JP2003147347A - Polymer phosphor and polymeric luminescent element made by using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a triarylamine based polymer phosphor which is excellent in e.g. the quantum efficiency of fluorescence and the luminous efficiency of an element made therefrom. SOLUTION: This polymer phosphor contains repeating units represented by formula (1) wherein Ar1 and Ar2 are each arylene or a divalent heterocyclic ring group; Ar3 is an aryl group having one or more substituents, through nuclear substitution, represented by the formula (2): -Y-Ar4 [wherein Ar4 is an aryl, a monovalent heterocyclic ring group or a monovalent aromatic amine group; and Y is -CR3 =CR4 - (wherein R3 and R4 are each H, an alkyl, an aryl, a monovalent heterocyclic ring group or cyano) or -C≡C-], or a monovalent heterocyclic ring group having one or more substituents, through nuclear substitution, represented by the formula (2); X is -CR1 =CR2 - (wherein R1 and R2 are each H, an alkyl, an aryl, a monovalent heterocyclic ring group or cyano) or -C≡C-; and n is 0 or 1} and has visible fluorescence in a solid state.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymeric fluorescent substance and a polymeric light emitting device (hereinafter sometimes referred to as polymeric LED) containing the polymeric fluorescent substance.

[0002]

2. Description of the Related Art A high molecular weight light emitting material (polymer fluorescent substance) is different from that of a low molecular weight type and is soluble in a solvent and can form a light emitting layer in a light emitting device by a coating method. A polymeric fluorescent substance containing a repeating unit derived from a reelamine (hereinafter sometimes referred to as a triarylamine-based polymeric fluorescent substance) is known. As an example thereof, JP-A-9-255774 discloses a compound comprising a repeating unit derived from a triarylamine and a repeating unit of polyetherketone, and WO 99/20675 discloses a triarylamine. A repeating unit derived from ## STR1 ## and a fluorene repeating unit are disclosed.

However, the above-mentioned known triarylamine-based polymeric fluorescent substance is still insufficient in the quantum yield of fluorescence, the luminous efficiency when formed into a device, and the like.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a triarylamine-based polymeric fluorescent substance which is excellent in the quantum yield of fluorescence and the luminous efficiency of a device.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a triarylamine-based polymeric fluorescent substance having a specific substituent in a side chain has a quantum yield of fluorescence, The inventors have found that the device has excellent luminous efficiency and the like, and have completed the present invention.

That is, the present invention comprises a repeating unit represented by the following formula (1), has visible fluorescence in the solid state, and has a polystyrene-equivalent number average molecular weight of 1 × 10 ³ to 1: 1.
The present invention relates to a polymeric fluorescent substance of × 10 ⁸ . [In the formula, Ar ₁ and Ar ₂ each independently represent an arylene group or a divalent heterocyclic group. Ar ₃ is an aryl group having one or more substituents represented by the following formula (2) as nuclear substitution or a monovalent heterocyclic group having one or more substituents represented by the following formula (2) as nuclear substitution. Represent X is
-CR ₁ = CR ₂ - or an -C≡C-. 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. n represents 0 or 1. ] -Y-Ar ₄ (2) wherein, Ar ₄ represents an aryl group, monovalent heterocyclic group or monovalent aromatic amine group. Y is, -CR ₃ = CR ₄
-Or-C represents C-. R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. ]

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Ar ₁ and Ar ₂ in the above formula (1) each independently represent an arylene group or a divalent heterocyclic group.

The term "arylene group" as used herein refers to an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and usually has about 6 to 60 carbon atoms. The carbon number does not include the carbon number of the substituent. The arylene group includes those having a condensed ring, and those in which two or more independent benzene rings or condensed rings are bonded directly or via a group such as vinylene. As the arylene group, a phenylene group (for example, formulas 1 to 1 shown below)
3), naphthalenediyl group (formulas 4 to 13 in the figure below), anthracenylene group (formulas 14 to 19 in the figure below), biphenylene group (formulas 20 to 25 in the figure below), triphenylene group (formulas 26 to 28 in the figure below), condensed ring Compound group (Formulas 29 to 3 in the figure below)
8) etc. are illustrated. Among them, a phenylene group, a biphenylene group, a fluorendiyl group (the following formulas 36 to 38)
Is preferred.

[0009]

[0010]

[0011]

[0012]

[0013]

The divalent heterocyclic group means an atomic group remaining after removing two hydrogen atoms from the heterocyclic compound and usually has about 2 to 60 carbon atoms. The carbon number does not include the carbon number of the substituent. Here, the heterocyclic compound means that among the organic compounds having a cyclic structure, not only the carbon atom is the element constituting the ring,
A hetero atom in the ring, such as oxygen, sulfur, nitrogen, phosphorus, boron, or arsenic.

Examples of the divalent heterocyclic group include the following. A divalent heterocyclic group containing nitrogen as a hetero atom; a pyridine-diyl group (the following formulas 39 to 4)
4), diazaphenylene group (formulas 45 to 48 in the following figure), quinolinediyl group (formulas 49 to 63 in the following figure), quinoxalinediyl group (formulas 64 to 68 in the following figure), acridinediyl group (formulas 69 to 72 in the following figure) , A bipyridyldiyl group (formulas 73 to 75 in the following figure), a phenanthrolinediyl group (formulas 76 to 78 in the following figure), and the like. Silicon, nitrogen as a hetero atom,
A group having a fluorene structure containing sulfur, selenium, oxygen and the like (Formulas 79 to 93 in the figure below). Silicon as a heteroatom,
5-membered heterocyclic group containing nitrogen, sulfur, selenium, oxygen, etc .:
(Equations 94 to 98 in the figure below). A 5-membered condensed heterocyclic group containing silicon, nitrogen, sulfur, selenium, oxygen and the like as a hetero atom: (Formulas 99 to 108 in the figure below). A 5-membered heterocyclic group containing silicon, nitrogen, sulfur, selenium or the like as a hetero atom, which is bonded at the α-position of the hetero atom to form a dimer or oligomer: (Formulas 109 to 110 in the figure below). A 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, oxygen and the like as a hetero atom, which is bonded to the phenyl group at the α-position of the hetero atom: (Formulas 111 to 117 in the figure below).

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

In the above formulas 1 to 117, each R is independently 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 or an arylalkoxy. Group, arylalkenyl group, arylalkynyl group, arylamino group, monovalent heterocyclic group or cyano group. In the above example, a plurality of Rs are included in one structural formula, but they may be the same or different groups. In order to increase the solubility in a solvent, it is preferable that at least one R in one structural formula is other than a hydrogen atom, and it is preferable that the shape of the repeating unit including the substituent has little symmetry.

The alkyl group may be linear, branched or cyclic, and the number of carbon atoms is usually about 1 to 20, specifically, methyl group, ethyl group, propyl group, i.
-Propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group , A lauryl group and the like, and a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group and a 3,7-dimethyloctyl group are preferable.

The alkoxy group may be linear, branched or cyclic, and the number of carbon atoms is usually about 1 to 20, specifically, methoxy group, ethoxy group, propyloxy group, i-propyloxy group, Butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group,
Examples thereof include an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group and a lauryloxy group, and a pentyloxy group, a hexyloxy group, an octyloxy group, 2
-Ethylhexyloxy group, decyloxy group, 3,7-
A dimethyloctyloxy group is preferred.

The alkylthio group may be linear, branched or cyclic, and the carbon number is usually about 1 to 20,
Specifically, methylthio group, ethylthio group, propylthio group, i-propylthio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group,
Octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group and the like, pentylthio group,
Hexylthio group, octylthio group, 2-ethylhexylthio group, decylthio group and 3,7-dimethyloctylthio group are preferred.

The alkylsilyl group may be linear, branched or cyclic and has a carbon number of usually about 1 to 60. Specifically, a methylsilyl group, an ethylsilyl group, a propylsilyl group, an 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-propyldimethylsilyl group, butyldimethylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group Group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group and the like, 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, and 3,7-dimethyloctyl-dimethylsilyl group are preferable.

The alkylamino group may be linear, branched or cyclic, may be a monoalkylamino group or a dialkylamino group, and has a carbon number of usually about 1 to 40, specifically, a methylamino group, Dimethylamino group,
Ethylamino group, diethylamino group, propylamino group, i-propylamino group, butylamino group, i-
Butylamino group, t-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-
Examples thereof include a dimethyloctylamino group and a laurylamino group, and a pentylamino group, a hexylamino group, an octylamino group, a 2-ethylhexylamino group, a decylamino group, and a 3,7-dimethyloctylamino group are preferable.

The aryl group usually has about 6 to 60 carbon atoms, specifically, a phenyl group and a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ have ₁ to ₁₂ carbon atoms). The same applies to the following.), C _{1 to} C ₁₂ alkylphenyl groups, 1-naphthyl groups, 2-naphthyl groups, and the like, and C _{1 to} C ₁₂ alkoxyphenyl groups, C _{1 to} C ₁₂
Alkylphenyl groups are preferred.

The aryloxy group usually has 6 to 6 carbon atoms.
0, specifically, a phenoxy group, C _{1 to} C ₁₂
Examples thereof include an alkoxyphenoxy group, a C _{1 to} C ₁₂ alkylphenoxy group, a 1-naphthyloxy group and a 2-naphthyloxy group, and a C _{1 to} C ₁₂ alkoxyphenoxy group,
C ₁ -C ₁₂ alkylphenoxy group are preferable.

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

The arylalkoxy group usually has 7 carbon atoms.
To about 60, specifically, phenyl-C _{1 to} C ₁₂
Alkoxy group, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C
₁₂ alkoxy groups, C ₁ -C ₁₂ alkylphenyl-C ₁ -C
₁₂ alkoxy group, 1-naphthyl-C ₁ -C ₁₂ alkoxy group, 2-naphthyl-C ₁ -C ₁₂ alkoxy group and the like are exemplified, and C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxy group, C ₁ ˜C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkoxy groups are preferred.

