (“C ₂ -C ₁₂ alkynyl” indicates that the alkynyl moiety has 2 to 12 carbon atoms, and the same applies hereinafter). , C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group, 1-naphthyl -C ₂ -C ₁₂ alkynyl group, 2-naphthyl -C etc. ₂ -C ₁₂ alkynyl group and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl group, a C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferred.

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 groups, 1-naphthylamino group, a 2-naphthylamino group and the like, C ₁ -C ₁₂ alkylphenyl group, di (C ₁ -C ₁₂ alkylphenyl) amino group are preferable.

In R, the monovalent heterocyclic group means the remaining atomic group obtained by removing one hydrogen atom from the heterocyclic compound. The monovalent heterocyclic group usually has about 4 to 60 carbon atoms (the carbon number does not include the carbon number of the substituent). A heterocyclic compound refers to an organic compound having a cyclic structure in which the atoms constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus and boron in the ring. Monovalent Specific examples of the heterocyclic group are thienyl groups, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, and the like C ₁ -C ₁₂ alkyl pyridyl group, a thienyl groups, C _{A 1 to} C ₁₂ alkyl thienyl group, a pyridyl group, and a C _{1 to} C ₁₂ alkyl pyridyl group are preferred.

  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 heteroatoms or groups containing heteroatoms include the following.

上記ヘテロ原子またはヘテロ原子を含む基の例示において、Ｒ’は、独立に、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、または炭素数４〜６０の１価の複素環基である。Ｒ’で表されるアルキル基、アリール基、１価の複素環基としては、上記アリーレン基の例示（上記式１〜３８、Ａ〜Ｉ、Ｋ）において、Ｒで表される置換基として説明し例示したものと同じである。

In the examples of the hetero atom or the group containing a hetero atom, R ′ is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, or a monovalent group having 4 to 60 carbon atoms. It is a heterocyclic group. The alkyl group, aryl group and monovalent heterocyclic group represented by R ′ are explained as the substituent represented by R in the examples of the arylene group (the above formulas 1 to 38, A to I and K). It is the same as illustrated.

In order to enhance the solubility of the polymer compound of the present invention in a solvent, it is preferable that the shape of the repeating unit is less symmetric, and one or more of R include a cyclic or branched alkyl chain. Is preferred. A plurality of R may be connected to form a ring. Of R, the substituent containing an alkyl chain is linear, branched or cyclic, or a combination thereof. Examples of if not linear, an isoamyl group, 2-ethylhexyl group, 3,7-dimethyl octyl group, a cyclohexyl group, and the like 4-C ₁ ~C ₁₂ alkyl cyclohexyl group.

  In the formula (1), the divalent heterocyclic group means an atomic group remaining after removing two hydrogen atoms from a heterocyclic compound. The divalent heterocyclic group usually has about 4 to 60 carbon atoms (note that the carbon number does not include the carbon number of the substituent). A heterocyclic compound refers to an organic compound having a cyclic structure in which the atoms constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus and boron in the ring. As the divalent heterocyclic group, a divalent aromatic heterocyclic group (that is, a divalent heterocyclic group having aromaticity) is preferable. Specific examples of the divalent heterocyclic group include the following.

a) 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), acridinediyl group (lower formulas 69-72), bipyridyldiyl group (lower formulas 73-75), phenanthroline diyl group (lower formulas 76-78), and the like.

  b) A fluorene structure containing silicon, nitrogen, oxygen, sulfur, selenium, etc. as a heteroatom (that is, one of the carbon atoms constituting the 5-membered ring in the fluorene ring is silicon, nitrogen, oxygen, sulfur, selenium, etc.) Or a group substituted with a group containing these atoms.) (The following formulas 79 to 93).

  c) A 5-membered heterocyclic group containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a hetero atom (the following formulas 94 to 98).

  d) A 5-membered condensed heterocyclic group containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a hetero atom (the following formulas 99 to 108).

  e) A 5-membered ring 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).

  f) A 5-membered heterocyclic group containing silicon, nitrogen, oxygen, sulfur, selenium or the like as a heteroatom and bonded to the phenyl group at the α-position of the heteroatom (the following formulas 111 to 117).

  In the examples of these divalent heterocyclic groups (the above formulas 39 to 117), R is explained and exemplified in the above-mentioned arylene group (as R in the above formulas 1 to 38, A to I and K). Is the same.

  In the formula (1), the divalent aromatic amine group means the remaining atomic group obtained by removing two hydrogen atoms from the aromatic amine. The divalent aromatic amine group usually has about 4 to 60 carbon atoms (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). However, the formula (3) has at least one substituent represented by the formula (2).

〔式中、Ａｒ₆およびＡｒ₈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、下記一般式（４）で表される基、または下記一般式（５）で表される基であり、Ａｒ₇は、置換基を有していてもよいアリール基、下記一般式（６）で表される基または下記一般式（７）で表される基を示し、Ａｒ₆とＡｒ₇の間、Ａｒ₆とＡｒ₈の間、またはＡｒ₇とＡｒ₈の間に環を形成していてもよい。

[In the formula, Ar ₆ and Ar ₈ are each independently an arylene group which may have a substituent, a group represented by the following general formula (4), or a group represented by the following general formula (5) Ar ₇ represents an aryl group which may have a substituent, a group represented by the following general formula (6) or a group represented by the following general formula (7), and Ar ₆ and Ar ₇ A ring may be formed between Ar ₆ and Ar ₈ , or Ar ₇ and Ar ₈ .

（式中、Ａｒ₉およびＡｒ₁₀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示し、Ｒ⁹およびＲ¹⁰は、それぞれ独立に、水素原子、アルキル基、アリール基、１価の複素環基またはシアノ基を示す。）

(In the formula, Ar ₉ and Ar ₁₀ each independently represent an arylene group which may have a substituent, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group, an aryl group, 1 A valent heterocyclic group or a cyano group.)

（式中、Ａｒ₁₁およびＡｒ₁₂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示し、Ａｒ₁₃は、置換基を有していてもよいアリール基であり、Ａｒ₁₁とＡｒ₁₃の間、Ａｒ₁₁とＡｒ₁₂の間、またはＡｒ₁₂とＡｒ₁₃の間に環を形成していてもよい。）

(In the formula, Ar ₁₁ and Ar ₁₂ each independently represent an arylene group which may have a substituent, Ar ₁₃ represents an aryl group which may have a substituent, and Ar ₁₁ and between Ar _13, ring may be the to form between between Ar ₁₁ and Ar _12, or Ar ₁₂ and Ar _13,.)

（式中、Ａｒ₁₄は、置換基を有していてもよいアリーレン基を示し、Ａｒ₁₇およびＡｒ₁₈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であり、Ａｒ₁₄とＡｒ₁₇の間、Ａｒ₁₄とＡｒ₁₈の間、またはＡｒ₁₇とＡｒ₁₈の間に環を形成していてもよい。）

(In the formula, Ar ₁₄ represents an arylene group which may have a substituent, Ar ₁₇ and Ar ₁₈ are each independently an aryl group which may have a substituent, and Ar ₁₄ and between Ar _17, ring may be the to form between between Ar ₁₄ and Ar _18, or Ar ₁₇ and Ar _18,.)

（式中、Ａｒ₁₅は、置換基を有していてもよいアリーレン基を示し、Ａｒ₁₆は、置換基を有していてもよいアリール基を示し、Ｒ¹¹およびＲ¹²は、それぞれ独立に、水素原子、アルキル基、アリール基、１価の複素環基またはシアノ基を示す。）

(In the formula, Ar ₁₅ represents an arylene group which may have a substituent, Ar ₁₆ represents an aryl group which may have a substituent, and R ¹¹ and R ¹² are each independently , A hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group.)

In the above formulas (3) to (7), the arylene group which may have a substituent represented by Ar ₆ , Ar _{8 to} Ar ₁₂ , Ar ₁₄ and Ar ₁₅ is the same as that in the formula (1) above. , Ar ₁ is the same as the arylene group described and exemplified as Ar ₁ (however, it may not have the substituent represented by the formula (2)). From the viewpoint of ease of monomer synthesis, a phenylene group is preferred.

In the above formulas (3) to (7), the aryl group which may have a substituent represented by Ar ₇ , Ar ₁₃ and Ar _{16 to} Ar ₁₈ is the same as that in the above-mentioned arylene group (the above formulas 1 to 1). 38, A to I, K) is the same as the aryl group in what is described and exemplified as R).

In the above formulas (3) to (7), the alkyl group, aryl group, and monovalent heterocyclic group represented by R ^{9 to} R ¹² are the same as those in the arylene group (the above formulas 1 to 38, A to I). And the same as the alkyl group, aryl group and monovalent heterocyclic group described and exemplified as R).

In the above formulas (3) to (7), Ar _{6 to} Ar ₁₈ are 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, It may have a substituent such as an arylalkenyl group, arylalkynyl group, arylamino group, monovalent heterocyclic group or cyano group.

  Specific examples of the divalent aromatic amine group include the following groups.

  In the examples of these divalent aromatic amine groups (the above formulas 118 to 122), R is described and exemplified in the above-mentioned arylene group (as R in the above formulas 1 to 38, A to I and K). Is the same.

