JP2000282025A - Material for light emission element and light emission element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject material capable of driving at a low voltage and emitting high luminance and excellent in durability even when repeatedly used by constituting the material with a polymer having a specific partial structure. SOLUTION: The objective light emitting material is obtained by constituting the material with a polymer having a partial structure expressed by formula I in a main chain and/or side chain of the polymer. As the polymer, a polymer containing at least one of repeating units expressed by formulas II, III or IV (R2c, R2d, R2e, R3c, R3d, R3f, R4c, R4d and R4f are each a substituent; R3e and R4e are each H or a substituent; 2p, 2q, 2r, 3p, 3r and 4r are each 0-4; 3q, 4p and 4q are each 0-3; L2, L3 and L4 are each a single bond or a divalent bonding group; R21 and R31 are each H, an alkyl or an aryl; m2, m3 and m4 are each >=1) is preferable. The number average molecular weight of the polymer having the partial structure expressed by formula I is preferably 2,000-500,000, and the weight average molecular weight is preferably 2,000-1,500,000. In formulas II-IV, m2, m3 and m4 are each preferably 60,000-100,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light emitting device material capable of emitting light by converting electric energy into light and a light emitting device using the same, and more particularly, to a display device, a display, a backlight, an electrophotograph, an illumination light source, and a recording device. The present invention relates to a light emitting element that can be suitably used in fields such as a light source, a reading light source, a sign, a signboard, and an interior.

[0002]

2. Description of the Related Art At present, research and development on various display elements are active. Among them, organic light-emitting elements have attracted attention as promising display elements because they can obtain high-luminance light emission at a low voltage. For example, a light emitting device that forms an organic thin film by vapor deposition of an organic compound is known (Applied
Physics Letters, 51, 913, 1987
Year). However, production of a light-emitting element involving an operation of vapor-depositing an organic compound has a problem in productivity, and production of a light-emitting element by a coating method is desirable from the viewpoint of simplification of a production process, workability, and increase in area.

As a light emitting device material used for manufacturing a light emitting device by a coating method which is advantageous in productivity, for example, a π-conjugated polymer represented by paraphenylene vinylene is known. Because of the chain, it is difficult to control the concentration of the light emitting material, and it is difficult to finely control the color tone and the light emission intensity. Similarly, as a light-emitting element using a coating method, for example, there is an element in which a low-molecular-weight fluorescent compound is dispersed in poly (N-vinylcarbazole) (JP-A-4-212286). In this method, since the kind of the fluorescent compound can be arbitrarily changed, it is relatively easy to adjust the color tone and the emission intensity.However, when the driving voltage is high, and when driving after a long time lapse or when driving continuously, There was also a problem in terms of durability, such as a tendency for brightness to drop.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, an object of the present invention is to provide a light-emitting element material that can be driven at low voltage and emit light with high luminance and has excellent durability even when used repeatedly, and a light-emitting element using the same.

[0005]

Means for solving the above problems are as follows. That is, <1> a light emitting element material comprising a polymer having a partial structure represented by the following general formula (I).

[0006]

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<2> A light-emitting element material comprising a polymer containing at least one repeating unit represented by the following general formula (II):

[0008]

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(In the general formula (II), R _2c , R _2d and R _2c
2e each independently represents a substituent. 2p, 2q and 2
r represents an integer of 0 to 4, respectively. 2p, 2q and 2
When r is 2 or more, R _2c , R _2d and R _2e are
Each may be the same or different from each other. L
₂ represents a single bond or a divalent linking group. R ₂₁ represents a hydrogen atom, an alkyl group or an aryl group. m ₂ represents an integer of 1 or more. <3> A light-emitting device material comprising a polymer containing at least one repeating unit represented by the following general formula (III).

[0010]

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[0011] (In the general formula (III), R _3e is, .R _3c represents a hydrogen atom or a substituent, R _3d and R _{3 f} are, .3P and 3r independently represent a substituent of 0-4 Represents an integer,
3q represents an integer of 0 to 3. When each of 3p, 3q, and 3r is 2 or more, R _3c , R _3d, and R _3f may be the same or different from each other. L ₃ represents a single bond or a divalent linking group. R ₃₁ represents a hydrogen atom, an alkyl group or an aryl group. m ₃ represents an integer of 1 or more. <4> A light-emitting device material comprising a polymer containing at least one repeating unit represented by the following general formula (IV).