The arylalkenyl group usually has about 8 to 60 carbon atoms, specifically, phenyl-C ₂
To C ₁₂ alkenyl group, C _{1 to} C ₁₂ alkoxyphenyl-
C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -
C ₂ -C ₁₂ alkenyl group, 1-naphthyl -C ₁ -C ₁₂ alkenyl groups, 2-naphthyl -C ₂ -C ₁₂ alkenyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂
Alkenyl group, C ₁ ~C _{1 2} alkylphenyl -C ₂ -C ₁₂
Alkenyl groups are preferred.

The arylalkynyl group usually has about 8 to 60 carbon atoms, specifically, phenyl-C ₂
To C ₁₂ alkynyl group, C _{1 to} C ₁₂ alkoxyphenyl-
C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -
C ₂ -C ₁₂ alkynyl group, 1-naphthyl -C ₂ -C ₁₂ alkynyl group, 2-naphthyl -C ₂ -C ₁₂ alkynyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂
Alkynyl group, C ₁ ~C _{1 2} alkylphenyl -C ₂ -C ₁₂
Alkynyl group is preferred

The arylamino group usually has 6 to 6 carbon atoms.
It is about 0 and is a phenylamino group, a diphenylamino group, a C _{1 to} C ₁₂ alkoxyphenylamino group, a di (C ₁ to
C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino group, 1-naphthylamino group, 2
Examples thereof include a naphthylamino group, and a C _{1 to} C ₁₂ alkylphenylamino group and a di (C _{1 to} C ₁₂ alkylphenyl) amino group are preferable.

The monovalent heterocyclic group usually has 4 to 60 carbon atoms.
And specifically, a thienyl group, a C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group,
C ₁ -C ₁₂ is like the illustration alkylpyridyl group, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, C ₁
~ C ₁₂ alkylpyridyl groups are preferred.

In R, the group containing an alkyl chain may be linear, branched or cyclic, or a combination thereof, and when it is not linear, for example, an isoamyl group, a 2-ethylhexyl group. , 3,7-
Dimethyloctyl group, cyclohexyl group, 4-C _1- C
Examples thereof include a ₁₂ alkylcyclohexyl group. In order to increase the solubility of the polymeric fluorescent substance in a solvent, it is preferable that at least one of Rs contains a cyclic or branched alkyl chain. Further, plural Rs may be linked to form a ring. Further, when R is a group containing an alkyl chain, the alkyl chain may be interrupted with a hetero atom or a group containing a hetero atom. Here, examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the hetero atom or the group containing the hetero atom include the following groups.

[0040] Here, as R ₃ , for example, a hydrogen atom, a carbon number of 1 to
Examples thereof include an alkyl group having 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, and a monovalent heterocyclic group having 3 to 60 carbon atoms.

Further, in the case where R contains an aryl group or a heterocyclic group as a part thereof, they may further have one or more substituents.

Ar ₃ in the above formula (1) is an aryl group having one or more substituents represented by the above formula (2) as nuclear substitution or one or more nuclear substituents represented by the above formula (2). Represents a monovalent heterocyclic group.

The aryl group has usually about 6 to 60 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, a triphenyl group, a pyrenyl group and a fluorenyl group. Of these, a phenyl group, a biphenyl group and a fluorenyl group are preferable.

The monovalent heterocyclic group means an atomic group remaining after removing one hydrogen atom from the heterocyclic compound and usually has about 2 to 60 carbon atoms. Examples of the monovalent heterocyclic group include the following. Monovalent heterocyclic group containing nitrogen as a hetero atom; pyridinyl group, diazaphenyl group, quinolinyl group, quinoxalinyl group, acridinyl group, bipyridinyl group, phenanthroline-yl group and the like.
A group having a fluorene structure containing silicon, nitrogen, sulfur, selenium, oxygen and the like as a hetero atom (the above formula, 79 to 9).
A group having a ring represented by 3), a 5-membered heterocyclic group containing silicon, nitrogen, sulfur, selenium, oxygen and the like as a hetero atom (group having a ring represented by the above formula, 94 to 98) hetero A 5-membered condensed heterocyclic group containing silicon, nitrogen, sulfur, selenium, oxygen or the like as an atom (group having a ring represented by the above formula, 99 to 108). A 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a hetero atom, which is bound to the hetero atom at the α-position to form a dimer or an oligomer (the above formulas, 109 to 110). Group with a ring). Silicon, nitrogen, sulfur, selenium as a hetero atom,
A 5-membered heterocyclic group containing oxygen and the like, which is bonded to a phenyl group at the α-position of the hetero atom (the above formulas, 111 to 11).
A group having a ring represented by 7).

Here, Ar ₃ may have a substituent other than the substituent represented by the above formula (2). When Ar ₃ has a plurality of substituents, they may be the same or different. As the substituent other than the group represented by the formula (2), 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. ,
Examples thereof include an arylalkynyl group, an arylamino group and a monovalent heterocyclic group.

In the above formula (1), X is -CR ₁ =
It represents CR ₂ — or —C≡C—, and —CR ₁ = CR ₂ is preferable from the viewpoint of stability. Here, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. n represents 0 or 1, and 0 is preferable from the viewpoint of photostability.

In the substituent represented by the above formula (2) which Ar ₃ has in the above formula (1), Ar ₄ is an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine group. Specific examples of the aryl group and the monovalent heterocyclic group include A
The same as r ₃ can be mentioned.

The monovalent aromatic amine group refers to an atomic group remaining after removing one hydrogen atom from an aromatic amine, and usually has about 4 to 60 carbon atoms. The carbon number does not include the carbon number of the substituent. As the monovalent aromatic amine group, for example,
Examples are groups represented by the following formulas 123 to 127.

[0049] In the above formulas 123 to 127, R is independently 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, or aryl. An alkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group is shown. In the above example, a plurality of Rs are included in one structural formula, but they may be the same,
It may be a different group.

In the equation (2), Y is -CR₃= CR_Four
-Or-C represents C-. R here ₃And R_FourIs it
Each independently a hydrogen atom, alkyl group, aryl group, monovalent
Represents a heterocyclic group or a cyano group.

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

Above all Is preferred. R is independently 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 is shown. In the above example, although one structure has a plurality of Rs, they may be the same or different groups.

[0053] As the repeating unit represented by formula (1) is preferably one Ar ₁ and Ar ₂ is an arylene group, in Ar ₁ and Ar ₂ is an arylene group, more preferably those wherein n is 0, Ar ₁ and Ar ₂ are arylene groups, n is 0, Ar ₃ and Ar ₄ are aryl groups, and Y
There -CR ₃ = CR ₄ - and it is particularly preferable. Above all Is preferred, Is more preferable. Here, R is independently 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 the above example, although one structure has a plurality of Rs, they may be the same or different groups.

In the polymeric fluorescent substance of the present invention, the formula (1)
The total number of repeating units represented by is usually 1 mol% or more and 100 mol% or less of all repeating units of the polymeric fluorescent substance. The polymeric fluorescent substance of the present invention may contain two or more kinds of repeating units represented by the formula (1).

Among the polymeric fluorescent substances of the present invention, those containing a repeating unit represented by the following formula (3) in addition to the repeating unit represented by the above formula (1) are preferable. —Ar ₅ — (Z) _p — (3) [In the formula, Ar ₅ represents an arylene group or a divalent heterocyclic group. Z is, -CR ₅ = CR ₆ - represents a or -C≡C-. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. p represents 0 or 1. ]

In the repeating unit represented by the formula (3), Ar ₅ is an arylene group or a divalent heterocyclic group. Among them, phenylene group, biphenylene group, fluorendiyl group, stilbenediyl (A to D in the following figure),
Distilbene diyl (E, F below) is preferred. Z
Represents —CR ₅ = CR ₆ — or —C≡C—. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. p is
Represents 0 or 1.

Specific examples of the repeating unit represented by the formula (3) include the above formulas 1 to 117 and the following formulas A to F.
The structure described in 1 is mentioned. Among them, a phenylene group (for example, formulas 1 to 3 in the above figure), a naphthalenediyl group (formulas 4 to 13 in the above figure), an anthracenylene group (formula 14 in the above figure)
˜19), biphenylene group (formulas 20 to 25 in the above figure), triphenylene group (formulas 26 to 28 in the above figure), condensed ring compound group (formulas 29 to 38 in the above figure), stilbenediyl (A to D in the following figure) ), Distilbene diyl (the following figures E and F) are preferably exemplified. Among them, a phenylene group, a biphenylene group, a fluorendiyl group (the above formulas 36 to 3
8), stilbene diyl (A to D below), and distilbene diyl (E and F below) are particularly preferable. Here, R is independently a hydrogen atom, 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 is shown. In the above example, although one structure has a plurality of Rs, they may be the same or different groups.

The combination of the repeating units represented by the formulas (1) and (3) of the polymeric fluorescent substance containing one or more kinds of the repeating units represented by the formulas (1) and (3) is represented by the formula (1 ) Of the repeating unit represented by
It is preferable that r ₁ and Ar ₂ are arylene groups and the repeating unit represented by the formula (3) is Ar _{5 which} is an arylene group or a divalent heterocyclic group, and the repeating unit represented by the formula (1) is , Ar ₁ and Ar ₂ are arylene groups,
n is 0 and A of the repeating unit represented by the formula (3)
It is more preferable that r ₅ is an arylene group or a divalent heterocyclic group and P is 0, and Ar ₁ and Ar _{2 of the} repeating unit represented by the formula (1) are an arylene group and n is 0,
Ar ₃ and Ar ₄ are aryl groups, and Y is —CR ₃ ═CR
₄ -, and the repeating unit represented by the formula (3), Ar ₅
Is more preferably an arylene group and P is 0.
Examples of the combination of repeating units represented by the formulas (1) and (3) in the form of structural units include the following.