Among the Ar _1, the following formula (8):

（式中、Ｒ¹³は、前記式（２）で示される基、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価の複素環基またはシアノ基を表し、あるいは複数あるＲ¹³は結合して芳香環または非芳香環を形成していてもよい。複数あるＲ¹³は同一であっても異なっていてもよい。但し、該式（８）は少なくとも１個の前記式（２）で示される基を有する。）
で示される２価の基；下記式（９）：

Wherein R ¹³ is a group represented by the formula (2), a hydrogen atom, 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 aryl It represents an alkoxy group, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group, or a plurality of R ¹³ may be bonded to form an aromatic ring or a non-aromatic ring. A plurality of R ¹³ may be the same or different, provided that the formula (8) has at least one group represented by the formula (2).
A divalent group represented by the following formula (9):

（式中、Ｒ¹³は前記と同じである。但し、該式（９）は少なくとも１個の前記式（２）で示される基を有する。）
で示される２価の基が好ましく、前記式（８）で示される２価の基がより好ましい。

(In the formula, R ¹³ is the same as described above, provided that the formula (9) has at least one group represented by the formula (2).)
A divalent group represented by the formula (8) is preferred, and a divalent group represented by the formula (8) is more preferred.

From the viewpoint of heat resistance, a benzofluorene-diyl group (for example, a group represented by the above formulas G, H, I, K) in which a plurality of R ¹³ are bonded to form an aromatic ring in the formula (8). It is particularly preferred.

In the formula (8) and (9), the group represented by R ^13, if not form an aromatic ring R ¹³ are bonded to, specifically, in terms of the arylene group (above formulas 1-38 , A to I, K) are the same as described and exemplified as R). Moreover, when R < ¹³ > couple | bonds and forms an aromatic ring or a non-aromatic ring, this aromatic ring and a non-aromatic ring may be substituted by the group etc. which are shown by said Formula (2).

In the above formula (1), X _1, -CR ¹ = CR ² - or -C≡C- represents, -CR ¹ = CR ² - is preferable from the standpoint of stability. N is 0 or 1, and 0 is preferable from the viewpoint of photooxidation stability.

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. These alkyl group, aryl group and monovalent heterocyclic group are the alkyl group and aryl group in those described and exemplified as R (in the above formulas 1 to 38, A to I and K) in the above-mentioned arylene group section. The same as a monovalent heterocyclic group.

In the formula (2), Ar ₂ is the same group as described and exemplified as Ar ₁ , but Ar ₂ may not have the substituent represented by the formula (2). In view of the ease of monomer synthesis, Ar ₂ is preferably a phenylene group.

In the formula (2), Ar ₅ represents a direct bond, an arylene group, a divalent heterocyclic group or a divalent aromatic amine group. These arylene group, divalent heterocyclic group and divalent aromatic amine group are the same groups as described and exemplified as Ar ₁ , but Ar ₅ has a substituent represented by the formula (2). You don't have to.

In the formula (2), R ³ and R ⁴ are each independently a direct bond, —R ⁵ —, —O—R ⁵ —, —R ⁵ —O—, —R ⁵ —C (O) O—. ^{, -R 5 -OC (O) -} , - R 5 -N (R 6) -, - O -, - S -, - C (O) O -, - C (O) -, - CR 7 = CR ⁸ represents-or -C≡C-, R ⁵ represents an alkylene group or an alkenylene group, and R ⁶ represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. However, when Ar ₅ is a direct bond, R ³ is a direct bond. Examples of the alkylene group represented by R ⁵ include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, 2-ethylhexylene group, nonylene group, decylene group, 3,7-dimethyloctylene group, laurylene group, etc. are mentioned, and pentylene group, hexylene group, heptylene group, octylene group, 2-ethylhexylene group, nonylene group, decylene group, 3,7-dimethyloctylene group are included. preferable. Examples of the alkenylene group include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octynylene group, a 2-ethylhexynylene group, and a 3,7-dimethyloctynylene group. R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. The alkyl group, aryl group and monovalent heterocyclic group represented by R ⁶ , R ⁷ and R ⁸ are described as R (in the above formulas 1 to 38, A to I and K) in the above-mentioned arylene group. This is the same as the alkyl group, aryl group and monovalent heterocyclic group in the examples.

In the formula (2), Ar ₃ and Ar ₄ each independently represents an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine group. Ar ₃ and Ar ₄ may have a substituent. Examples of the substituent that Ar ₃ and Ar ₄ may have include, for example, 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, and an arylalkenyl group. Group, arylalkynyl group, arylamino group, monovalent heterocyclic group and the like. These substituents are specifically alkyl groups, alkoxy groups, alkylthio groups in R (of the above formulas 1 to 38, A to I, and K) described and exemplified in the section of the divalent arylene group. , Alkylsilyl group, alkylamino group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group and arylamino group. The aryl group and monovalent heterocyclic group are as follows.

The aryl group represented by Ar ₃ and Ar ₄ usually has about 6 to 60 carbon atoms. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, a triphenyl group, a pyrenyl group, a fluorenyl group, a benzofluorenyl group, a stilbenyl group, and a distilbenyl group. . Among these, a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, a benzofluorenyl group, a stilbenyl group, and a distilbenyl group are preferable, and a phenyl group is more preferable in terms of ease of monomer synthesis. .

The monovalent heterocyclic group represented by Ar ₃ and Ar ₄ means the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound. The monovalent heterocyclic group usually has about 2 to 60 carbon atoms (note that the carbon number does not include the carbon number of the substituent). In addition, the heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus and boron in the ring. means. Specific examples of the monovalent heterocyclic group include the following.

a) A monovalent heterocyclic group containing nitrogen as a hetero atom, such as pyridinyl group, diazaphenyl group, quinolinyl group, quinoxalinyl group, acridinyl group, bipyridinyl group, phenanthroline-yl group.

  b) a group containing silicon, nitrogen, oxygen, sulfur, selenium or the like as a hetero atom and having a fluorene structure (the group represented by the above formulas 79 to 93, wherein one of the two bonds is R) .

  c) 5-membered ring heterocyclic group containing silicon, nitrogen, oxygen, sulfur, selenium or the like as a hetero atom (a group represented by the above formulas 94 to 98, wherein one of the two bonds is R) ).

  d) a 5-membered condensed heterocyclic group containing silicon, nitrogen, oxygen, sulfur, selenium, etc. as a heteroatom (a group represented by the above formulas 99 to 108, wherein one of the two bonds is R some stuff).

  e) a 5-membered ring heterocyclic group containing sulfur as a heteroatom and bonded in the α-position of the heteroatom to form a two-bodies or an oligomer (groups represented by the above formulas 109 to 110, 2 One of the bonding hands is R).

  f) A group (a group represented by the above formulas 111 to 117) which is a 5-membered heterocyclic group containing silicon, nitrogen, oxygen, sulfur, selenium or the like as a hetero atom and bonded to the phenyl group at the α-position of the hetero atom. And one of the two bonds is R).

Furthermore, the monovalent heterocyclic group represented by Ar ₃ or Ar ₄ includes, for example, a group derived from a triplet light-emitting complex and the like, and includes a monovalent complex group (for example, as shown below) Monovalent metal complex group, etc.).

The “monovalent aromatic amine group” represented by Ar ₃ and Ar ₄ means the remaining atomic group obtained by removing one hydrogen atom from the aromatic amine. The monovalent aromatic amine group usually has about 4 to 60 carbon atoms (the carbon number does not include the carbon number of the substituent). Specific examples of the monovalent aromatic amine group include groups represented by the following formulas 123 to 127.

  In the examples of these monovalent aromatic amine groups (the above formulas 123 to 127), R is described and exemplified in the above-mentioned arylene group (as R in the above formulas 1 to 38, A to I and K). However, it may not have the substituent represented by the formula (2).

  In the formula (2), Y represents the following formula:

、または

Or

を表す。

Represents.

  Specific examples of the group represented by the formula (2) include the following.

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

  In the polymer compound of the present invention, the total of repeating units represented by the formula (1) is usually 1 mol% or more and 100 mol% or less of all repeating units of the polymer compound. From the viewpoint of the fluorescence intensity of the polymer compound, it is preferably 2 mol% or more and 50 mol% or less, and more preferably 5 mol% or more and 50 mol% or less of all repeating units of the polymer compound.

The polymer compound of the present invention includes a repeating unit represented by the following formula (10) in addition to the repeating unit represented by the above formula (1), from the viewpoint of solubility and film formability of the polymer compound. To preferred.
_{- [Ar 19 - (X 2} ) p] - (10)
[In the formula, Ar ₁₉ represents an arylene group, a divalent heterocyclic group, a divalent aromatic amine group or a divalent aromatic phosphine group, and X ₂ represents —CR ¹⁴ = CR ¹⁵ — (where , R ¹⁴ and R ¹⁵ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group.) Or —C≡C—, and p represents 0 or 1. ]

In the formula (10), the arylene group represented by Ar ₁₉ , the divalent heterocyclic group, and the divalent aromatic amine group are the same as those described and exemplified as Ar ₁ , but have a substituent. In this case, the substituent is 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. A monovalent heterocyclic group or a cyano group. In other words, the substituent is not represented by the formula (2) and does not contain a phosphorus atom.

In the formula (10), the divalent aromatic phosphine group represented by Ar ₁₉ means the remaining atomic group obtained by removing two hydrogen atoms from the aromatic phosphine. The divalent aromatic phosphine group generally has about 4 to 60 carbon atoms (the carbon number does not include the carbon number of the substituent). Examples of the divalent aromatic phosphine group include groups represented by the following formulas 200 to 203.