[0012]

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[0013] (In the general formula (IV), R _4e is .R _4c represents a hydrogen atom or a substituent, R _4d and R _{4 f} is .4P and 4q each independently represents a substituent, respectively 0 Represents an integer of 3. 4r represents an integer of 0 to 4. When 4p, 4q and 4r are each 2 or more, R _4c , R _4d and R
_4f may be the same or different from each other. L ₄ represents a single bond or a divalent linking group. m ₄ represents an integer of 1 or more. <5> m ₂ in the general formula (II) is from 6 to 1,000.
00 is the light emitting device material according to <2>. <6> m ₃ in the general formula (III) is from 6 to 1,000.
00 is the light emitting device material according to <3>. <7> m ₄ in the general formula (IV) is from 6 to 1000
00 is the light emitting device material according to <4>. <8> In a light-emitting element having a light-emitting layer or a plurality of organic compound thin layers including the light-emitting layer between a pair of electrodes, at least one of the light-emitting element materials according to any one of the above <1> to <7> Is a light emitting element characterized by containing <9> In a light emitting element having a light emitting layer or a plurality of organic compound thin layers including the light emitting layer between a pair of electrodes, at least one of the light emitting element materials according to any one of the above <1> to <7> A light-emitting element characterized in that it is a layer formed by applying a liquid crystal.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the light emitting device material of the present invention will be described in detail. [Light Emitting Element Material] The light emitting element material of the present invention is composed of a polymer having a partial structure represented by the following general formula (I), and the polymer is a substance that controls light emission in the present invention.

[0015]

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The polymer in the present invention has a partial structure represented by the above general formula (I) in the main chain and / or side chain of the polymer, and preferably has the following general formula (II):
It is a polymer containing at least one repeating unit represented by (III) or (IV).

[0017]

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[0018]

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[0019]

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In the above general formulas (II) to (IV), R _2c , R _2d ,
_{R 2e, R 3c, R 3d} , R 3f, R 4c, R 4 d and R _4f are each independently represent a substituent. R _2c , R _2d , R _2e , R _3c , R
_{As the} substituent represented by _3d , R _3f , R _4c , R _4d and R _4f , for example, an alkyl group (preferably having 1 to 30 carbon atoms,
More preferably, it has 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl , Cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 carbon atoms)
-20, particularly preferably 2-10 carbon atoms, such as vinyl, allyl, 2-butenyl, 3-pentenyl and the like. ), An alkynyl group (preferably having 2 to 3 carbon atoms)
It has 0, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include propargyl and 3-pentynyl. ),

An aryl group (preferably having 6 to 30 carbon atoms;
More preferably, it has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, and naphthyl. ), An amino group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, for example, amino,
Methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, di (4-methoxyphenyl) amino, N-phenyl-N-
(1-Naphthyl) amino, N-phenyl-N- (1-thienyl) amino and the like. ), An alkoxy group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 2 carbon atoms)
0, particularly preferably 1 to 10 carbon atoms, for example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy and the like. ), An aryloxy group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, and 2-naphthyloxy. No.),

An acyl group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, particularly preferably having 2 carbon atoms)
To 12, for example, acetyl, benzoyl, formyl, pivaloyl and the like. ), An alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 12 carbon atoms,
For example, methoxycarbonyl, ethoxycarbonyl and the like can be mentioned. ), An aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably having 7 to 20 carbon atoms,
Particularly preferably, it has 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonyl. ), An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy). Has 2 to 30 carbon atoms,
More preferably, it has 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and includes, for example, acetylamino, benzoylamino and the like. ), An alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 12 carbon atoms, and examples include methoxycarbonylamino).

An aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms, more preferably having 7 to 2 carbon atoms)
0, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino. ), A sulfonylamino group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 1 carbon atoms)
2, for example, methanesulfonylamino, benzenesulfonylamino and the like. ), A sulfamoyl group (preferably having 0 to 30, more preferably 0 to 20, and particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl) A carbamoyl group (preferably having 1 to 30 carbon atoms).
More preferably, it has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl. ), An alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio and ethylthio).