Combination example 1 Combination example 2 Combination example 3 Combination example 4 Combination example 5 Combination example 6 Combination example 7

Among them, the combination examples 1, 2, 4, 5,
6,7 are preferred. Here, R is independently 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. Base,
An arylamino group, a monovalent heterocyclic group or a cyano group is shown. In the above example, although one structure has a plurality of Rs, they may be the same or different groups.

In the polymeric fluorescent substance containing the repeating units represented by the formulas (1) and (3), the total of the repeating units represented by the formulas (1) and (3) is the polymeric fluorescent substance. 50 mol% or more of all the repeating units having, and 2 mol% or more and 90 mol% of the repeating unit represented by the formula (1) based on the total of the repeating units represented by the formulas (1) and (3). The following are more preferable from the viewpoint of heat resistance.

The polymeric fluorescent substance of the present invention has visible fluorescence in a solid state, and typically has a polystyrene reduced number average molecular weight of 10 ³ to 10 ⁸ and 2 × 10 ³ to 10 ⁷ . It is preferable.

The terminal group of the polymeric fluorescent substance of the present invention is protected by a stable group because if the polymerization active group remains as it is, the emission characteristics and life of the device may be reduced. May be. Those having a conjugated bond which is continuous with the conjugated structure of the main chain are preferable, and for example, a structure which is bonded to an aryl group or a heterocyclic group via a vinylene group may be used. Specifically, JP-A-9-45478
Substituents and the like described in Chemical formula 10 of the publication are exemplified.

Further, the polymeric fluorescent substance of the present invention may contain a repeating unit other than the repeating units represented by the formulas (1) and (3) as long as the fluorescent property and the charge transport property are not impaired. Further, the repeating units may be linked by vinylene or a non-conjugated portion, or the repeating units may include those vinylene or a non-conjugated portion. The bonding structure containing the non-conjugated portion, the following, a combination of the following and a vinylene group,
And a combination of two or more of the following. Here, R is a group selected from the same substituents as those described above, and Ar represents a hydrocarbon group having 6 to 60 carbon atoms.

[0065] Further, the polymeric fluorescent substance of the present invention may be a random, block or graft copolymer, or a polymer having an intermediate structure between them, for example, a random copolymer having a block property. Good. From the viewpoint of obtaining a polymeric fluorescent substance having a high fluorescence quantum yield, a random copolymer having a block property or a block or graft copolymer is preferable to a completely random copolymer. It also includes a case where the main chain is branched and has three or more terminal portions, and a dendrimer.

Good solvents for the polymeric fluorescent substance of the present invention include chloroform, methylene chloride, dichloroethane,
Tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, n-butylbenzene and the like are exemplified. Depending on the structure and molecular weight of the polymeric fluorescent substance,
Usually, 0.1% by weight or more can be dissolved in these solvents.

Next, a method for producing the polymeric fluorescent substance of the present invention will be described. As a method for producing the polymeric fluorescent substance of the present invention, when the main chain has a vinylene group, for example, the method described in JP-A-5-202355 can be mentioned.
That is, polymerization 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 by Wittig reaction, a compound having a vinyl group and a compound having a halogen group, or a vinyl group Polymerization by Heck reaction of a compound having a halogen group, Horner-Wadsworth-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
Polymerization by Emmons method, polycondensation of compounds having two or more methyl halide groups by dehydrohalogenation method, polycondensation of compounds having two or more sulfonium bases by sulfonium salt decomposition method, aldehyde groups A method such as polymerization of a compound having an acetonitrile group and a compound having an aldehyde group and an acetonitrile group by Knoevenagel reaction, a method of polymerization of a compound having two or more aldehyde groups by McMurry reaction, and the like. It is illustrated.

When the main chain does not have a vinylene group, for example, a method of polymerizing from a corresponding monomer by Suzuki coupling reaction, a method of polymerizing by Grignard reaction, a method of polymerizing by Ni (0) catalyst, FeCl ₃ Examples of the method include a method of polymerizing with an oxidizing agent such as, an electrochemical method of oxidative polymerization, and a method of decomposing an intermediate polymer having a suitable leaving group. Of these, polymerization by Wittig reaction, Heck
Polymerization by reaction, Horner-Wadsworth-
Polymerization by the Emmons method, polymerization by the Knoevenagel reaction, polymerization by the Suzuki coupling reaction, polymerization by the Grignard reaction, and polymerization by a Ni (0) catalyst are preferable because the structure control is easy. Specifically, if necessary, a compound having a plurality of reactive substituents, which becomes a monomer,
It can be dissolved in an organic solvent and reacted, for example, with an alkali or a suitable catalyst at a temperature not lower than the melting point and not higher than the boiling point of the organic solvent. For example, “Organic Reactions (O
organic reactions) ", Volume 14, 2
70-490, John Wiley and Sons (J
ohn Wiley & Sons, Inc. ), 1965
Year, "Organic Reactions (Organic
Reactions) ", vol. 27, 345-390.
Page, John Wiley and Sons (John Wi
ley & Sons, Inc. ), 1982, "Organic Synthesis"
es) ”, Collective Vol. 6 (Collective
Volume VI, pp. 407-411, John Wiley & Sons (John Wiley & So)
ns, Inc. ), 1988, Chemical Review (Chem. Rev.), Vol. 95, p. 2457 (19).
1995), Journal of Organometallic Chemistry (J. Organomet. Chem.),
Volume 576, p. 147 (1999), Journal of Practical Chemistry (J. Prakt.
Chem. ), 336, 247 (1994),
Macromolecular Chemistry Macromolecular Symposium (Makromol. Chem., M
acromol. Symp. ), Vol. 12, p. 229 (1987) and the like can be used.

Although the organic solvent varies depending on the compound and reaction used, it is generally preferable to sufficiently deoxidize the solvent used and to allow the reaction to proceed in an inert atmosphere in order to suppress side reactions. Further, it is preferable to perform dehydration treatment in the same manner. (However, this is not the case in the case of a reaction in a two-phase system with water such as the Suzuki coupling reaction.)

For the reaction, an alkali or a suitable catalyst is added. These may be selected according to the reaction used. The alkali or catalyst is preferably one that is sufficiently dissolved in the solvent used for the reaction. The method for mixing the alkali or the catalyst is to slowly add the solution of the alkali or the catalyst while stirring the reaction solution under an inert atmosphere such as argon or nitrogen, or, conversely, slowly add the reaction solution to the solution of the alkali or the catalyst. The method of adding is illustrated.

More specifically, the reaction conditions will be described. Wittig reaction, Horner reaction, Knoev reaction.
In the case of an angel reaction or the like, the reaction is performed using an equivalent amount or more, preferably 1 to 3 equivalents of alkali with respect to the functional group of the monomer. The alkali is not particularly limited,
For example, potassium-t-butoxide, sodium-t-
A metal alcoholate such as butoxide, sodium ethylate, and lithium methylate, a hydride reagent such as sodium hydride, and an amide such as sodium amide can be used. As the solvent, N, N-dimethylformamide, tetrahydrofuran, dioxane, toluene and the like are used. The reaction temperature is usually room temperature to about 150 ° C. to allow the reaction to proceed. The reaction time is, for example, 5 minutes to 40 hours, but it may be any time as long as the polymerization proceeds sufficiently, and it is not necessary to leave it for a long time after the reaction is completed.
24 hours. If the concentration during the reaction is too dilute, the efficiency of the reaction will be poor, and if it is too high, the control of the reaction will be difficult. It is in the range of 1 wt% to 20 wt%. In the case of Heck reaction, a palladium catalyst is used to react the monomers in the presence of a base such as triethylamine. N, N-dimethylformamide and N-
Using a solvent with a relatively high boiling point such as methylpyrrolidone,
The reaction temperature is about 80 to 160 ° C., and the reaction time is about 1 hour to 100 hours.

In the case of the Suzuki coupling reaction,
As the catalyst, for example, palladium [tetrakis (triphenylphosphine)], palladium acetates or the like is used, and an inorganic base such as potassium carbonate, sodium carbonate or barium hydroxide, an organic base such as triethylamine or an inorganic salt such as cesium fluoride is used as a monomer. Or more, and preferably 1 to 10 equivalents are added for the reaction. The inorganic salt may be used as an aqueous solution and reacted in a two-phase system. As a solvent,
Examples 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 preferably used. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 1 hour to 200 hours.

In the case of Grignard reaction, a halide and a metal Mg are reacted in an ether solvent such as tetrahydrofuran, diethyl ether or dimethoxyethane to prepare a Grignard reagent solution, which is mixed with a monomer solution prepared separately. An example is a method in which a nickel or palladium catalyst is added while paying attention to excessive reaction, and then the temperature is raised to carry out the reaction while refluxing. Grig
The Nard 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. When the polymerization is performed by a method other than these, the reaction can be performed according to a known method.

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

In this case, adding a neutral ligand
It is preferable from the viewpoint of improving the yield and increasing the molecular weight. Here, the neutral ligand is a ligand having no anion or cation, and is 2,2′-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline, N, N′-tetramethylethylenediamine. Examples of nitrogen-containing ligands such as; triphenylphosphine, tritolylphosphine, tributylphosphine, triphenoxyphosphine, and other tertiary phosphine ligands are exemplified, and nitrogen-containing ligands are preferable in terms of versatility and low cost. , 2,2'-bipyridyl is highly reactive,
It is particularly preferable in terms of high yield.

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

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

When a neutral ligand is used, the amount used is usually about 0.5 to 10 mol with respect to 1 mol of the zero-valent nickel complex, and the cost performance ( 0.9 from the viewpoint of high yield and inexpensive input)
Molar to 1.1 mol is preferred. When the polymerization is performed by a method other than these, the reaction can be performed according to a known method.

When the polymeric fluorescent substance of the present invention is used as a light emitting material for a polymeric LED, the purity thereof affects the light emitting characteristics. Therefore, the monomer before polymerization is purified by a method such as distillation, sublimation purification, recrystallization and the like. It is preferable to polymerize afterwards,
Further, after the synthesis, it is preferable to carry out purification treatment such as reprecipitation purification and fractionation by chromatography.