In these examples of the divalent aromatic phosphine group (the above formulas 200 to 203), R ^** is an arylene group represented by Ar ₁₉ , a divalent heterocyclic group, or a substitution of a divalent aromatic amine group. Same as group. Among these, the group represented by the above formula 200 is preferable from the viewpoint of ease of monomer synthesis.

Ar ₁₉ is 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, monovalent group The heterocyclic group may have a substituent of a cyano group. When Ar ₁₉ has a plurality of substituents, they may be the same or different. Details of these substituents are other than the groups represented by the above formula (2) among those specifically explained and exemplified as R in the above-described examples of the arylene group (the above formulas 1 to 38, A to K). Is the same.

Ar ₁₉ is preferably an arylene group or a divalent heterocyclic group from the viewpoint of the fluorescence intensity of the polymer compound. Among these, a phenylene group, a naphthalenediyl group, a biphenylene group, a fluorene-diyl group (the above formulas 36 to 38), a stilbene-diyl group (the above formulas A to D), a distilbene-diyl group (the above formulas E and F), Benzofluorene-diyl group (the above formulas G, H, I, K), a group containing silicon, nitrogen, oxygen, sulfur, selenium or the like as a hetero atom and having a fluorene structure (the above formulas 79 to 93), sulfur as a hetero atom A 5-membered ring heterocyclic group containing a dimer or oligomer by bonding at the α-position of the hetero atom (the above formulas 109 to 110), as a hetero atom, silicon, nitrogen, oxygen, sulfur, A 5-membered ring heterocyclic group containing selenium or the like and a group bonded to the phenyl group at the α-position of the hetero atom (the above formulas 111 to 117) is more preferable.

（式中、ＸはＡ環上の２個の原子とＢ環上の２個の原子と一緒になって５員環又は６員環を形成する原子又は２価の基を表し、Ｒ^aは置換基を表し、ｍは独立に０〜５の整数を表し、ｎは独立に０〜３の整数を表す。Ｒ^a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。）
のいずれかで示される２価の基がより好ましい。 Among Ar ₁₉ , from the viewpoint of heat resistance and fluorescence intensity of the polymer compound, the following formulas (2a) to (2d):

(Wherein, X represents two atoms and B atoms to form two 5-membered or 6-membered ring together with the atoms on the ring or a divalent group of the A ring, R ^a is Represents ^a substituent, m independently represents an integer of 0 to 5, and n independently represents an integer of 0 to 3. When ^a plurality of R ^a are present, they may be the same or different. Good.)
A divalent group represented by any of the above is more preferred.

In the formulas (2a) to (2d), examples of the divalent group represented by X include -C (R ¹⁸ ) (R ¹⁹ )-, -C (R ²⁰ ) (R ²¹ )- C (R ²² ) (R ²³ )-, -O-, -S-, -SO _2- , -Se-, -Te-, -N (R ²⁴ )-, -Si (R ²⁵ ) (R ²⁶ ) -C (R ¹⁸ ) (R ¹⁹ )-, -C (R ²⁰ ) (R ²¹ ) -C (R ²² ) () from the viewpoint of ease of synthesis of the polymer compound and fluorescence intensity. R ²³ ) —, —O—, —S—, and —N (R ²⁴ ) — are preferred. Here, R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryl An oxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group is shown. These groups are the same as those explained and exemplified in the above-mentioned arylene group (as R in the above formulas 1 to 38, A to I and K). However, the substituent shown by Formula (2) is not included. R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. Here, the alkyl group, aryl group, arylalkyl group, and monovalent heterocyclic group represented by R ²⁴ , R ²⁵ , and R ²⁶ are the same as those in the arylene group (the above formulas 1 to 38, A to I, The same as described and exemplified (as R for K).

In the above formulas (2a) to (2d), the substituent represented by R ^a is the same as described and exemplified in the above-mentioned arylene group (as R in the above formulas 1 to 38, A to I and K). It is. However, the substituent shown by Formula (2) is not included.

（式中、Ｒは、前記と同じである。但し、Ｒは前記式（２）で示される基ではない。）
等が挙げられ、高分子化合物の蛍光強度の観点からは、

（式中、Ｒは、前記と同じである。但し、Ｒは前記式（２）で示される基ではない。）
が好ましい。 As the repeating unit represented by the formulas (2a) to (2d), for example,

(In the formula, R is the same as defined above, provided that R is not a group represented by the formula (2).)
From the viewpoint of the fluorescence intensity of the polymer compound,

(In the formula, R is the same as defined above, provided that R is not a group represented by the formula (2).)
Is preferred.

（式中、Ｒは、前記と同じである。但し、Ｒは前記式（２）で示される基ではない。）
が特に好ましい。 Among these,

(In the formula, R is the same as defined above, provided that R is not a group represented by the formula (2).)
Is particularly preferred.

  In the above formula, one structural formula has a plurality of Rs, which may be the same or different. In the above formula, the group represented by R is the same as described and exemplified in the above-mentioned arylene group (as R in the above formulas 1 to 38, A to I and K). However, the substituent represented by the formula (2) is not included.

In the formula (10), X ₂ is -CR ¹⁴ = CR ¹⁵ - represents or -C≡C-, -CR ¹⁴ = CR ¹⁵ - is preferable from the standpoint of stability. R ¹⁴ and R ¹⁵ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. p represents 0 or 1; From the viewpoint of photooxidation stability of the polymer compound, p is preferably 0.

R ¹⁴ and R ¹⁵ are the same as those described and exemplified for R ¹ and R ² above.

  In addition, 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 (10) within a range not impairing the fluorescence property and the charge transport property. Also good.

  In a preferred embodiment of the present invention, the polymer compound is substantially composed of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (10). Here, “substantially” means that in the polymer compound of the present invention, the total of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (10) is 50 with respect to all repeating units. Means 100 mol%, preferably 80-100 mol%, more preferably 90-100 mol%.

  As a specific example of the polymer compound of this preferred embodiment, as a repeating unit represented by the formula (1), the following formula:

から選ばれる１種類以上と、前記式（１０）で示される繰り返し単位として、下記式：

As one or more types selected from the above and the repeating unit represented by the formula (10), the following formula:

から選ばれる１種類以上との共重合体が挙げられる。

And a copolymer with at least one selected from the group consisting of

  In the exemplification of those substantially consisting of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (10), R represents the above-mentioned arylene group (the above formulas 1 to 38, A to I). The same as those described and exemplified as R in K) (provided that R in the examples exemplified as the repeating unit represented by the formula (10) does not include the substituent represented by the formula (2)). is there.

  Among the polymer compounds containing the repeating unit represented by the formula (1) and the repeating unit represented by the formula (10), the repeating unit represented by the formula (1) and the repetition represented by the formula (10) The total of the units is 50 mol% or more of the total repeating units of the polymer compound, and the total of the repeating units represented by the formula (1) and the formula (10) From the viewpoint of heat resistance, the repeating unit represented by the formula (1) is preferably 2 mol% or more and 90 mol% or less.

-Characteristics of polymer compounds-
The polymer compound of the present invention preferably has a polystyrene-equivalent number average molecular weight of 1 × 10 ³ to 1 × 10 ⁸ , and more preferably 2 × 10 ³ to 1 × 10 ⁷ . The polymer compound of the present invention preferably has fluorescence and / or phosphorescence in the solid state.

  In the polymer compound of the present invention, when a group (usually referred to as polymerization active group) involved in polymerization remains in a group located at the molecular chain terminal (that is, terminal group), the polymer compound is converted into a light emitting device. Since the light emission characteristics and the lifetime when used in the case may be reduced, they may be protected with a stable group not involved in polymerization. The terminal group preferably has a conjugated bond continuous with the substantial conjugated structure of the molecular chain main chain. Further, for example, a structure in which an aryl group or a heterocyclic group is bonded via a vinylene group may be used. Specific examples include substituents described in Chemical formula 10 of JP-A-9-45478.

  In the polymer compound of the present invention, the molecular chain main chain is generally substantially conjugated. In the present specification, “substantially conjugated” means usually 50 to 100 mol%, preferably 80 to 100 mol%, more preferably based on all repeating units constituting the molecular chain main chain. It means that 90 to 100 mol% of repeating units constitute a conjugated system of the molecular chain main chain.

  Moreover, the repeating unit may be connected with a vinylene group and a non-conjugated part, or the repeating unit may contain a vinylene group and a non-conjugated part. Examples of the bonding structure including the non-conjugated moiety include those shown below, a combination of the following and a vinylene group, and a combination of two or more of the following.

In the examples of the bond structure containing these non-conjugated moieties, R ^* represents the same group as R ′. Ar represents a hydrocarbon group having 6 to 60 carbon atoms (specifically, for example, a group in which a hydrogen atom such as benzene, biphenyl, terphenyl, naphthalene, or anthracene is a bond).

  The polymer compound of the present invention may be any of a random copolymer, a block copolymer, or a graft copolymer, or a polymer having an intermediate structure thereof, for example, a random having a block property. A copolymer may also be used. From the viewpoint of obtaining a polymer compound having high fluorescence intensity, a random copolymer, block copolymer or graft copolymer having a block property is preferable to a complete random copolymer. The polymer compound of the present invention includes a dendrimer or the like when the main chain is branched and there are three or more terminal portions.