An arylthio group (preferably having 6 to 3 carbon atoms)
It has 0, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio. ), A sulfonyl group (preferably having 1 to 30 carbon atoms,
More preferably, it has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include mesyl and tosyl. ), Sulfinyl group (preferably having 1 to 30 carbon atoms,
More preferably, it has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methanesulfinyl, benzenesulfinyl and the like. ), A ureido group (preferably 1 to 30 carbon atoms, more preferably 1 to 2 carbon atoms)
0, particularly preferably 1 to 12 carbon atoms, for example, ureido, methylureide, phenylureide and the like. ), A phosphoric amide group (preferably having 1 to 3 carbon atoms)
0, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, diethylphosphoramide,
And phenylphosphoramide. ), Hydroxy, mercapto, halogen (eg, fluorine, chlorine, bromine, iodine), cyano, sulfo, carboxyl, nitro, hydroxamic acid, sulfino, hydrazino, imino ,

A heterocyclic group (preferably having 1 to 30 carbon atoms;
More preferably, it has 1 to 12 carbon atoms, and as the hetero atom, for example, a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, benzoxazolyl, Benzimidazolyl, benzthiazolyl, furyl, thienyl and the like. ), A silyl group (preferably having 3 carbon atoms)
-40, more preferably 3-30 carbon atoms, particularly preferably 3-24 carbon atoms, for example, trimethylsilyl,
Triphenylsilyl and the like. ) And the like. These substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be linked to form a ring.

The above R _2c , R _2d , R _2e , R _3c , R _3d ,
R _3f , R _4c , R _4d and R _4f are preferably an alkyl group, an alkenyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group,
Acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group,
Sulfamoyl group, carbamoyl group, alkylthio group,
An arylthio group, a sulfonyl group, a halogen atom, a cyano group, and a heterocyclic group, more preferably an alkyl group, an alkenyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a halogen atom, and an aromatic heterocyclic group And particularly preferably an alkyl group, an alkenyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, and an aromatic heterocyclic group.

In the general formulas (II) to (IV), 2p, 2q,
2r, 3p, 3r and 4r each represent an integer of 0 to 4, preferably 0, 1, 2, 3; more preferably 0, 1, 2; and particularly preferably 0, 1. 3
q, 4p and 4q each represent an integer of 0 to 3, preferably 0, 1, or 2, more preferably 0 or 1, and particularly preferably 0. 2p, 2q, 2r,
3p, 3q, 3r, 4p, 4q and 4r are each 2
In the above case, R _2c , R _2d , R _2e , R _3c , R _3d ,
R _3f , R _4c , R _4d and R _4f may be the same,
They may be different from each other. Further, they may be connected to each other to form a ring if possible.

In the above general formulas (III) and (IV), R _3e and R 3
_4e each independently represents a hydrogen atom or a substituent. Examples of the substituent represented by R _3e and R _4e include, for example, an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms,
For example, methyl, ethyl, iso-propyl, tert
-Butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), Alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, for example, vinyl, allyl,
2-butenyl, 3-pentenyl and the like. ), An alkynyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 10 carbon atoms, and examples thereof include propargyl and 3-pentynyl).

An aryl group (preferably having 6 to 30 carbon atoms;
More preferably, it has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, and naphthyl. ), An acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, for example, acetyl, benzoyl, formyl, pivaloyl, etc.), and alkoxy. Carbonyl group (preferably having 2 carbon atoms)
-30, more preferably 2-20 carbon atoms, particularly preferably 2-12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl and the like. ), An aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably having 7 to 20 carbon atoms, particularly preferably having 7 to 7 carbon atoms)
12, for example, phenyloxycarbonyl and the like. ), A sulfamoyl group (preferably having 0 carbon atoms)
-30, more preferably 0-20, particularly preferably 0-12, examples of which include sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl and the like. ),

Carbamoyl group (preferably having 1 to 3 carbon atoms)
It has 0, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl. ), A sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, particularly preferably having 1 to 12 carbon atoms, and examples thereof include mesyl and tosyl.) And a sulfinyl group (preferably It has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methanesulfinyl, benzenesulfinyl and the like.), A phosphoric amide group (preferably 1 carbon atom) -30, more preferably 1-20 carbon atoms, particularly preferably 1-12 carbon atoms, for example, diethylphosphoramide, phenylphosphoramide and the like.)

A heterocyclic group (preferably having 1 to 30 carbon atoms;
More preferably, it has 1 to 12 carbon atoms, and as the hetero atom, for example, a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, benzoxazolyl, Benzimidazolyl, benzthiazolyl, furyl, thienyl and the like. ), A silyl group (preferably having 3 carbon atoms)
-40, more preferably 3-30 carbon atoms, particularly preferably 3-24 carbon atoms, for example, trimethylsilyl,
Triphenylsilyl and the like. ) And the like. These substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be linked to form a ring.