The polymeric fluorescent substance of the present invention can be used not only as a light emitting material, but also as an organic semiconductor material, an optical material, or a conductive material by doping.

Next, the polymer LED of the present invention will be described. The polymer LED of the present invention has a light emitting layer between electrodes composed of an anode and a cathode, and the light emitting layer contains the polymer fluorescent substance of the present invention. Further, as the polymer LED of the present invention, a polymer LED having an electron transport layer provided between a cathode and a light emitting layer, a polymer LED having a hole transport layer provided between an anode and a light emitting layer, An example is a polymer LED in which an electron transport layer is provided between the cathode and the light emitting layer and a hole transport layer is provided between the anode and the light emitting layer.

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

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

There is no limitation on the method of forming the light emitting layer, but a method of forming a film from a solution is exemplified.

As a film forming method from a solution, a spin coating method, a casting method, a microgravure coating method,
A coating method such as a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method or an inkjet printing method can be used. When a polymer LED of the present invention soluble in an organic solvent is used to form a polymer LED, when a film is formed from a solution, it is sufficient to remove the solvent by coating and drying the solution. The same method can be applied when mixing transport materials and luminescent materials.
It is very advantageous in manufacturing.

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

In the polymer LED of the present invention, a light emitting material other than the above polymer phosphor may be mixed and used in the light emitting layer. Further, in the polymer LED of the present invention, a light emitting layer containing a light emitting material other than the polymer fluorescent substance may be laminated with a light emitting layer containing the polymer fluorescent substance. As the light emitting material, known materials can be used. Examples of low molecular weight compounds include naphthalene derivatives, anthracene or its derivatives, perylene or its derivatives, polymethine-based, xanthene-based, coumarin-based, cyanine-based dyes, metal complexes of 8-hydroxyquinoline or its derivatives, and aromatic amines. , Tetraphenylcyclopentadiene or its derivative, or tetraphenylbutadiene or its derivative can be used.
Specifically, for example, JP-A-57-51781 and 59
Known ones such as those described in JP-A-194393 can be used.

When the polymer LED of the present invention has a hole-transporting layer, the hole-transporting material used is polyvinylcarbazole or its derivative, polysilane or its derivative, and an aromatic amine in the side chain or main chain. Polysiloxane derivative, pyrazoline derivative, arylamine derivative, stilbene derivative, triphenyldiamine derivative, polyaniline or its derivative, polythiophene or its derivative, polypyrrole or its derivative, poly (p-phenylenevinylene) or its derivative, or poly (2, 5-thienylene vinylene) or a derivative thereof and the like.

Specifically, as the hole transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359 and JP-A-2-13536 are used.
No. 1, gazette No. 2-209988, gazette No. 3-3799
Examples are those described in JP-A No. 2 and JP-A No. 3-152184.

Among these, as the hole transport material used in the hole transport layer, polyvinylcarbazole or its derivative, polysilane or its derivative, polysiloxane derivative having an aromatic amine compound group in its side chain or main chain, polyaniline or Derivatives thereof, polythiophene or derivatives thereof, poly (p-phenylene vinylene)
Alternatively, a polymer hole transport material such as a derivative thereof, poly (2,5-thienylene vinylene) or a derivative thereof is preferable, and more preferably polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof,
It is a polysiloxane derivative having an aromatic amine in the side chain or main chain. In the case of a low molecular weight hole transport material, it is preferable to use it by dispersing it in a polymer binder.

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

As the polysilane or its derivative,
Chemical Review (Chem. Rev.) Vol. 89,
1359 (1989), British Patent GB230019
The compounds and the like described in No. 6 publication are exemplified. As the synthetic method, the methods described in these can be used, but the Kipping method is particularly preferably used.

Since polysiloxane or its derivative has almost no hole transporting property in the siloxane skeleton structure,
Those having the structure of the above-mentioned low molecular weight hole transport material in the side chain or the main chain are preferably used. Particularly, those having a hole-transporting aromatic amine in the side chain or the main chain are exemplified.

The method for forming the hole transport layer is not limited,
For the low molecular weight hole transport material, a method of forming a film from a mixed solution with a polymer binder is exemplified. For the polymer hole transport material, a method of forming a film from a solution is exemplified.

The solvent used for film formation from the solution is not particularly limited as long as it dissolves the hole transport material.
As the solvent, chlorine-based solvents such as chloroform, methylene chloride and dichloroethane, ether-based solvents such as tetrahydrofuran, aromatic hydrocarbon-based solvents such as toluene and xylene, ketone-based solvents such as acetone and methyl ethyl ketone,
Examples thereof include ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate.

As a film forming method from a solution, a spin coating method from a solution, a casting method, a microgravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method. Method, screen printing method, flexo printing method,
A coating method such as an offset printing method or an inkjet printing method can be used.

As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those showing no strong absorption of visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

The film thickness of the hole transport layer varies depending on the material used, and may be selected so that the driving voltage and the luminous efficiency have appropriate values, but at least a thickness that does not cause pinholes. Is necessary, and if it is too thick,
The driving voltage of the device becomes high, which is not preferable. Therefore, the film thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

When the polymer LED of the present invention has an electron-transporting layer, known electron-transporting materials can be used, including an oxadiazole derivative, anthraquinodimethane or its derivative, benzoquinone or its derivative, Naphthoquinone or its derivative, anthraquinone or its derivative, tetracyanoanthraquinodimethane or its derivative, fluorenone derivative, diphenyldicyanoethylene or its derivative, diphenoquinone derivative, or a metal complex of 8-hydroxyquinoline or its derivative, polyquinoline or its derivative, Examples thereof include polyquinoxaline or its derivative, polyfluorene or its derivative, and the like.

Specifically, JP-A-63-70257, JP-A-63-175860, and JP-A-2-1353.
No. 59, No. 2-135361, No. 2-209.
No. 988, No. 3-37992, and No. 3-152.
Examples include those described in Japanese Patent No. 184.

Of these, oxadiazole derivatives,
Benzoquinone or a derivative thereof, anthraquinone or a derivative thereof, a metal complex of 8-hydroxyquinoline or a derivative thereof, polyquinoline or a derivative thereof, polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof, and 2- (4-biphenylyl) -5 is preferable. -(4-t-butylphenyl) -1,
More preferred are 3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline.

The method for forming the electron transport layer is not particularly limited, but for low molecular weight electron transport materials, the vacuum deposition method from powder or the method by film formation from a solution or a molten state is used as a polymer electron transport material. Then, a method of forming a film from a solution or a molten state is exemplified. When forming a film from a solution or a molten state, a polymer binder may be used together.

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

The film formation method from a solution or a molten state includes spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating. A coating method such as a method, a screen printing method, a flexographic printing method, an offset printing method, an inkjet printing method or the like can be used.

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

The film thickness of the electron transport layer varies depending on the material used, and may be selected so that the driving voltage and the luminous efficiency have appropriate values, but at least a thickness that does not cause pinholes. Is necessary, and if it is too thick,
The driving voltage of the device becomes high, 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, in the charge transport layer provided adjacent to the electrode, it has a function of improving the charge injection efficiency from the electrode,
Those having an effect of lowering the drive voltage of the element are generally called a charge injection layer (hole injection layer, electron injection layer) in particular.

Further, in order to improve the adhesion to the electrode and the charge injection from the electrode, the above-mentioned charge injection layer or an insulating layer having a film thickness of 2 nm or less may be provided adjacent to the electrode.
A thin buffer layer may be inserted at the interface of the charge transport layer or the light emitting layer in order to improve the adhesion at the interface, prevent mixing, and the like. The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of luminous efficiency and device life.

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

As a concrete example of the charge injection layer, a layer containing a conductive polymer, which is provided between the anode and the hole transport layer,
A layer containing a material having an ionization potential of an intermediate value between the anode material and the hole transport material contained in the hole transport layer, provided between the cathode and the electron transport layer, and included in the cathode material and the electron transport layer. Examples thereof include a layer including a material having an electron affinity that is an intermediate value with respect to the electron transport material.

When the charge injection layer is a layer containing a conductive polymer, the electric conductivity of the conductive polymer is 10 ⁻⁵ S / cm.
It is preferably 10 ³ S / cm or less, and in order to reduce the leak current between the light emitting pixels, 10 ⁻⁵ S / c
m or more and 10 ² S / cm or less are more preferable, and 10 ^-5 S / cm
More preferably, it is not less than 10 cm and not more than 10 ¹ S / cm. Usually, the electric conductivity of the conductive polymer is 10 ^-5 S / cm or more 10
^The conductive polymer is doped with an appropriate amount of ions in order to achieve ³ S / cm or less.

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

The material used for the charge injection layer may be appropriately selected in relation to the material of the electrode and the adjacent layer. Polyaniline and its derivative, polythiophene and its derivative, polypyrrole and its derivative, polyphenylenevinylene and its derivative, poly Thienylene 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 phthalocyanines (copper phthalocyanine, etc.), carbon, etc. It is illustrated.

The insulating layer having a film thickness of 2 nm or less has a function of facilitating charge injection. Examples of the material of the insulating layer include metal fluorides, metal oxides, organic insulating materials and the like. Polymer LE with an insulating layer having a thickness of 2 nm or less
Examples of D include a polymer LED having an insulating layer having a thickness of 2 nm or less adjacent to a cathode and a polymer LED having an insulating layer having a thickness of 2 nm or less adjacent to an anode.