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

-Method for producing polymer compound-
Next, the method for producing a polymer compound of the present invention includes the case where the polymer compound has (i) a vinylene group in the main chain (that is, n = 1 in the above formula (1)), and (ii) ) The case where no vinylene group is present (that is, in the case of n = 0 in the above formula (1)) will be described separately.

  (i) As a production method when the polymer compound of the present invention has a vinylene group in the main chain, for example, the method described in JP-A-5-202355 can be mentioned. 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 atom, or a vinyl group Polymerization of a compound having a halogen group by Heck reaction, polymerization 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 by the Horner-Wadsworth-Emmons method, halogenation Polycondensation of a compound having two or more methyl groups by dehydrohalogenation method, polycondensation of a compound having two or more sulfonium bases by sulfonium salt decomposition method, formation of aldehyde group Examples include a method such as polymerization by a Knoevenagel reaction of a compound having an acetonitrile group and a compound having an aldehyde group and an acetonitrile group, and a method such as polymerization by a McMurry reaction of a compound having two or more aldehyde groups. Is done. These reactions are preferably performed in an inert atmosphere such as nitrogen gas or argon gas.

(ii) In the case where the main chain does not have a vinylene group, for example, a method of polymerizing from a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a Ni (0) catalyst, FeCl ₃ or the like Examples thereof include a method of polymerizing with an oxidizing agent, a method of electrochemically oxidatively polymerizing, a method of decomposing an intermediate polymer having an appropriate leaving group, and the like. These reactions are preferably performed in an inert atmosphere such as nitrogen gas or argon gas.

  Among these, polymerization by Wittig reaction, polymerization by Heck reaction, polymerization by Horner-Wadsworth-Emmons method, polymerization by Knoevenagel reaction, polymerization method by Suzuki coupling reaction, polymerization method by Grignard reaction, Ni (0) catalyst The method of polymerizing is preferable because the structure can be easily controlled.

  Specifically, a compound having a plurality of reactive groups as a monomer can be dissolved in an organic solvent as necessary, and reacted with an alkali or an appropriate catalyst at a temperature not lower than the melting point of the organic solvent and not higher than the boiling point. it can. For example, “Organic Reactions”, Vol. 14, pages 270-490, John Wiley & Sons, Inc., 1965, “Organic Reactions”, Vol. 27, 345-390, John Wiley & Sons, Inc., 1982, "Organic Synthesis", Collective Volume VI, 407-411, John Wiley and Sons (407-411). John Wiley & Sons, Inc.), 1988, Chem. Rev., 95, 24. 7 (1995), Journal of Organometallic Chemistry (J. Organomet. Chem.), 576, 147 (1999), Journal of Practical Chemistry (J. Prakt. Chem.), 336, 247 (1994), Macromolecular Chemistry Macromolecular Symposium (Macromol. Chem., Macromol. Symp.), Vol. 12, p. 229 (1987), etc. can be used.

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

  In order to accelerate the reaction, an alkali and an appropriate catalyst are added as appropriate. These may be selected according to the reaction used. These alkalis and catalysts are preferably those that are sufficiently soluble in the solvent used in the reaction. As a method of mixing the alkali and catalyst, slowly add the alkali or catalyst solution while stirring the reaction solution under an inert atmosphere such as argon or nitrogen, or slowly add the reaction solution to the alkali or catalyst solution. The method of adding is illustrated.

  The reaction conditions will be described more specifically. In the case of Wittig reaction, Horner reaction, Knoevenagel reaction, etc., the reaction is carried out using an equivalent or more, preferably 1 to 3 equivalents of alkali with respect to the reactive group of the monomer. Examples of the alkali include, but are not limited to, metal alcoholates such as potassium tert-butoxide, sodium tert-butoxide, sodium ethylate and lithium methylate, hydride reagents such as sodium hydride, and amides such as sodium amide. Etc. can be used. As the solvent, N, N-dimethylformamide, tetrahydrofuran, dioxane, toluene and the like are used. The reaction can be allowed to proceed at a reaction temperature of usually from room temperature to about 150 ° C. The reaction time is, for example, 5 minutes to 40 hours, but may be any time that allows sufficient polymerization to proceed, and it is not necessary to leave the reaction for a long time after the reaction is completed. is there. 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 using a palladium catalyst in the presence of a base such as triethylamine. A solvent having a relatively high boiling point such as N, N-dimethylformamide and 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 the Suzuki coupling reaction, for example, palladium [tetrakis (triphenylphosphine)], palladium acetates, etc. are used as a catalyst, inorganic bases such as potassium carbonate, sodium carbonate, barium hydroxide, and organic bases such as triethylamine. In addition, an inorganic salt such as cesium fluoride is added in an equivalent amount or more, preferably 1 to 10 equivalents, with respect to the monomer. An inorganic salt may be used as an aqueous solution and reacted in a two-phase system. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. Although it depends on the solvent, a temperature of about 50 to 160 ° C. is suitably selected. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 1 hour to 200 hours.

  In the case of the Grignard reaction, a halide and metal Mg are reacted in an ether solvent such as tetrahydrofuran, diethyl ether, dimethoxyethane or the like to form a Grignard reagent solution, which is mixed with a separately prepared monomer solution, and nickel or An example is a method in which a palladium catalyst is added while paying attention to excess reaction, and then reacted while heating to reflux. The Grignard reagent is used in an equivalent amount or more, preferably 1 to 1.5 equivalents, more preferably 1 to 1.2 equivalents, relative to the monomer. Also in the case of polymerizing by a method other than these, the reaction can be carried out according to a known method.

  When using a zero-valent nickel complex, in an ether solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran or 1,4-dioxane, or an aromatic hydrocarbon solvent such as toluene. The method of making a halide react using a zerovalent nickel complex is illustrated. Examples of the zero-valent nickel complex include bis (1,5-cyclooctadiene) nickel (0), (ethylene) bis (triphenylphosphine) nickel (0), tetrakis (triphenylphosphine) nickel, and the like. (1,5-cyclooctadiene) nickel (0) is preferred.

  When using a zerovalent nickel complex, it is preferable to add a compound that becomes a neutral ligand from the viewpoint of improving the yield of the polymer compound and increasing the molecular weight. A neutral ligand is a ligand having no anion or cation. Specific examples of the compound serving as a neutral ligand include compounds serving as nitrogen-containing ligands such as 2,2′-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline, N, N′-tetramethylethylenediamine; Examples include compounds that serve as third phosphine ligands such as triphenylphosphine, tolylphosphine, tributylphosphine, and triphenoxyphosphine, and compounds that serve as nitrogen-containing ligands are preferred in terms of versatility and low cost. 2'-bipyridyl is particularly preferable in terms of high reactivity and high yield.

  In particular, from the viewpoint of increasing the molecular weight of the polymer, there is a system in which 2,2′-bipyridyl is added as a compound serving as a neutral ligand to a system containing bis (1,5-cyclooctadiene) nickel (0). preferable.

  The amount of the zero-valent nickel complex is not particularly limited as long as it does not inhibit the polymerization reaction, but if it is too small, the polymerization reaction time becomes long, while if it is too much, post-treatment becomes difficult. Therefore, it is 0.1 mol or more, preferably 1 mol or more with respect to 1 mol of the monomer. If the amount used is too small, the molecular weight tends to be small. The upper limit is not limited, but if the amount is too large, post-treatment tends to be difficult, so 5.0 mol or less is preferable.

  Moreover, when using the compound used as a neutral ligand, the usage-amount is normally about 0.5-10 mol with respect to 1 mol of zerovalent nickel complexes, but cost performance (high From the viewpoint of yield and inexpensive input amount), 0.9 mol to 1.1 mol is preferable. Also in the case of polymerizing by a method other than these, the reaction can be carried out according to a known method.

  A method of polymerizing with a Ni (0) catalyst is particularly preferred because of the availability of raw materials and the simplicity of the polymerization reaction operation.

-Luminescent material-
The polymer compound of the present invention is useful as a light emitting material. That is, the light emitting material of the present invention comprises the polymer compound. If necessary, the light emitting material may contain components other than the polymer compound (for example, a light emitting material other than the polymer compound, a hole transport material, an electron transport material, etc.).

-Applications of polymer compounds-
The polymer compound of the present invention is useful as, for example, an organic semiconductor material, an optical material, and the like in addition to the light emitting material. Furthermore, it can also be used as a conductive material by doping.

  When the polymer compound of the present invention is used as a light-emitting material (for example, a light-emitting material of a polymer light-emitting device), the purity affects the light-emitting characteristics. Polymerization is preferably performed after purification by the above method, and after the synthesis, purification treatment such as reprecipitation purification and fractionation by chromatography is preferably performed.

<Liquid composition>
The liquid composition of the present invention contains the polymer compound and a solvent. The liquid composition may contain the polymer compound of the present invention. Specific examples thereof 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 Derivatives, poly (benzofluorene vinylene) and its derivatives, poly (dibenzofuranvinylene) and its derivatives, and the like.

  The liquid composition of the present invention is useful for production of light-emitting elements such as polymer light-emitting elements and organic transistors. 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 luminescent metal complexes, aromatic amines, tetraphenylcyclopentadiene, tetraphenylcyclopentadiene Derivative, tetraphenylcyclobutadiene, tetraphenylcyclobutadiene derivative, stilbene, silicon-containing aromatic, oxazole, furoxan, thiazole, tetraarylmethane, thiadiazole, pyrazole, metacyclophane, Emitting 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.