R _3e and R _4e are preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, and a heterocyclic group, more preferably an alkyl group, An aryl group and an aromatic heterocyclic group are preferable, an aryl group and an aromatic heterocyclic group are more preferable, and an aryl group is particularly preferable.

In the above general formulas (II) to (IV), L_Two, L_Threeas well as
L_FourRepresents a single bond or a divalent linking group, respectively. Said
L_Two, L_ThreeAnd L_FourThe divalent linking group represented by
And may be linear, branched or cyclic, for example, -O
-, -S-, -SO-, -SO_Two-, -N (R₁)-(R
₁Represents a hydrogen atom or a substituent, and the substituent includes R
_2c, R_2d, R _2e, R_3c, R_3d, R_3f, R_4c, R_4dAnd R
_4fThe examples given as examples of the substituent represented by are applicable.
You. R₁Preferably a hydrogen atom, an aliphatic hydrocarbon
Group, aryl group or heterocyclic group, more preferably water
Atom, alkyl group, aryl group, heterocyclic group
You. ), -N =, -N = N-, -CO-, -SiR
_Two(R_Three)-(R_TwoAnd R_ThreeIs a hydrogen atom, an aliphatic
Represents a hydrocarbon group, an aryl group, or a heterocyclic group, and is preferably
Is an aliphatic hydrocarbon group, an aryl group, a heterocyclic group,
More preferably an aliphatic hydrocarbon group, an aryl group,
Particularly preferred are an alkyl group, an alkenyl group, and an aryl group
It is. ) Divalent aliphatic hydrocarbon group (alkylene group,
Alkenylene group, alkynylene group, or a combination thereof
), An arylene group, a divalent heterocyclic group,
Groups composed of these combinations are exemplified. These groups are substituted
And may have a group represented by R_2cOf the substituent
The ones mentioned as examples can be applied.

L ₂ is preferably a divalent linking group containing a single bond, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, and an aromatic heterocyclic group, more preferably a single bond, an arylene group, And a divalent aromatic heterocyclic group, more preferably a single bond and an arylene group, particularly preferably a single bond, a phenylene group and a biphenylene group, and most preferably a phenylene group. Preferred examples of the L _2, in addition to a single bond, include the linking group represented by the following structural formula.

[0035]

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[0036]

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[0037]

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L ₃ is preferably a single bond, —O
—, —N (R ₁ ) —, —CO—, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent aromatic heterocyclic group, and a divalent linking group composed of a combination thereof. Preferred are a single bond, an arylene group and a divalent aromatic heterocyclic group, more preferred are a single bond and an arylene group, and particularly preferred is a single bond. Preferred specific examples of L ₃ include a single bond and a linking group represented by the following structural formula.

[0039]

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[0040]

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L ₄ is preferably a single bond, —O
—, —N (R ₁ ) —, —CO—, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent aromatic heterocyclic group, and a divalent linking group composed of a combination thereof. Preferably a single bond, -O-, -N
(R ₁ ) —, —CO—, an alkylene group, an alkenylene group, an arylene group, a divalent aromatic heterocyclic group, and a divalent linking group composed of a combination thereof. Preferred specific examples of L ₄ include a single bond and a linking group represented by the following structural formula.

[0042]

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[0043]

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[0044]

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[0045]

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In the general formulas (II) and (III), R ₂₁ and R
₃₁ represents a hydrogen atom, an alkyl group or an aryl group, respectively. As the alkyl group represented by R ₂₁ and R ₃₁ ,
Preferably it has 1 to 30 carbon atoms, more preferably 1 to 30 carbon atoms.
20, particularly preferably 1 to 10 carbon atoms, for example,
Examples include methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. As the aryl group represented by R ₂₁ and R ₃₁ ,
Preferably it has 6 to 30 carbon atoms, more preferably 6 to 30 carbon atoms.
20, particularly preferably having 6 to 12 carbon atoms, for example, phenyl, p-methylphenyl, naphthyl and the like.

An alkyl group represented by R ₂₁ and R ₃₁ ,
The aryl group may have a substituent, and as the substituent,
For example, those exemplified as the substituent for R _2c can be applied. R ₂₁ and R ₃₁ are preferably a hydrogen atom and an alkyl group, more preferably a hydrogen atom and a lower alkyl group, still more preferably a hydrogen atom and a methyl group, and particularly preferably a hydrogen atom.

In the general formulas (II) to (IV), m ₂ , m ₃ and m ₄ each represent an integer of 1 or more, preferably 6 to
100,000, more preferably 10 to 10,000
And particularly preferably 10 to 5000.