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

The substrate forming the polymer LED of the present invention is
Any material that does not change when an electrode is formed and an organic material layer is formed may be used, and examples thereof include glass, plastics, polymer films, and silicon substrates. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

In the present invention, it is usually preferable that at least one of the electrodes consisting of an anode and a cathode is transparent or semitransparent, and the anode side is transparent or semitransparent.
A conductive metal oxide film, a semitransparent metal thin film, or the like is used as the material of the anode. Specifically, a film (NESA) formed using a conductive glass made of indium oxide, zinc oxide, tin oxide, and a composite material thereof such as indium tin oxide (ITO) and indium zinc oxide. Etc.), gold, platinum, silver, copper, etc. are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the manufacturing method include a vacuum vapor deposition method, a sputtering method, an ion plating method, a plating method and the like. Further, as the anode, an organic transparent conductive film such as polyaniline or a derivative thereof and polythiophene or a derivative thereof may be used. The film thickness of the anode is
Although it can be appropriately selected in consideration of light transmittance and electric conductivity, it is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 5 nm.
It is 0 nm to 500 nm. In order to facilitate charge injection on the anode, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or an average film thickness of 2 nm made of a metal oxide, a metal fluoride, an organic insulating material, or the like.
The following layers may be provided.

As a material of the cathode used in the polymer LED of the present invention, a material having a small work function is preferable. For example,
Lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium,
Metals such as samarium, europium, terbium, ytterbium, and alloys of two or more of them, or one or more of them, and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten,
Alloys with one or more of tin, graphite, graphite intercalation compounds, etc. are used. Examples of alloys 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 etc. are mentioned. The cathode may have a laminated structure of two or more layers. The thickness of the cathode can be appropriately selected in consideration of electrical conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1
μm, and more preferably 50 nm to 500 nm.

As a method for producing the cathode, a vacuum vapor 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 and having an average film thickness of 2 nm or less may be provided between the cathode and the organic layer. A protective layer for protecting the polymer LED may be attached. In order to stably use the polymer LED for a long term, 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, polymer compounds, metal oxides, metal fluorides, metal borides and the like can be used. As the protective cover, a glass plate, a plastic plate whose surface has been subjected to low water permeability treatment, or the like can be used, and a method in which the cover is bonded to the element substrate with a heat-effect resin or a photocurable resin and sealed is preferable. Used for. If the space is maintained by using the spacer, it is easy to prevent the element from being scratched. If an inert gas such as nitrogen or argon is filled in the space, oxidation of the cathode can be prevented. Further, by installing a desiccant such as barium oxide in the space, moisture adsorbed in the manufacturing process can be prevented. It becomes easy to suppress that the element gives an image. It is preferable to take any one or more of these measures.

The polymer light emitting device of the present invention can be used as a surface light source, a segment display device, a dot matrix display device, a backlight of a liquid crystal display device and the like.

In order to obtain planar light emission using the polymer LED of the present invention, the planar anode and cathode may be arranged so as to overlap each other. Further, in order to obtain a patterned light emission, a method of installing a mask having a patterned window on the surface of the planar light emitting element, and forming the organic layer of the non-light emitting portion to be extremely thick, There are a method of emitting light, and a method of forming either or both of the anode and the cathode in a pattern. By forming a pattern by one 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, etc. can be obtained.
Further, in order to form a dot matrix device, both the anode and the cathode may be formed in stripes and arranged so as to be orthogonal to each other. Partial color display and multi-color display are possible by a method of separately coating a plurality of types of polymeric fluorescent substances having different emission colors or a method of using a color filter or a fluorescence conversion filter. The dot matrix element can be passively driven, or may be actively driven in combination with a TFT or the like. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like. Further, 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. Further, if a flexible substrate is used, it can be used as a curved light source or a display device.

[0123]

EXAMPLES Examples will be shown below to explain the present invention in more detail, but the present invention is not limited to these. Here, regarding the number average molecular weight, the polystyrene equivalent number average molecular weight was determined by gel permeation chromatography (GPC) using chloroform as a solvent.

Example 1 <Synthesis of polymeric fluorescent substance 1> 0.277 g of 4,4'-dibromuu {4 ''-(4-ethylphenyl) ethenyl} triphenylamine and 9,9-dioctyl-2,7
-Fluo orange boric acid ethylene glycol ester 0.
After 265 g and 0.55 g of potassium carbonate were dissolved in 8 g of toluene and 2 g of ion-exchanged water, bubbling with nitrogen gas was performed to replace the inside of the system with nitrogen gas. After adding 0.08 g of palladium catalyst {Pd (PPh ₃ ) ₄ } and 0.1 g of phase transfer catalyst Aliquat 336 to this solution, reaction was carried out at 80 ° C. for 6 hours. The reaction was carried out in a nitrogen gas atmosphere. After cooling this reaction liquid, about 50 g of a mixed solution of methanol / ion-exchanged water = 10/1 was added to collect the formed precipitate. Next, this precipitate was washed with methanol, dissolved in a small amount of chloroform, and methanol was added to this solution for reprecipitation purification. This precipitate was collected and dried under reduced pressure to obtain 0.27 g of a polymer. The obtained polymer is called polymeric fluorescent substance 1.

The polystyrene reduced number average molecular weight of the polymeric fluorescent substance 1 was 4.4 × 10 ³ . The structure of the repeating unit contained in polymeric fluorescent substance 1 estimated from the charging is shown below.

Example 2 <Synthesis of polymeric fluorescent substance 2> 0.533 g of 4,4′-dibromuu {4 ″-(4-ethylphenyl) ethenyl} triphenylamine and 9,9-bis (3,7) -Dimethyloctyl) -2,7-fluorange boric acid 0.53
After dissolving 4 g and 0.55 g of potassium carbonate in 7 g of toluene and 7 g of ion-exchanged water, bubbling with nitrogen gas was performed to replace the system with nitrogen gas. To this solution, 0.15 g of palladium catalyst {Pd (PPh ₃ ) ₄ } was added, and then 80 ° C.
And reacted for 6 hours. The reaction was carried out in a nitrogen gas atmosphere. After cooling this reaction liquid, 7 g of toluene and 7 g of ion-exchanged water were added, and the mixture was stirred, allowed to stand still, and separated to collect a toluene layer. The collected solution was filtered and then poured into methanol to collect the generated precipitate. Next, this precipitate was washed with ethanol and then dried under reduced pressure to obtain 0.32 g of a polymer. The obtained polymer is called polymeric fluorescent substance 2.

The polystyrene reduced number average molecular weight of the polymeric fluorescent substance 2 was 2.5 × 10 ³ . The structure of the repeating unit contained in polymeric fluorescent substance 2 estimated from the charging is shown below.

Example 3 <Synthesis of polymeric fluorescent substance 3> 2.1 g of 4,4′-dibromuu {4 ″-(4-t-butylphenyl) ethenyl} triphenylamine and 2,2′-bipyridyl 1 .3
After dissolving 8 g and 100 g of tetrahydrofuran (dehydrated), nitrogen gas was bubbled to replace the inside of the system with nitrogen gas. To this solution, 2.5 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added, stirred for about 10 minutes at room temperature, then heated to react at 60 ° C. for 6 hours. did. The reaction was carried out in a nitrogen gas atmosphere. After cooling this reaction liquid, a mixed solution of 25% ammonia water 25 ml / methanol 100 ml / ion-exchanged water 100 ml was added, and the mixture was stirred for about 1 hour. This solution was allowed to stand overnight at room temperature, and the generated precipitate was collected by filtration. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was poured into methanol for reprecipitation purification.
The produced precipitate was collected, washed with ethanol, and then dried under reduced pressure to obtain 0.4 g of a polymer. The obtained polymer is called polymeric fluorescent substance 3.

The polystyrene reduced number average molecular weight of the polymeric fluorescent substance 3 was 2 × 10 ⁴ . The structure of the repeating unit contained in polymeric fluorescent substance 3 estimated from the charging is shown below.

Example 4 <Synthesis of polymeric fluorescent substance 4> 0.25 g of 4,4'-dibromuu {4 ''-(4-t-butylphenyl) ethenyl} triphenylamine and 9,9-dioctyl-2 ，
0.51 g of 7-dibromofluorene and 0.55 g of 2,2'-bipyridyl were added to 40 g of tetrahydrofuran (dehydrated).
Then, the inside of the system was replaced with nitrogen gas. To this solution, 1.0 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added, and the mixture was stirred at room temperature for about 10 minutes and then heated to 60 ° C. for 6 minutes.
Reacted for hours. The reaction was carried out in a nitrogen gas atmosphere. After cooling this reaction liquid, 25% ammonia water 10
ml / methanol 100 ml / ion exchanged water 100 ml
The mixed solution was added and stirred for about 1 hour. After leaving this solution at room temperature overnight, by filtering the generated precipitate,
Recovered. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was poured into methanol for reprecipitation purification. After collecting the generated precipitate and washing with ethanol,
This was dried under reduced pressure to obtain 0.3 g of a polymer. The obtained polymer is called polymeric fluorescent substance 4.

The polystyrene reduced number average molecular weight of the polymeric fluorescent substance 4 was 4.1 × 10 ⁴ , and the weight average molecular weight thereof was 1.2 × 10 ⁵ . The structure of the repeating unit contained in polymeric fluorescent substance 4 estimated from the charging is shown below.

Example 5 <Measurement of absorption spectrum and fluorescence spectrum> The polymeric fluorescent substance 1 could be easily dissolved in chloroform. The 0.2% chloroform solution was spin-coated on a quartz plate to form a polymer thin film. The UV-visible absorption spectrum and the fluorescence spectrum of this thin film were measured using a self-recording spectrophotometer UV365 manufactured by Shimadzu and a fluorescence spectrophotometer 850 manufactured by Hitachi, respectively.

Example 6 <Production and Evaluation of Element> 150 nm by a sputtering method
On a glass substrate having an ITO film with a thickness of 50 nm by spin coating with a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Bayer, Baytron) to a thickness of 50 nm.
It was dried at 20 ° C. for 5 minutes. Next, 1. of the polymeric fluorescent substance 1.
A film having a thickness of 70 nm was formed by spin coating using a 5 wt% chloroform solution. Furthermore, this is depressurized to 80
After drying at ℃ for 1 hour, aluminum lithium alloy (lithium 0.5wt%) 50nm vapor deposition as a cathode,
A polymer LED was prepared. The degree of vacuum at the time of vapor deposition was 1 to 8 × 10 ⁻⁶ Torr. By applying a voltage to the obtained device, EL light emission from the polymeric fluorescent substance 1 was obtained. The light emission starting voltage is about 7V, the maximum luminous efficiency is about 0.01 cd / A, and the maximum luminance is about 20 cd / m.
It was 2. The EL peak wavelength is almost the same as the fluorescence peak wavelength of the thin film of polymeric fluorescent substance 1,
EL emission was confirmed.