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

  The ratio of the solvent in the liquid composition is usually 1% by weight to 99.9% by weight, preferably 60% by weight to 99.9% by weight, and more preferably 90% by weight with respect to the total weight of the liquid composition. % By weight to 99.8% by weight. The viscosity of the liquid composition varies depending on the printing method, but it is preferably in the range of 0.5 to 500 mPa · s at 25 ° C. 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 less than 180 ° C. 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 less than 180 ° C. 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 contains 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. This organic transistor includes the polymer compound of the present invention.

  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. As a film-forming method from a solution obtained by dissolving an organic solvent-soluble polymer compound in a solvent, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating Application methods such as a method, a dip coating method, a spray 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 after the production of the polymer field-effect transistor until sealing, without exposing it to the atmosphere (for example, in a dry nitrogen gas atmosphere or in a vacuum).

-Organic solar cells-
Next, an organic solar cell will be described. This organic solar cell includes the polymer compound of the present invention. 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).

<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 includes an electrode composed of an anode and a cathode, and a light emitting layer provided between the electrodes and having the polymer compound. The polymer light-emitting device of the present invention further includes a polymer light-emitting device in which an electron transport layer is provided between the cathode and the light-emitting layer; and a polymer in which a hole transport layer is provided between the anode and the light-emitting layer. A light emitting element; and a polymer light emitting element in which an electron transport layer is further provided between the cathode and the light emitting layer, and a hole transport layer is provided between the anode and the light emitting layer.

Examples of the specific structure of the polymer light-emitting device of the present invention include the following a) to d).
a) Anode / light emitting layer / cathode b) Anode / hole transport layer / light emitting layer / cathode c) Anode / light emitting layer / electron transport layer / cathode d) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (Here, / indicates that each layer is laminated adjacently, and so on.)

  The “light emitting layer” is a layer having a function of emitting light. The “hole transport layer” is a layer having a function of transporting holes. The “electron transport layer” is a layer having a function of transporting electrons. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. These light emitting layer, hole transporting layer, and electron transporting layer may be independently one layer or two or more layers.

  Although there is no restriction | limiting in the film-forming method of a light emitting layer, For example, the method by the film-forming from a solution is mentioned. The “method by film formation from a solution” applied to the formation of a light emitting layer is a solution obtained by dissolving the polymer compound of the present invention in a solvent such as toluene, xylene, mesitylene, decalin, limonene or the like. The film is formed by coating by the following coating method.

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

  When forming a film from a solution using the polymer compound of the present invention when preparing a polymer light-emitting device, it is only necessary to remove the solvent by drying after applying the obtained solution, and charge transport materials and light-emitting materials Since the same method can be applied to the case of mixing, it is very advantageous in production.

  The film thickness of the light emitting layer varies depending on the material used, and may be adjusted so that the driving voltage and the light emission efficiency become the desired values. For example, the 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 in the light emitting layer. In addition, 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 such as a low molecular compound can be used. Examples of the low molecular weight compound include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine-based, xanthene-based, coumarin-based, cyanine-based pigments, 8-hydroxyquinoline or metal complexes of derivatives thereof, aromatics, and the like. Examples include amine, tetraphenylcyclopentadiene or a derivative thereof, and tetraphenylbutadiene or a derivative thereof. Specifically, for example, known ones such as those described in JP-A-57-51781 and 59-194393 can be used.

  Furthermore, as the light emitting material, a metal complex that emits light from a triplet excited state (a triplet light emitting complex: for example, phosphorescent light emission or a complex in which fluorescent light emission is observed in addition to the phosphorescent light emission) is included. Those conventionally used as low-molecular EL light-emitting materials can also be used. These triplet light-emitting complexes are described in, for example, Nature, (1998), 395, 151, Appl. Phys. Lett. (1999), 75 (1), 4, Proc. SPIE-Int. Soc. Opt. Eng. ), 4105 (Organic Light-Emitting Materials and Devices IV), 119, J. Am. Chem. Soc., (2001), 123, 4304, Appl. Phys. Lett., (1997), 71 (18), 2596, Syn. Met., (1998), 94 (1), 103, Syn. Met., (1999), 99 (2), 1361, Adv. Mater., (1999), 11 (10), 852 etc. Has been.

  When the polymer light-emitting device of the present invention has a hole transport layer (usually, the hole transport layer contains a low-molecular or high-molecular hole transport material), Polyvinylcarbazole or derivative thereof, polysilane or derivative thereof, polysiloxane derivative having aromatic amine in the side chain or main chain, pyrazoline derivative, arylamine derivative, stilbene derivative, triphenyldiamine derivative, polyaniline or derivative thereof, polythiophene or derivative thereof , Polypyrrole or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, or poly (2,5-thienylenevinylene) or a derivative thereof. Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992, Examples thereof include a hole transport material described in JP-A-3-152184.

  Among these, as the hole transport material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, polyaniline or a derivative thereof, Polymeric hole transport materials such as polythiophene or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thienylene vinylene) or derivatives thereof are preferred, polyvinyl carbazole or derivatives thereof, polysilane or derivatives thereof More preferred are derivatives, polysiloxane derivatives having aromatic amines in the side chain or main chain. When the hole transport material used is a low molecule, it is preferable to use the hole transport material dispersed in a polymer binder.

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

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

  Since polysiloxane or a derivative thereof has almost no hole transporting property in the siloxane skeleton structure, a polysiloxane or a derivative thereof having a low molecular structure in the hole transporting material in the side chain or main chain is preferably used. Particularly, those having a hole transporting aromatic amine compound group 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, When using a 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 using a polymer hole transport material, a method by film formation from a solution is exemplified.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transport material and / or a polymer binder. Examples of the solvent include chloro solvents such as chloroform, methylene chloride, 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. Examples thereof include ester solvents such as ethyl cellosolve acetate.

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

  As the polymer binder, those that do not extremely inhibit charge transport are preferable, and those that do not strongly absorb visible light are preferably used. 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 varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  When the polymer light-emitting device of the present invention has an electron transport layer (usually, the electron transport layer contains a low-molecular or high-molecular electron transport material), known electron transport materials are used. Oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, Examples include diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline or its derivatives, polyquinoline or its derivatives, polyquinoxaline or its derivatives, polyfluorene or its derivatives, and the like. Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992, Examples thereof include an electron transport material described in JP-A-3-152184.

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

  The method for forming the electron transport layer is not particularly limited, but when a low molecular electron transport material is used, a vacuum deposition method from powder, or a method by film formation from a solution or a molten state is exemplified. In the case of using a polymer electron transport material, a method by film formation from a solution or a molten state is exemplified. In film formation from a solution or a molten state, a polymer binder may be used in combination.

  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, Examples include ester solvents such as ethyl cellosolve acetate.

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

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

  The film thickness of the electron transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the film thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

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

  Further, in order to improve adhesion with the electrode and charge injection from the electrode, the charge injection layer or the insulating layer (usually 0.5 mm to 4 mm in average film thickness, which is adjacent to the electrode, hereinafter the same) In addition, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer in order to improve the adhesion at the interface or prevent mixing.

  The order and number of layers to be stacked, and the thickness of each layer may be adjusted as appropriate 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.

Specific examples of the structure of the polymer light-emitting device of the present invention include the following e) to p).
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 an ionization potential of a value, a layer provided between a cathode and an electron transport layer, and a layer containing a material having an electron affinity of an intermediate value between the cathode material and the electron transport material contained in the electron transport layer, etc. Is mentioned.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less. in order to reduce the current, more preferably less 10 ^-5 S / cm or more and 10 ² S / cm, more preferably less 10 ^-5 S / cm or more and 10 ¹ S / cm.

Usually, the conductive polymer is doped with an appropriate amount of ions in order to set the electric conductivity of the conductive polymer to 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less.

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

  The 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. Specifically, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof , Polythienylene vinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanine (such as copper phthalocyanine), carbon Etc. are exemplified.

  The insulating layer has a function of facilitating charge injection. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. Examples of the polymer light emitting device provided with the insulating layer include a polymer light emitting device provided with an insulating layer adjacent to the cathode and a polymer light emitting device provided with an insulating layer adjacent to the anode.

Specific examples of the polymer light-emitting device of the present invention include the following q) to ab).
q) anode / insulating layer / light emitting layer / cathode r) anode / light emitting layer / insulating layer / cathode s) anode / insulating layer / light emitting layer / insulating layer / cathode t) anode / insulating layer / hole transport layer / light emitting layer / Cathode u) anode / hole transport layer / light emitting layer / insulating layer / cathode v) anode / insulating layer / hole transport layer / light emitting layer / insulating layer / cathode w) anode / insulating layer / light emitting layer / electron transport layer / Cathode x) anode / light emitting layer / electron transport layer / insulating layer / cathode y) anode / insulating layer / light emitting layer / electron transport layer / insulating layer / cathode z) anode / insulating layer / hole transport layer / light emitting layer / Electron transport layer / cathode aa) anode / hole transport layer / light emitting layer / electron transport layer / insulating layer / cathode ab) anode / insulating layer / hole transport layer / light emitting layer / electron transport layer / insulating layer / cathode

  The 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 glass, plastic, polymer film, and silicon substrate. The 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 of the anode, for example, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film made of conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of a method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. Further, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.