The polymer containing at least one repeating unit represented by the general formula (II) is more preferably a polymer containing at least one repeating unit represented by the following general formula (II-A). .

[0050]

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In the general formula (II-A), R_2c, R_2d, R
_2e, 2p, 2q, 2r, R_{twenty one}And m _TwoAre respectively
It is synonymous with those in formula (II) and is also preferred
The same is true for the range. In the general formula (II-A), n_TwoIs
Represents an integer of 0 to 4, preferably 0, 1, 2, 3
And more preferably 0, 1, and 2, still more preferably
It is 0 or 1 and particularly preferably 1.

The polymer having the partial structure represented by the general formula (I) may be a homopolymer or a copolymer with another monomer. Further, it may be a random copolymer or a block copolymer. The number average molecular weight (Mn) of the polymer having the partial structure represented by the general formula (I) varies depending on the type of the substituent and is not uniform, but is preferably from 2000 to 500,000, more preferably 3000. ３０300,000, particularly preferably 3,000 to 200,000. Weight average molecular weight (M
w) also varies depending on the type of the substituent, and thus is not uniform.
It is preferably 2000 to 1.5 million, more preferably 3000 to 1,000,000, and particularly preferably 3000 to 1,000,000.
500,000.

Further, the polymer in the present invention may contain a skeleton portion having a hole transporting function, an electron transporting function or a light emitting function in the compound. Hereinafter, specific examples of the polymer in the present invention are shown, but the present invention is not limited to these.

[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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The polymerization method of the polymer in the present invention is not particularly limited, and examples thereof include a radical polymerization method, an ionic polymerization method, and an oxidative polymerization method, and a radical polymerization method is preferable. Examples of the initiator of the radical polymerization method include azo compounds and peroxides, and azobisisobutyronitrile, azobisisobutyric acid diester derivatives, and dibenzoyl peroxide are preferred.

The polymerization solvent is not particularly limited. For example, aromatic hydrocarbons (eg, benzene, toluene, etc.), halogenated hydrocarbons (eg, dichloroethane, chloroform, etc.), ethers (eg, tetrahydrofuran,
Dioxane), amides (eg, dimethylformamide, dimethylacetamide, etc.), esters (eg, ethyl acetate, etc.), alcohols (eg, methanol, etc.), ketones (eg, acetone, cyclohexanone, etc.). . Depending on the selection of the solvent, solution polymerization in which polymerization is performed in a homogeneous system or precipitation polymerization in which the generated polymer precipitates can be performed.

Hereinafter, the method for synthesizing the polymer according to the present invention will be described with reference to specific examples. Synthesis example. Synthesis of Exemplified Compound 16

[0082]

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9H-Tribenz [b, d, f] azepine (J. Org. Chem., 56, 3906 (199)
9.2 g (38 mmol), 1,4
-Dibromobenzene 44.8 g (190 mmol), potassium hydroxide 5.6 g (100 mmol), copper powder 1.6
g (25 mmol) and 50 ml of decalin,
The mixture was heated and stirred at an external temperature of 200 ° C. for 36 hours under a nitrogen stream. After the reaction solution was returned to near room temperature, chloroform was added thereto, and the mixture was filtered through celite to remove insolubles, and the filtrate was concentrated. To remove decalin, add n-hexane to the residue and filter the solid,
The resulting solid is purified by silica gel column chromatography to give 9- (4-bromophenyl) -9H-tribenz [b, d, f] azepine (A).
Was obtained (yield 25%).

Next, 3.0 g of the azepine (A) (7.
5 mmol) in 20 ml of tetrahydrofuran,
41 mg (0.075 mmol) of (1,3-bisdiphenylphosphinopropane) dichloronickel was contained therein.
1) In addition, the mixture was stirred at 0 ° C. under a nitrogen stream. Into it, 9.0 ml (9.0 mmol) of a 0.1 M solution of vinylmagnesium bromide in tetrahydrofuran was added using a syringe.
After about 2 hours, water was added to the reaction solution, extracted with chloroform, post-treated and concentrated, and the purified product was purified by silica gel column chromatography to obtain 1.9 g of a vinyl monomer (B) (yield). 74%).