Example 7 <Synthesis of polymeric fluorescent substance 5> 0.5 g of 4,4'-dibromuu {4 ''-(4-t-butylphenyl) ethenyl} triphenylamine and 4,4'-dibromo- Three
After dissolving 3.37 g of 3'-di (3,7-dimethyloctyloxy) stilbene and 1.1 g of 2,2'-bipyridyl in 80 g of tetrahydrofuran (dehydrated), bubbling with a nitrogen gas was performed and the system was replaced with nitrogen. The gas was replaced. To this solution, 2.0 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added, stirred for about 10 minutes at room temperature, then heated up and reacted at 60 ° C. for 3 hours. did. In addition,
The reaction was carried out in a nitrogen gas atmosphere. After cooling the reaction liquid, 25% ammonia water 20 ml / methanol 100
A mixed solution of ml / ion-exchanged water (150 ml) was added, and the mixture was stirred for about 1 hour. This solution was allowed to stand overnight at room temperature, and the generated precipitate was collected by filtration. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was poured into methanol for reprecipitation purification. The generated precipitate was collected, washed with ethanol, and then dried under reduced pressure to obtain 0.75 g of a polymer. The obtained polymer is called polymeric fluorescent substance 5.

Example 8 <Synthesis of polymeric fluorescent substance 6> 1.05 g of 4,4'-dibromuit {4 ''-(4-t-butylphenyl) ethenyl} triphenylamine and 1-methoxy-4-isoamyloxy- After dissolving 2.98 g of 2,5-dibromobenzene and 2.75 g of 2,2′-bipyridyl in 200 g of tetrahydrofuran (dehydrated), bubbling with nitrogen gas was performed to replace the inside of the system with nitrogen gas. Add bis (1,5-cyclooctadiene) nickel (0) {Ni (C
OD) ₂ } 5.0 g, and after stirring at room temperature for about 10 minutes,
The temperature was raised and the reaction was carried out at 60 ° C. for 3.5 hours. The reaction was carried out in a nitrogen gas atmosphere, and after cooling the reaction solution, 50 ml of 25% ammonia water was used.
/ Ethanol 100 ml / Ion-exchanged water 150 ml mixed solution was added, and the mixture was stirred for about 1 hour. This solution was allowed to stand overnight at room temperature, and the generated precipitate was collected by filtration. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was poured into methanol for reprecipitation purification. Collect the generated precipitate,
After washing with ethanol, this was dried under reduced pressure to obtain 0.15 g of a polymer. The obtained polymer is called polymeric fluorescent substance 6.

Example 9 <Synthesis of polymeric fluorescent substance 7> 0.44 g of 4,4'-dibromuu {4 ''-(4-t-butylphenyl) ethenyl} triphenylamine and 1-methoxy-4-isoamyloxy- After dissolving 2.38 g of 2,5-dibromobenzene and 2.75 g of 2,2′-bipyridyl in 200 g of tetrahydrofuran (dehydrated), bubbling with nitrogen gas was performed to replace the inside of the system with nitrogen gas. Add bis (1,5-cyclooctadiene) nickel (0) {Ni (C
OD) ₂ } 5.0 g, and after stirring at room temperature for about 10 minutes,
The temperature was raised and the reaction was carried out at 60 ° C. for 3.5 hours. The reaction was carried out in a nitrogen gas atmosphere, and after cooling the reaction solution, 50 ml of 25% ammonia water was used.
/ Ethanol 100 ml / Ion-exchanged water 150 ml mixed solution was added, and the mixture was stirred for about 1 hour. This solution was allowed to stand overnight at room temperature, and the generated precipitate was collected by filtration. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was washed with a 1N hydrochloric acid aqueous solution, and then further washed with ion-exchanged water. Next, toluene was distilled off from this toluene solution to obtain a precipitate. This precipitate was washed with ethanol and then dried under reduced pressure to give 0.37 g of a polymer.
Got The obtained polymer is called polymeric fluorescent substance 7.

Example 10 <Synthesis of polymeric fluorescent substance 8> 0.21 g of 4,4'-dibromuu {4 ''-(4-t-butylphenyl) ethenyl} triphenylamine and 9,9-dioctyl-2 ，
3.9 g of 7-dibromofluorene and 2.75 g of 2,2′-bipyridyl were dissolved in 200 g of tetrahydrofuran (dehydrated).
Then, the inside of the system was replaced with nitrogen gas. To this solution, 5.0 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added, stirred at room temperature for about 10 minutes, then heated to 3.5 at 60 ° C. Reacted for hours. The reaction was carried out in a nitrogen gas atmosphere, and after cooling the reaction solution, 50 ml of 25% ammonia water was used.
/ Methanol 100 ml / ion exchanged water 150 ml mixed solution was added, and the mixture was stirred for about 1 hour. This solution was allowed to stand overnight at room temperature, and the generated precipitate was collected by filtration. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with silica gel. Next, this toluene solution was poured into methanol for reprecipitation purification. The generated precipitate was collected, washed with ethanol, and then dried under reduced pressure to obtain 1.0 g of a polymer. The obtained polymer is used as polymeric fluorescent substance 8
Call.

Example 11 <Synthesis of polymeric fluorescent substance 9> 1.09 g of 4,4'-dibromuu {4 ''-(β, β-diphenyl) ethenyl} triphenylamine and 1,4-di (3,3) 7-Dimethyloctyloxy) -2,5-dibromobenzene 3.1 g
And 2.75 g of 2,2'-bipyridyl were dissolved in 200 g of tetrahydrofuran (dehydrated), and then nitrogen gas was bubbled to replace the system with nitrogen gas. Add bis (1,5-cyclooctadiene) nickel (0) {Ni (C
OD) ₂ } 5.0 g, and after stirring at room temperature for about 10 minutes,
The temperature was raised and the reaction was carried out at 60 ° C. for 3.5 hours. The reaction was carried out in a nitrogen gas atmosphere, and after cooling the reaction solution, 50 ml of 25% ammonia water was used.
/ Methanol 100 ml / ion exchanged water 150 ml mixed solution was added, and the mixture was stirred for about 1 hour. This solution was allowed to stand overnight at room temperature, and the generated precipitate was collected by filtration. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was poured into methanol for reprecipitation purification. Collect the generated precipitate,
After washing with ethanol, this was dried under reduced pressure to obtain 0.3 g of a polymer. The obtained polymer is called polymeric fluorescent substance 9.

Example 12 <Synthesis of polymeric fluorescent substance 10> 0.5 g of 4,4′-dibromuu {4 ″-(β, β-diphenyl) ethenyl} triphenylamine and 9,9-dioctyl-2 After dissolving 1.55 g of 7-dibromofluorene and 1.37 g of 2,2′-bipyridyl in 100 g of tetrahydrofuran (dehydrated), bubbling with nitrogen gas was performed to replace the inside of the system with nitrogen gas. To this solution, 2.5 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added,
After stirring at room temperature for about 10 minutes, the temperature was raised and the reaction was carried out at 60 ° C. for 3 hours. The reaction was conducted in a nitrogen gas atmosphere. After cooling the reaction solution, 25% ammonia water 25 ml /
A mixed solution of 100 ml of methanol / 150 ml of ion-exchanged water was added, and the mixture was stirred for about 1 hour. This solution was allowed to stand overnight at room temperature, and the generated precipitate was collected by filtration. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with silica gel. Next, this toluene solution was poured into methanol for reprecipitation purification. The produced precipitate was collected, washed with ethanol, and then dried under reduced pressure to obtain 0.4 g of a polymer. The polymer obtained is used as polymeric fluorescent substance 1
Call it 0.

Example 13 <Synthesis of polymeric fluorescent substance 11> 1.04 g of 4,4'-dibromuu {4 ''-(4-t-butylphenyl) ethenyl} triphenylamine and 4,4'-dibromo- Three
After 1.22 g of 3'-di (3,7-dimethyloctyloxy) stilbene and 1.37 g of 2,2'-bipyridyl were dissolved in 100 g of tetrahydrofuran (dehydrated), bubbling with nitrogen gas was performed to purge the system with nitrogen. The gas was replaced. To this solution, 2.5 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added, stirred for about 10 minutes at room temperature, then heated up and reacted at 60 ° C. for 3 hours. did. In addition,
The reaction was carried out in a nitrogen gas atmosphere. After cooling the reaction solution, 25% ammonia water 25 ml / methanol 100
A mixed solution of ml / ion-exchanged water (150 ml) was added, and the mixture was stirred for about 1 hour. This solution was allowed to stand overnight at room temperature, and the generated precipitate was collected by filtration. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with silica gel. Next, this toluene solution was poured into methanol for reprecipitation purification. The generated precipitate was collected, washed with ethanol, and then dried under reduced pressure to obtain 1.0 g of a polymer.
The obtained polymer is called polymeric fluorescent substance 11.

Example 14 <Synthesis of polymeric fluorescent substance 12> 0.14 g of 4,4'-dibromuu {4 ''-(4-t-butylphenyl) ethenyl} triphenylamine and 4,4'-dibromo- Three
After dissolving 3.75 g of 3'-di (3,7-dimethyloctyloxy) stilbene and 1.1 g of 2,2'-bipyridyl in 80 g of tetrahydrofuran (dehydrated), bubbling with a nitrogen gas was performed, and the system was replaced with nitrogen. The gas was replaced. To this solution, 2.0 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added, stirred for about 10 minutes at room temperature, then heated up and reacted at 60 ° C. for 3 hours. did. In addition,
The reaction was carried out in a nitrogen gas atmosphere. After cooling the reaction liquid, 25% ammonia water 20 ml / methanol 100
A mixed solution of ml / ion-exchanged water (150 ml) was added, and the mixture was stirred for about 1 hour. This solution was allowed to stand overnight at room temperature, and the generated precipitate was collected by filtration. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was poured into methanol for reprecipitation purification. The generated precipitate was collected, washed with ethanol, and then dried under reduced pressure to obtain 0.14 g of a polymer. The obtained polymer is called polymeric fluorescent substance 12.