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

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

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

  Although the film thickness of a cathode can be suitably adjusted in consideration of electric conductivity and durability, it 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, polymers (for example, gas barrier polymers such as polyvinylidene chloride and copolymers thereof, polyester, polyacrylonitrile, aromatic polyamide, liquid crystal polyester, etc.), metal oxides, metal fluorides, metal borides Etc. can be used. Further, as the protective cover, for example, a glass plate, a plastic plate having a surface subjected to low water permeability treatment, or the like can be used. As a method for protecting the element with the protective cover, a method in which the cover is bonded to the element substrate with a thermosetting resin or a photo-curing resin and sealed is preferable. 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 one or more measures.

-Applications of polymer light emitting devices-
The polymer light-emitting device of the present invention is useful for, for example, a display device such as a planar light source, a flat panel display device, a segment display device, a dot matrix display device, a liquid crystal display device, or a backlight thereof.

  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 and a method of forming either one of the anode or the cathode or both electrodes in a pattern. By forming a pattern by any of these methods and arranging some electrodes so that they can be turned on / off independently, a segment type display element capable of displaying numbers, letters, simple symbols and the like can be obtained. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multicolor 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 driven actively in combination with TFTs. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

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

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples. The molecular weights of the compounds determined in the examples are the number average molecular weight and weight average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. The glass transition temperature (Tg) was measured by differential scanning calorimetry (DSC, trade name: DSC2920, manufactured by TA Instruments). Specifically, the sample was held at 200 ° C. for 5 minutes, then rapidly cooled to −50 ° C. and held for 30 minutes. Subsequently, after raising the temperature to 30 ° C., the measurement was performed up to 300 ° C. at a temperature rising rate of 5 ° C. per minute.

<Synthesis Example 1>
1.54 g of phosphonic acid ester obtained by reacting 2-bromomethyl-1,4-dibromobenzene with triethyl phosphite and 1.1 g of 2- (diphenylphosphino) benzaldehyde were added to 30 g of tetrahydrofuran (dehydrated). A solution prepared by previously dissolving 0.7 g of potassium tert-butoxide in 10 g of tetrahydrofuran (dehydrated) was added dropwise to the solution dissolved in After the dropping, the reaction was continued at room temperature for 10 hours. The reaction was performed in a nitrogen gas atmosphere.

After completion of the reaction, acetic acid was added to the obtained reaction solution to neutralize the reaction solution, and then poured into methanol for reprecipitation. The produced precipitate was filtered and collected. This precipitate was washed with methanol and then dried under reduced pressure to obtain 0.75 g of a monomer (PP-TPP) (specific structure is as described later).
MS (APPI (+)): (M + H) ^<+> 523

・単量体（ＰＰ−ＴＰＰ）

<Example 1>
・ Monomer (1)

・ Monomer (PP-TPP)

-Synthesis of polymer compound 1-
Monomer (1) (manufactured by JFE Chemical Co., Ltd.) 0.58 g, monomer (PP-TPP) 0.23 g and 2,2′-bipyridyl 0.66 g were charged into a reaction vessel, Replaced with nitrogen gas. To this was added 70 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. Next, 1.15 g of bis (1,5-cyclooctadiene) nickel (0) was added to the obtained mixed solution, stirred at room temperature for 10 minutes, and reacted at 60 ° C. for 3 hours. The reaction was performed in a nitrogen gas atmosphere.

After completion of the reaction, the reaction solution was cooled. Next, a mixed solution of methanol 60 ml / ion exchanged water 60 ml was poured into the obtained reaction solution and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. The obtained toluene solution was filtered to remove insoluble matters, and then the toluene solution was washed with about 1N hydrochloric acid aqueous solution, allowed to stand and liquid-separated, and then the toluene solution was recovered. The recovered toluene solution was washed with about 3% by weight aqueous ammonia, allowed to stand and liquid-separated, and then the toluene solution was recovered. Next, the recovered toluene solution was washed with ion-exchanged water, allowed to stand and separated, and then the toluene solution was recovered. Next, the recovered toluene solution was poured into methanol and purified by reprecipitation. Next, the produced precipitate was collected and washed with methanol, and then this precipitate was dried under reduced pressure to obtain 0.07 g of a polymer. This polymer is referred to as polymer compound 1. The obtained polymer compound 1 had a polystyrene equivalent weight average molecular weight of 1.5 × 10 ⁴ and a number average molecular weight of 7.7 × 10 ³ . Moreover, the glass transition temperature (Tg) was 71 degreeC.

  The structure of the repeating unit contained in the polymer compound 1 estimated from the preparation is shown below. The polymer compound 1 is composed of a molar ratio of repeating unit A: repeating unit B = 7: 3 (estimated value from preparation).

・繰り返し単位Ｂ

・ Repeating unit A

・ Repeating unit B

<Synthesis Example 2>
-Synthesis of monomer (2)-
Synthesis of compound a

Under an inert atmosphere, in a 300 ml three-necked flask, 5.00 g (29 mmol) of 1-naphthaleneboronic acid, 6.46 g (35 mmol) of 2-bromobenzaldehyde, 10.0 g (73 mmol) of potassium carbonate, 36 ml of toluene and 36 ml of ion-exchanged water And argon bubbling was performed for 20 minutes with stirring at room temperature. Next, 16.8 mg (0.15 mmol) of tetrakis (triphenylphosphine) palladium was added, and argon was bubbled for 10 minutes while stirring at room temperature. The temperature was raised to 100 ° C. and reacted for 25 hours. After cooling to room temperature, the organic layer was extracted with toluene, dried over sodium sulfate, and then the solvent was distilled off. Toluene: cyclohexane = 1: 2 (volume ratio) By producing on a silica gel column using a mixed solvent as a developing solvent, 5.18 g (yield 86%) of compound a was obtained as white crystals.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 7.39-7.62 (m, 5H), 7.70 (m, 2H), 7.94 (d, 2H), 8.12 (dd, 2H), 9.63 (s, 1H)
MS (APCI (+)): (M + H) ^<+> 233

Synthesis of compound b

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

Synthesis of compound c

Under an inert atmosphere, 5.00 g (14.4 mmol) of Compound b (mixture of isomers) and 74 ml of dehydrated dichloromethane were placed in a 500 ml three-necked flask, and dissolved by stirring at room temperature. Then, an etherate complex of boron trifluoride was added dropwise at room temperature over 1 hour, and after completion of the addition, the mixture was stirred at room temperature for 4 hours. While stirring, 125 ml of ethanol was slowly added. When the exotherm subsided, the organic layer was extracted with chloroform, washed twice with water, and dried over magnesium sulfate. After distilling off the solvent, the residue was purified by a silica gel column using hexane as a developing solvent to obtain 3.22 g (yield 68%) of compound c as a colorless oil.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 3H), 1.03-1.26 (m, 14H), 2.13 (m, 2H), 4.05 (t, 1H), 7.35 (dd, 1H), 7 .46-7.50 (m, 2H), 7.59-7.65 (m, 3H), 7.82 (d, 1H), 7.94 (d, 1H), 8.35 (d, 1H) ), 8.75 (d, 1H)
MS (APCI (+)): (M + H) ^<+> 329

Synthesis of compound d

Under an inert atmosphere, 20 ml of ion-exchanged water was placed in a 200 ml three-necked flask, and 18.9 g (0.47 mol) of sodium hydroxide was added little by little with stirring to dissolve. After the aqueous solution was cooled to room temperature, 20 ml of toluene, 5.17 g (15.7 mmol) of compound c and 1.52 g (4.72 mmol) of tributylammonium bromide were added, and the temperature was raised to 50 ° C. N-Octyl bromide was added dropwise, and after completion of the addition, the mixture was reacted at 50 ° C. for 9 hours. After completion of the reaction, the organic layer was extracted with toluene, washed twice with water, and dried over sodium sulfate. Purification by a silica gel column using hexane as a developing solvent gave 5.13 g (yield 74%) of compound d as a yellow oil.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.52 (m, 2H), 0.79 (t, 6H), 1.00-1.20 (m, 22H), 2.05 (t, 4H), 7.34 (d, 1H), 7 40 to 7.53 (m, 2H), 7.63 (m, 3H), 7.83 (d, 1H), 7.94 (d, 1H), 8.31 (d, 1H), 8. 75 (d, 1H)
MS (APCI (+)): (M + H) ^<+> 441

・ Synthesis of compound e

Under an inert atmosphere, 4.00 g (9.08 mmol) of Compound d and 57 ml of a mixed solvent of acetic acid: dichloromethane = 1: 1 (volume ratio) were placed in a 50 ml three-necked flask, and stirred at room temperature to dissolve. Next, 7.79 g (20.0 mmol) of benzyltrimethylammonium tribromide was added and stirred, and zinc chloride was added until the benzyltrimethylammonium tribromide was completely dissolved. After stirring at room temperature for 20 hours, the reaction was stopped by adding 10 ml of 5% by weight aqueous sodium hydrogen sulfite solution, the organic layer was extracted with chloroform, washed twice with aqueous potassium carbonate solution, and dried over sodium sulfate. After purification twice with a flash column using hexane as a developing solvent and silica gel as a packing material, recrystallization is performed with a mixed solvent of ethanol: hexane = 1: 1 (volume ratio) and then with a mixed solvent of 10: 1 (volume ratio). As a result, 4.13 g (yield 76%) of compound e was obtained as white crystals.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.60 (m, 2H), 0.91 (t, 6H), 1.01-1.38 (m, 22H), 2.09 (t, 4H), 7.62-7.75 (m, 3H), 7.89 (s, 1H), 8.20 (d, 1H), 8.47 (d, 1H), 8.72 (d, 1H)
MS (APPI (+)): (M + H) ^<+> 598

The compound e thus obtained is designated as monomer (2).
・ Monomer (2)

<Example 2>
-Synthesis of polymer compound 2-
After charging 0.63 g of monomer (2), 0.23 g of monomer (PP-TPP), and 0.66 g of 2,2′-bipyridyl, the inside of the reaction system was replaced with nitrogen gas. To this was added 70 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. To the obtained mixed solution, 1.15 g of bis (1,5-cyclooctadiene) nickel (0) was added, stirred at room temperature for 10 minutes, and reacted at 60 ° C. for 3 hours. The reaction was performed in a nitrogen gas atmosphere.