Example 15 <Synthesis of polymeric fluorescent substance 13> 0.5 g of 4,4′-dibromuu {4 ″-(4-t-butylphenyl) ethenyl} triphenylamine and 4,4′-dibromo- Three
0.68 g of 3'-di (3,7-dimethyloctyloxy) stilbene, 0.37 g of 1-methoxy-4-isoamyloxy-2,5-dibromobenzene and 1.1 g of 2,2'-bipyridyl were added to tetrahydrofuran (dehydrated). ) 80 g
Then, the inside of the system was replaced with nitrogen gas. To this solution, 2.0 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added, and the mixture was stirred at room temperature for about 10 minutes and then heated to 60 ° C. for 3 minutes.
Reacted for hours. The reaction was conducted in a nitrogen gas atmosphere. After cooling the reaction solution, 25% ammonia water 20
ml / methanol 100 ml / ion exchanged water 150 ml
The mixed solution was added and stirred for about 1 hour. After leaving this solution at room temperature overnight, by filtering the generated precipitate,
Recovered. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was poured into methanol for reprecipitation purification. The produced precipitate was collected, washed with ethanol, and then dried under reduced pressure to obtain 0.55 g of a polymer. The obtained polymer is called polymeric fluorescent substance 13.

Example 16 <Synthesis of polymeric fluorescent substance 14> 0.14 g of 4,4'-dibromuu {4 ''-(4-t-butylphenyl) ethenyl} triphenylamine and 4,4'-dibromo- Three
0.88 g of 3'-di (3,7-dimethyloctyloxy) stilbene, 0.48 g of 1-methoxy-4-isoamyloxy-2,5-dibromobenzene and 1.1 g of 2,2'-bipyridyl were added to tetrahydrofuran (dehydrated). ) 80 g
Then, the inside of the system was replaced with nitrogen gas. To this solution, 2.0 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added, and the mixture was stirred at room temperature for about 10 minutes and then heated to 60 ° C. for 3 minutes.
Reacted for hours. The reaction was conducted in a nitrogen gas atmosphere. After cooling the reaction solution, 25% ammonia water 20
ml / methanol 100 ml / ion exchanged water 150 ml
The mixed solution was added and stirred for about 1 hour. After leaving this solution at room temperature overnight, by filtering the generated precipitate,
Recovered. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was poured into methanol for reprecipitation purification. The produced precipitate was collected, washed with ethanol, and then dried under reduced pressure to obtain 0.48 g of a polymer. The obtained polymer is called polymeric fluorescent substance 14.

Example 17 <Synthesis of polymeric fluorescent substance 15> 0.5 g of 4,4'-dibromuu {4 ''-(4-t-butylphenyl) ethenyl} triphenylamine and 4,4'-dibromo- Three
0.68 g of 3'-di (3,7-dimethyloctyloxy) stilbene, 0.58 g of 9,9-dioctyl-2,7-dibromofluorene and 1.1 g of 2,2'-bipyridyl
After dissolving and in 80 g of tetrahydrofuran (dehydrated),
The inside of the system was replaced with nitrogen gas by bubbling with nitrogen gas.
To this solution, 2.0 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added, and about 10
After stirring for 1 minute, the temperature was raised and the reaction was carried out at 60 ° C. for 3 hours. The reaction was conducted in a nitrogen gas atmosphere. After cooling the reaction liquid, 25% aqueous ammonia 20 ml / methanol 1
A mixed solution of 00 ml / 150 ml of ion-exchanged water was added, and the mixture was stirred for about 1 hour. This solution was allowed to stand overnight at room temperature, and the generated precipitate was collected by filtration. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with alumina.
Next, this toluene solution is poured into methanol,
It was reprecipitated and purified. The generated precipitate was collected, washed with ethanol, and then dried under reduced pressure to obtain 0.65 g of a polymer. The obtained polymer is called polymeric fluorescent substance 15.

Example 18 <Synthesis of polymeric fluorescent substance 16> 0.34 g of 4,4'-dibromuu {4 ''-(4-t-butylphenyl) ethenyl} triphenylamine and 4,4'-dibromo- Three
0.2 g of 3'-di (3,7-dimethyloctyloxy) stilbene, 0.74 of 1-methoxy-4-isoamyloxy-2,5-dibromobenzene and 1.1 g of 2,2'-bipyridyl were mixed with tetrahydrofuran (dehydrated). ) After being dissolved in 80 g, the inside of the system was replaced with nitrogen gas by bubbling with nitrogen gas. To this solution, 2.0 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added,
After stirring at room temperature for about 10 minutes, the temperature was raised and the reaction was carried out at 60 ° C. for 3 hours. The reaction was conducted in a nitrogen gas atmosphere. After cooling this reaction liquid, 20 ml of 25% aqueous ammonia /
A mixed solution of 100 ml of methanol / 150 ml of ion-exchanged water was added, and the mixture was stirred for about 1 hour. This solution was allowed to stand overnight at room temperature, and the generated precipitate was collected by filtration. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was poured into methanol for reprecipitation purification. Collect the generated precipitate,
After washing with ethanol, this was dried under reduced pressure to obtain 0.18 g of a polymer. The obtained polymer is used as polymeric fluorescent substance 16
Call.

Example 19 <Synthesis of polymeric fluorescent substance 17> Instead of 0.74 g of 1-methoxy-4-isoamyloxy-2,5-dibromobenzene, 9,9-dioctyl-2,7-dibromofluorene 1. A polymer (0.36 g) was obtained in the same manner as in Example 18 except that 15 g was used. The obtained polymer is called polymeric fluorescent substance 17.

Example 20 <Synthesis of polymeric fluorescent substance 18> 0.65 g of 4,4'-dibromuu {4 ''-(β, β-diphenyl) ethenyl} triphenylamine and 1-methoxy-4-isoamyloxy-2 , 5-dibromobenzene 0.93g and 2,2
After dissolving 1.38 g of'-bipyridyl in 100 g of tetrahydrofuran (dehydrated), bubbling with nitrogen gas was performed to replace the inside of the system with nitrogen gas. Add bis (1,
5-Cyclooctadiene) nickel (0) {Ni (COD) ₂ }
After adding 2.5 g and stirring at room temperature for about 10 minutes, it heated up and reacted at 60 degreeC for 3 hours. The reaction was conducted in a nitrogen gas atmosphere. After cooling this reaction liquid, a mixed solution of 20% 25% ammonia water / 100 ml methanol / 150 ml ion-exchanged water was added, and the mixture was stirred for about 1 hour. This solution was allowed to stand overnight at room temperature, and the generated precipitate was collected by filtration. Then, after drying this precipitate,
Dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was poured into methanol for reprecipitation purification. The generated precipitate was collected, washed with ethanol, and then dried under reduced pressure to obtain 0.1 g of a polymer. The obtained polymer is called polymeric fluorescent substance 18.

Example 21 <Synthesis of polymeric fluorescent substance 19> 1.18 g of 4,4'-dibromuu {4 ''-(4-t-butylphenyl) ethenyl} triphenylamine and 9,9-dioctyl-2 ，
After 0.49 g of 7-dibromofluorene and 1.1 g of 2,2'-bipyridyl were dissolved in 80 g of tetrahydrofuran (dehydrated), nitrogen gas was bubbled to replace the inside of the system with nitrogen gas. To this solution, 2.0 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added,
After stirring at room temperature for about 10 minutes, raise the temperature to 3.5 at 60 ° C.
Reacted for hours. The reaction was conducted in a nitrogen gas atmosphere. After cooling the reaction solution, 25% ammonia water 20
ml / methanol 150 ml / ion exchanged water 150 ml
The mixed solution was added and stirred for about 1 hour. After leaving this solution at room temperature overnight, by filtering the generated precipitate,
Recovered. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was poured into methanol for reprecipitation purification. The produced precipitate was collected, washed with ethanol, and then dried under reduced pressure to obtain 0.4 g of a polymer. The polymer obtained is used as polymeric fluorescent substance 1
Call it 9.

Example 22 <Synthesis of polymeric fluorescent substance 20> 1.18 g of 4,4'-dibromuu {4 ''-(4-t-butylphenyl) ethenyl} triphenylamine and 9,9-dioctyl-2 ，
Instead of 0.49 g of 7-dibromofluorene, 4,
0.84 g of 4'-dibromuu {4 ''-(4-t-butylphenyl) ethenyl} triphenylamine and 4,4
As in Example 21, except that 0.49 g of'-dibromo-3,3'-di (3,7-dimethyloctyloxy) stilbene and 0.41 g of 9,9-dioctyl-2,7-dibromofluorene were used. By the above method, 0.45 g of polymer was obtained. The obtained polymer is called polymeric fluorescent substance 20.

Example 23 <Synthesis of polymeric fluorescent substance 21> 4,4′-dibromuu {4 ″-(4-t-butylphenyl) ethenyl} triphenylamine 1.18 g and 4,4′-dibromo- Three
A polymer was prepared in the same manner as in Example 22 except that 0.29 g of 3'-di (3,7-dimethyloctyloxy) stilbene and 0.25 g of 9,9-dioctyl-2,7-dibromofluorene were used. 0.25 g was obtained. The obtained polymer is called polymeric fluorescent substance 21.