After completion of the reaction, the reaction solution was cooled. Next, a mixed solution of methanol 40 ml / ion-exchanged water 40 ml was poured into this solution and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. This toluene solution was filtered to remove insoluble matters, and then this toluene solution was washed with about 1N aqueous hydrochloric acid solution, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was washed with about 3% by weight ammonia water, allowed to stand and liquid-separated, and then the toluene solution was recovered. The recovered toluene solution was washed with ion-exchanged water, allowed to stand and separated, and then the toluene solution was recovered. Next, the recovered toluene solution was poured into methanol and purified by reprecipitation. Next, the produced precipitate was collected and washed with methanol, and then this precipitate was dried under reduced pressure to obtain 0.05 g of a polymer. This polymer is referred to as polymer compound 2. The obtained polymer compound 2 had a polystyrene equivalent weight average molecular weight of 1.0 × 10 ⁴ and a number average molecular weight of 5.9 × 10 ³ . The glass transition temperature (Tg) was 101 ° C.

  The structure of the repeating unit contained in the polymer compound 2 estimated from the preparation is shown below. The polymer compound 2 is composed of a molar ratio of repeating unit C: repeating unit B = 7: 3 (estimated value from preparation).

・繰り返し単位Ｂ

・ Repeat unit C

・ Repeating unit B

で表される単量体原料（Ａ）１．９５ｇと２−（ジフェニルホスフィノ）ベンズアルデヒド（アルドリッチ社製）１．１６ｇとを、反応容器に仕込んだ後、反応系内を窒素ガスで置換した。これに、テトラヒドロフラン（脱水）５０ｍｌを加えた。得られた混合溶液に、あらかじめカリウム−ｔ−ブトキシド０．６７ｇをテトラヒドロフラン（脱水）５ｍｌに溶解させた溶液を、室温で滴下した。滴下後、引き続き室温で２４時間反応させた。なお、反応は窒素ガス雰囲気下で行った。 <Synthesis Example 3>
-Synthesis of monomer (F-TPP)-
The following structural formula:

The monomer raw material (A) represented by the formula (1) 1.95 g and 2- (diphenylphosphino) benzaldehyde (Aldrich) 1.16 g were charged in a reaction vessel, and the reaction system was replaced with nitrogen gas. . To this, 50 ml of tetrahydrofuran (dehydrated) was added. To the obtained mixed solution, a solution prepared by dissolving 0.67 g of potassium tert-butoxide in 5 ml of tetrahydrofuran (dehydrated) was added dropwise at room temperature. After the dropping, the reaction was continued at room temperature for 24 hours. The reaction was performed in a nitrogen gas atmosphere.

  After completion of the reaction, acetic acid was added to the resulting reaction solution to neutralize the reaction solution, and then methanol was added. Next, the solvent was distilled off from this solution under reduced pressure. The obtained solid was washed with methanol and then filtered to collect a precipitate. This precipitate was dissolved in toluene. The toluene solution was filtered to remove insoluble matters, and the obtained toluene solution was purified through an alumina column. Next, the solvent was distilled off from the toluene solution under reduced pressure. The obtained product was washed with methanol and dried under reduced pressure to obtain 1.3 g of a monomer (F-TPP) (specific structure is as described later).

で表される単量体（Ｆ−ＴＰＰ）０．１９ｇと２，２’−ビピリジル０．５７ｇとを反応容器に仕込んだ後、反応系内を窒素ガスで置換した。これに、あらかじめアルゴンガスでバブリングして、脱気したテトラヒドロフラン（脱水溶媒）６０ｇを加えた。得られた混合溶液に、ビス（１，５−シクロオクタジエン）ニッケル（０）を１．０ｇ加え、室温で２３時間反応した。なお、反応は、窒素ガス雰囲気下で行った。 <Example 3>
-Synthesis of polymer compound 3-
Monomer (2) 0.81 g and the following structural formula:

The monomer (F-TPP) 0.19g and 2,2'-bipyridyl 0.57g which were represented by these were charged to reaction container, and the inside of the reaction system was substituted by nitrogen gas. To this was added 60 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. To the obtained mixed solution, 1.0 g of bis (1,5-cyclooctadiene) nickel (0) was added and reacted at room temperature for 23 hours. The reaction was performed in a nitrogen gas atmosphere.

After completion of the reaction, this reaction solution was poured into a mixed solution of 40 ml of methanol / 40 ml of ion-exchanged water for reprecipitation, followed by stirring for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution was filtered to remove insolubles, and then the toluene solution was washed with about 5% by weight acetic acid aqueous solution, allowed to stand and liquid-separated, and then the toluene solution was recovered. Next, this toluene solution was washed with 4 wt% aqueous ammonia, allowed to stand and liquid-separated, and then the toluene solution was recovered. The recovered toluene solution was washed with ion-exchanged water, allowed to stand and separated, and then the toluene solution was recovered. Next, the recovered toluene solution was poured into methanol and purified by reprecipitation. Next, the produced precipitate was recovered and washed with methanol, and then this precipitate was dried under reduced pressure to obtain 0.23 g of a polymer. This polymer is referred to as polymer compound 3. The obtained polymer compound 3 had a polystyrene equivalent weight average molecular weight of 7.0 × 10 ⁴ and a polystyrene equivalent number average molecular weight of 2.2 × 10 ⁴ . Moreover, the glass transition temperature (Tg) was 121 degreeC.

  The structure of the repeating unit contained in the polymer compound 3 estimated from the preparation is shown below. The polymer compound 3 is composed of a molar ratio of repeating unit C: repeating unit F = 9: 1 (estimated value from preparation).

・繰り返し単位Ｆ

・ Repeat unit C

・ Repeating unit F

<Synthesis Example 4>
-Synthesis of monomer (F-TPA)-
1.95 g of monomer raw material (A) and 1.09 g of 4- (N, N-diphenylamino) benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. . To this, 50 ml of tetrahydrofuran (dehydrated) was added. To the obtained mixed solution, a solution prepared by dissolving 0.67 g of potassium tert-butoxide in 5 ml of tetrahydrofuran (dehydrated) was added dropwise at room temperature. After the dropping, the reaction was continued at room temperature for 24 hours. The reaction was performed in a nitrogen gas atmosphere.

で表される単量体（Ｆ−ＴＰＡ）１．６ｇを得た。 After completion of the reaction, acetic acid was added to the resulting reaction solution to neutralize the reaction solution, and then methanol was added. Next, the solvent was distilled off from this solution under reduced pressure. The obtained solid was washed with methanol and then filtered to collect a precipitate. This precipitate was dissolved in toluene. The toluene solution was filtered to remove insoluble matters, and the obtained toluene solution was purified through an alumina column. Next, the solvent was distilled off from the toluene solution under reduced pressure. The obtained product was washed with methanol and then dried under reduced pressure to obtain the following structural formula:

The monomer (F-TPA) represented by these was obtained.

<Comparative Example 1>
-Synthesis of polymer compound 4-
After charging 0.81 g of the monomer (2), 0.18 g of the monomer (F-TPA) and 0.57 g of 2,2′-bipyridyl, the reaction system was replaced with nitrogen gas. . To this was added 60 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas. To the obtained mixed solution, 1.0 g of bis (1,5-cyclooctadiene) nickel (0) was added and reacted at room temperature for 23 hours. The reaction was performed in a nitrogen gas atmosphere.

After completion of the reaction, this reaction solution was poured into a mixed solution of 40 ml of methanol / 40 ml of ion-exchanged water for reprecipitation, followed by stirring for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution was filtered to remove insolubles, and then the toluene solution was washed with about 5% by weight acetic acid aqueous solution, allowed to stand and liquid-separated, and then the toluene solution was recovered. Next, this toluene solution was washed with 4 wt% aqueous ammonia, allowed to stand and liquid-separated, and then the toluene solution was recovered. The recovered toluene solution was washed with ion-exchanged water, allowed to stand and separated, and then the toluene solution was recovered. Next, the recovered toluene solution was poured into methanol and purified by reprecipitation. Next, the produced precipitate was recovered and washed with methanol, and then this precipitate was dried under reduced pressure to obtain 0.31 g of a polymer. This polymer is referred to as polymer compound 4. The obtained polymer compound 4 had a polystyrene equivalent weight average molecular weight of 3.1 × 10 ⁵ and a number average molecular weight of 6.9 × 10 ⁴ . Moreover, the glass transition temperature (Tg) was 128 degreeC.

  The structure of the repeating unit contained in the polymer compound 4 estimated from the preparation is shown below. The polymer compound 4 is composed of a molar ratio of repeating unit C: repeating unit G = 9: 1 (estimated value from preparation).