Example 24 <Synthesis of polymeric fluorescent substance 22> 0.5 g of 4,4'-dibromuu {4 ''-(β-naphthyl) ethenyl} triphenylamine and 9,9-dioctyl-2,7- 1.15 g of dibromofluorene and 1.1 g of 2,2'-bipyridyl
After dissolving and in 80 g of tetrahydrofuran (dehydrated),
The inside of the system was replaced with nitrogen gas by bubbling with nitrogen gas.
To this solution, 2.0 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } was added, and about 10
After stirring for 1 minute, the temperature was raised and the reaction was carried out at 60 ° C. for 3 hours. The reaction was conducted in a nitrogen gas atmosphere. After cooling the reaction liquid, 25% aqueous ammonia 20 ml / methanol 1
A mixed solution of 00 ml / 150 ml of ion-exchanged water was added, and the mixture was stirred for about 1 hour. This solution was allowed to stand overnight at room temperature, and the generated precipitate was collected by filtration. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with alumina.
Next, this toluene solution is poured into methanol,
It was reprecipitated and purified. The produced precipitate was collected, washed with ethanol, and then dried under reduced pressure to obtain 0.8 g of a polymer. The obtained polymer is called polymeric fluorescent substance 22.

Example 25 <Synthesis of polymeric fluorescent substance 23>4,4'-dibromuu {4 "-(β-naphthyl) ethenyl} triphenylamine Instead of 0.5 g of 4,4'-dibromomu { 0.39 g of a polymer was obtained by the same method as in Example 24 except that 0.52 g of 4 ″-(β-biphenyl) ethenyl} triphenylamine was used. The obtained polymer is called polymeric fluorescent substance 23.

Example 26 <Synthesis of polymeric fluorescent substance 24>4,4'-dibromuu {4 ''-(β-naphthyl) ethenyl} triphenylamine Instead of 0.5 g of 4,4'-dibromomu { 0.66 g of a polymer was obtained in the same manner as in Example 24 except that 0.48 g of 4 ″-(4-methoxyphenyl) ethenyl} triphenylamine was used. The obtained polymer is called polymeric fluorescent substance 24.

Example 27 <Synthesis of polymeric fluorescent substance 25> 0.6 g of 4,4'-dibromuu {4 ''-(4-methoxyphenyl) ethenyl} triphenylamine and 1-methoxy-4-isoamyloxy-2 , 5-dibromobenzene 0.92g and 2,2
After dissolving 1.38 g of'-bipyridyl in 100 g of tetrahydrofuran (dehydrated), bubbling with nitrogen gas was performed to replace the inside of the system with nitrogen gas. Add bis (1,
5-Cyclooctadiene) nickel (0) {Ni (COD) ₂ }
After adding 2.5 g and stirring at room temperature for about 10 minutes, it heated up and reacted at 60 degreeC for 3 hours. The reaction was conducted in a nitrogen gas atmosphere. After cooling this reaction liquid, a mixed solution of 20% 25% ammonia water / 100 ml methanol / 150 ml ion-exchanged water was added, and the mixture was stirred for about 1 hour. This solution was allowed to stand overnight at room temperature, and the generated precipitate was collected by filtration. Then, after drying this precipitate,
Dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was poured into methanol for reprecipitation purification. The produced precipitate was collected, washed with ethanol, and then dried under reduced pressure to obtain 0.4 g of a polymer. The obtained polymer is called polymeric fluorescent substance 25.

Example 28 <Synthesis of polymeric fluorescent substance 26> 4,4′-dibromuu {4 ″-(β-cyano-β- (4-methoxyphenyl)) ethenyl} triphenylamine 1.26 g and 9,
9-Dioctyl-2,7-dibromofluorene 2.88
g and 2.75 g of 2,2′-bipyridyl were dissolved in 200 g of tetrahydrofuran (dehydrated), and then bubbling with nitrogen gas was performed to replace the inside of the system with nitrogen gas. To this solution was added bis (1,5-cyclooctadiene) nickel (0) {Ni
(COD) ₂ } 5.0 g was added, and the mixture was stirred at room temperature for about 10 minutes, heated, and reacted at 60 ° C. for 3 hours. The reaction was conducted in a nitrogen gas atmosphere. After cooling this reaction liquid, a mixed solution of 100 ml of methanol / 200 ml of ion-exchanged water was added, and the mixture was stirred for about 1 hour. This solution was allowed to stand overnight at room temperature, and the generated precipitate was collected by filtration. Next, this precipitate was dried and then dissolved in toluene. After removing the insoluble matter by filtering, the toluene solution was purified by passing through a column packed with silica gel. Next, this toluene solution was poured into methanol for reprecipitation purification. The generated precipitate was collected, washed with ethanol, and then dried under reduced pressure to obtain 1.0 g of a polymer. The obtained polymer is used as polymeric fluorescent substance 2
Call 6.

Example 29 <Synthesis of polymeric fluorescent substance 27>4,4'-dibromuu {4 "-(β-naphthyl) ethenyl} triphenylamine Instead of 0.5 g of 4,4'-dibromuu { 4 ″-(2,4-dimethoxyphenyl) ethenyl}
0.37 g of a polymer was obtained by the same method as in Example 24 except that 0.45 g of triphenylamine was used. The obtained polymer is called polymeric fluorescent substance 27.

Example 30 <Synthesis and fluorescent characteristics of polymeric fluorescent substances 5 to 27> The charging ratios of the monomers used for the synthetic polymeric fluorescent substances 5 to 27 and the structures of repeating units are shown in Table 1. Further, the fluorescence spectra of polymeric fluorescent substances 4 to 27 were measured by the same method as in Example 5. Table 2 shows the average molecular weights of the polymeric fluorescent substances 5 to 27, the relative values of the fluorescent peak wavelength and the fluorescent intensity. All polymeric fluorescent substances had strong visible fluorescence. In addition, the fluorescence intensity when excited at 350 nm was used for the calculation of the fluorescence intensity. The area of the fluorescence spectrum plotted with the wave number plotted on the horizontal axis was divided by the absorbance at 350 nm to determine the relative value of the fluorescence intensity.

[0158]

[Table 1]

Abbreviations for repeating units and structure F8: ST10: PP5: PP10: (Here, C ₁₀ H ₂₁ represents a 3,7-dimethyloctyl group and C ₅ H ₁₁ represents an isoamyl group.) TPAST-tBu: TLAST-Ph2: TLAST-N: TLAST-BPh: TLAST-OMe: TLAST (CN) Ph: TLAST- (OMe) 2:

[0160]

[Table 2]

Examples 31 to 40 <Fabrication and Evaluation of Device> A 1.5 wt% toluene solution of each polymeric fluorescent substance was spin-coated to form a light-emitting layer, and a cathode was charged with about 4 n of lithium fluoride.
A polymer LED was produced in the same manner as in Example 6, except that m, calcium of about 5 nm, and aluminum of about 50 nm were sequentially deposited. By applying a voltage to the obtained device, EL light emission was obtained from each polymeric fluorescent substance used. The characteristics are shown in Table 3.

[0162]

[Table 3] Here, the light emission start voltage means a voltage (V) when light emission of 1 cd or more is observed.

[0163]

INDUSTRIAL APPLICABILITY The polymeric fluorescent substance of the present invention is a triarylamine-based polymeric fluorescent substance, and is excellent in the quantum yield of fluorescence and the luminous efficiency of a device. Therefore, the polymer LED using the polymer fluorescent substance can be preferably used as a device such as a planar light source as a backlight and a flat panel display.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05B 33/22 H05B 33/22 ZF term (reference) 2H091 FA43Z FA45Z LA17 LA18 3K007 AB03 AB18 BA06 DB03 EA00 FA01 4J032 CA12 CA14 CB03 CG02 CG08

Claims (11)

[Claims] 1. A repeating unit represented by the following formula (1), having visible fluorescence in a solid state, and having a polystyrene-equivalent number average molecular weight of 1 × 10 ³ to 1 × 10 ^8. Polymer fluorescent substance. [In the formula, Ar ₁ and Ar ₂ each independently represent an arylene group or a divalent heterocyclic group. Ar ₃ is an aryl group having one or more substituents represented by the following formula (2) as nuclear substitution or a monovalent heterocyclic group having one or more substituents represented by the following formula (2) as nuclear substitution. Represent X is
-CR ₁ = CR ₂ - or an -C≡C-. 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. n represents 0 or 1. ] -Y-Ar ₄ (2) wherein, Ar ₄ represents an aryl group, monovalent heterocyclic group or monovalent aromatic amine group. Y is, -CR ₃ = CR ₄
-Or-C represents C-. R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. ] 2. The polymeric fluorescent substance according to claim 1, further comprising a repeating unit represented by the formula (3). —Ar ₅ — (Z) _p — (3) [In the formula, Ar ₅ represents an arylene group or a divalent heterocyclic group. Z is, -CR ₅ = CR ₆ - represents a or -C≡C-. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. p represents 0 or 1. ] 3. The polymeric fluorescent substance according to claim 1, wherein the total of the repeating units represented by the formula (1) is 1 mol% or more and 100 mol% or less of all the repeating units. 4. The polymeric fluorescent substance according to claim 2, wherein the total of repeating units represented by the formulas (1) and (3) is 50 mol% or more of all repeating units contained in the polymeric fluorescent substance. And the repeating unit represented by the formula (1) is 2 mol% or more and 90 mol% or less with respect to the total of the repeating units represented by the formulas (1) and (3). The polymeric fluorescent substance described. 5. A polymer light emitting device having a light emitting layer between electrodes composed of an anode and a cathode, wherein the light emitting layer contains the polymer fluorescent substance according to any one of claims 1 to 4. . 6. The polymer light emitting device according to claim 5, wherein a layer containing a conductive polymer is provided between at least one electrode and the light emitting layer adjacent to the electrode. 7. The polymer light emitting device according to claim 5, wherein an insulating layer having a film thickness of 2 nm or less is provided between at least one electrode and the light emitting layer adjacent to the electrode. 8. A planar light source comprising the polymer light emitting device according to claim 5. 9. A segment display device comprising the polymer light emitting device according to claim 5. 10. A dot matrix display device comprising the polymer light emitting device according to claim 5. 11. A liquid crystal display device comprising the polymer light emitting device according to claim 5 as a backlight.