・繰り返し単位Ｇ

・ Repeat unit C

・ Repeating unit G

<Fluorescence characteristic evaluation>
Each of the polymer compounds 1 to 6 was spin-coated on a quartz plate from a 0.8 wt% toluene solution of the polymer compound to prepare a thin film of the polymer compound. The fluorescence spectrum of this thin film was determined by measuring at an excitation wavelength of 350 nm using a fluorescence spectrophotometer (manufactured by JOBINYVON-SPEX, trade name: Fluorolog). In order to obtain the relative fluorescence intensity in the thin film, the intensity of the Raman line of water was used as a standard, the fluorescence spectrum plotted with the wavenumber was integrated in the spectrum measurement range, and a spectrophotometer (Varian, Cary 5E) was used. The measured value assigned by the absorbance at the excitation wavelength was determined.

  Table 1 shows the measurement results of the fluorescence peak wavelength and the fluorescence intensity. The polymer compound 3 of the present invention had higher fluorescence intensity than the polymer compound 4 having a triphenylamine structure in the side chain.

で表されるイリジウム錯体Ａ（高分子化合物２に対して２重量％）との混合物の１．５重量％キシレン溶液を調製した。
スパッタ法により１５０ｎｍの厚みでＩＴＯ膜を付けたガラス基板に、ポリ（エチレンジオキシチオフェン）／ポリスチレンスルホン酸の溶液（バイエル社、ＢａｙｔｒｏｎＰ）を用いてスピンコートにより５０ｎｍの厚みで成膜し、ホットプレート上で２００℃で１０分間乾燥した。次に、上記調製したキシレン溶液を用いてスピンコートにより８００ｒｐｍの回転速度で成膜した。膜厚は約７０ｎｍであった。これを窒素ガス雰囲気下１３０℃で１時間乾燥した後、陰極としてバリウムを約５ｎｍ、次いでアルミニウムを約８０ｎｍ蒸着して、ＥＬ素子を作製した。なお、真空度が、１×１０^-4Ｐａ以下に到達した後、金属の蒸着を開始した。
得られたＥＬ素子に電圧を引加することにより、イリジウム錯体からの強いＥＬ発光（ピーク波長６３０ｎｍ）が得られた。該素子は印加電圧９．２Ｖで１００ｃｄ／ｍ²の輝度の発光を示し、最大輝度は約２４０ｃｄ／ｍ²で、高輝度が得られた。 <Example 4>
-Creation and evaluation of elements-
Polymer compound 1 and the following structural formula:

A 1.5 wt% xylene solution of a mixture with iridium complex A represented by the formula (2 wt% based on polymer compound 2) was prepared.
A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is used to form a film with a thickness of 50 nm by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Bayer, BaytronP). Dried on plate for 10 minutes at 200 ° C. Next, a film was formed at a rotation speed of 800 rpm by spin coating using the prepared xylene solution. The film thickness was about 70 nm. This was dried at 130 ° C. for 1 hour in a nitrogen gas atmosphere, and then barium was deposited as a cathode at about 5 nm, and then aluminum was deposited at about 80 nm to produce an EL device. Note that, after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.
By applying a voltage to the obtained EL device, strong EL emission (peak wavelength: 630 nm) from the iridium complex was obtained. The device showed light emission of 100 cd / m ² at an applied voltage of 9.2 V, and the maximum luminance was about 240 cd / m ² , and high luminance was obtained.

<Example 5>
A 1.5 wt% xylene solution of a mixture of the polymer compound 2 and iridium complex A (2 wt% with respect to the polymer compound 2) was prepared, and an EL device was produced in the same manner as in Example 4. The light emitting layer was formed by spin coating at a rotation speed of 800 rpm. The film thickness was about 70 nm. By applying voltage to the resulting device, strong EL emission (peak wavelength: 635 nm) from the iridium complex was obtained. The device showed light emission of 100 cd / m ² at an applied voltage of 10.4 V, and the maximum luminance was about 160 cd / m ² , and high luminance was obtained.

<Example 6>
-Preparation of solution-
The polymer compound 3 obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.8% by weight.
-Production of EL elements-
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer, BaytronP CH8000) is filtered through a 0.2 μm membrane filter on a glass substrate with an ITO film having a thickness of 150 nm formed by sputtering. Using the solution, a thin film having a thickness of 60 nm was formed by spin coating and dried on a hot plate at 200 ° C. for 10 minutes. Next, the xylene solution obtained above was used to form a film at a rotational speed of 3200 rpm by spin coating. The film thickness after film formation was about 70 nm. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then barium was deposited as a cathode at about 5 nm, and then aluminum was deposited at about 80 nm to produce an EL device. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
-Performance of EL element-
By applying voltage to the resulting device, EL light emission having a peak at 450 nm was obtained from this device. EL emission color at a luminance of 100 cd / m ² I. E. In terms of color coordinate values, x = 0.161 and y = 0.139. The intensity of EL emission was almost proportional to the current density. The device started to emit light at an applied voltage of 4.2 V, and the maximum light emission efficiency was 0.20 cd / A.

Claims (15)

The high molecular compound containing the repeating unit shown by following formula (1).
-[Ar _1- (X ₁ ) _n ]-(1)
[In the formula, Ar ₁ represents an arylene group having a group represented by the following formula (2), a divalent heterocyclic group having a group represented by the following formula (2), or a group represented by the following formula (2). X ₁ represents —CR ¹ ═CR ² — (wherein R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, an aryl group, or a monovalent heterocyclic group) Or represents a cyano group) or —C≡C—, and n represents 0 or 1. ]

[In the formula, Ar ₂ represents an arylene group, divalent heterocyclic group or divalent aromatic amine group, and Ar ₅ represents a direct bond, an arylene group, a divalent heterocyclic group or a divalent aromatic group. Represents an amine group, and R ³ and R ⁴ are each independently a direct bond, —R ⁵ —, —O—R ⁵ —, —R ⁵ —O—, —R ⁵ —C (O) O—, —R. ⁵ —OC (O) —, —R ⁵ —N (R ⁶ ) —, —O—, —S—, —C (O) O—, —C (O) —, —CR ⁷ ═CR ⁸ — or —C≡C— (wherein R ⁵ represents an alkylene group or an alkenylene group, and R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or represents.) of a cyano group, Ar ₃ and Ar ₄ each independently represent an aryl group, a monovalent heterocyclic group or monovalent aromatic amine group, Y is represented by the following formula

Or

Represents. However, when Ar ₅ is a direct bond, R ³ is a direct bond. ] Ar ₁ is represented by the following formula (8):

Wherein R ¹³ is a group represented by the formula (2), a hydrogen atom, 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 aryl It represents an alkoxy group, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group, or a plurality of R ¹³ may be bonded to form an aromatic ring or a non-aromatic ring. A plurality of R ¹³ may be the same or different, provided that the formula (8) has at least one group represented by the formula (2).
The polymer compound according to claim 1, which is a divalent group represented by: Ar ₁ is represented by the following formula (9):

(In the formula, R ¹³ is the same as described above, provided that the formula (9) has at least one group represented by the formula (2).)
The polymer compound according to claim 1, which is a divalent group represented by: Furthermore, the high molecular compound as described in any one of Claims 1-3 containing the repeating unit shown by following formula (10).
_{- [Ar 19 - (X 2} ) p] - (10)
[In the formula, Ar ₁₉ represents an arylene group, a divalent heterocyclic group, a divalent aromatic amine group or a divalent aromatic phosphine group, and X ₂ represents —CR ¹⁴ = CR ¹⁵ — (where , R ¹⁴ and R ¹⁵ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group.) Or —C≡C—, and p represents 0 or 1. ] Ar ₁₉ represents the following formulas (2a) to (2d):

(Wherein, X represents two atoms and B atoms to form two 5-membered or 6-membered ring together with the atoms on the ring or a divalent group of the A ring, R ^a is Represents ^a substituent, m independently represents an integer of 0 to 5, and n independently represents an integer of 0 to 3. When ^a plurality of R ^a are present, they may be the same or different. Good.)
The polymer compound according to claim 4, which is a divalent group represented by any one of: In the formulas (2a) to (2d), X represents —C (R ¹⁸ ) (R ¹⁹ ) —, —C (R ²⁰ ) (R ²¹ ) —C (R ²² ) (R ²³ ) —, —O— , -S- or -N (R ²⁴⁾ - ^{[R 18, R 19, R 20} , R 21, R 22 and R ²³ each independently represent a hydrogen atom, an alkyl group, alkoxy group, alkylthio group, alkylsilyl A group, an alkylamino group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group; R ²⁴ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. The polymer compound according to claim 5. The polymer compound according to any one of claims 1 to 6, which has a polystyrene-reduced number average molecular weight of 1 x 10 ³ to 1 x 10 ⁸ .   The luminescent material containing the high molecular compound as described in any one of Claims 1-7.   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 1-7.   A planar light source using the polymer light emitting device according to claim 9.   A display device using the polymer light emitting device according to claim 9.   A liquid composition comprising the polymer compound according to any one of claims 1 to 7 and a solvent.   The thin film containing the high molecular compound as described in any one of Claims 1-7.   The organic transistor containing the high molecular compound as described in any one of Claims 1-7.   The solar cell containing the high molecular compound as described in any one of Claims 1-7.