10 g of the vinyl monomer (B) was dissolved in 70 ml of toluene, and azobisisobutyronitrile (AIBN) was added to 0.3 ml of the solution while stirring at 75 ° C. under a nitrogen atmosphere.
g was added and stirred for 2 hours. After that, further increase AIBN by 0.3
g, and the mixture was stirred for 4 hours, cooled to room temperature, added with methanol, and reprecipitated. The precipitate was filtered, washed with methanol, and then dried to give 7.8 g of Exemplified Compound 16.
Obtained. As a result of measuring GPC, the weight average molecular weight (in terms of polystyrene) was 40,200.

The light emitting device material of the present invention comprising the polymer described above may be used for any of a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and a light emitting layer in a light emitting device. And preferably a hole injection layer, a hole transport layer, and a light emitting layer, and more preferably a hole injection layer and a hole transport layer.

[Light Emitting Element] Hereinafter, the light emitting element of the present invention will be described. The light-emitting element of the present invention is an element having a plurality of organic compound thin layers including a light-emitting layer or a light-emitting layer between a pair of anode and cathode electrodes, and in addition to the light-emitting layer, a hole injection layer, a hole transport layer, An organic compound thin layer such as an electron injection layer and an electron transport layer, a protective layer, and the like may be provided, and each of these layers may have another function.
At least one of the organic compound thin layers contains the light emitting device material of the present invention. The light emitting device material of the present invention to be contained may be used alone or in combination of two or more.

The anode supplies holes to the hole injection layer, the hole transport layer, the light emitting layer and the like, and uses a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof. And a material having a work function of 4 eV or more. Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO); metals such as gold, silver, chromium, and nickel; and those metals and conductive metal oxides. And mixtures thereof, copper iodide, inorganic conductive substances such as copper sulfide, polyaniline, polythiophene, organic conductive materials such as polypyrrole, and a laminate of these with ITO, and the like.
Preferably, a conductive metal oxide, particularly, productivity,
ITO is preferable in terms of high conductivity, transparency, and the like. The thickness of the anode can be appropriately selected depending on the material.
0 nm to 5 μm is preferable, 50 nm to 1 μm is more preferable, and 100 nm to 500 nm is particularly preferable.

The anode is usually formed of a layer on soda lime glass, non-alkali glass, a transparent resin substrate or the like. When glass is used, it is preferable to use non-alkali glass in order to reduce ions eluted from the glass. Further, when soda lime glass is used, it is preferable to use a glass coated with a barrier coat such as silica. The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength. When glass is used, the thickness is usually 0.2 mm or more, preferably 0.7 mm or more. For the production of the anode,
Various methods are used depending on the material.
In the case of O, a film is formed by a method such as an electron beam method, a sputtering method, a resistance heating evaporation method, a chemical reaction method (such as a sol-gel method), or a method of applying a dispersion of indium tin oxide. The anode can reduce the driving voltage of the element or increase the luminous efficiency by washing or other treatment. For example, I
In the case of TO, UV-ozone treatment or the like is effective.

The cathode supplies electrons to the electron injection layer, the electron transport layer, the light emitting layer, and the like. The negative electrode, such as the electron injection layer, the electron transport layer, and the light emitting layer, has adhesion and ionization. It is selected in consideration of potential, stability, etc. As the material of the cathode, a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used,
Specific examples include alkali metals (eg, Li, Na,
K or the like, a fluoride thereof, an alkaline earth metal (for example,
Mg, Ca, etc.) or fluorides thereof, gold, silver, lead, aluminum, sodium-potassium alloy or mixed metal thereof, lithium-aluminum alloy or mixed metal thereof, magnesium-silver alloy or mixed metal thereof, indium, Rare earth metals such as ytterbium;
Preferably, the material has a work function of 4 eV or less, and more preferably, aluminum, a lithium-aluminum alloy or a mixed metal thereof, a magnesium-silver alloy or a mixed metal thereof, or the like.

The thickness of the cathode can be appropriately selected depending on the material, but is usually preferably 10 nm to 5 μm, and 50 nm
m-1 μm is more preferable, and 100 nm-1 μm is particularly preferable. A method such as an electron beam method, a sputtering method, a resistance heating evaporation method, or a coating method is used for manufacturing the cathode, and a metal can be evaporated alone or two or more components can be evaporated simultaneously. Furthermore, it is possible to form an alloy electrode by simultaneously depositing a plurality of metals, or an alloy prepared in advance may be deposited. The sheet resistance of the anode and the cathode is preferably low, and several hundred Ω /
□ The following is preferred.

The material of the light emitting layer is capable of injecting holes from an anode, a hole injecting layer, or a hole transporting layer and applying electrons from a cathode, an electron injecting layer, or an electron transporting layer when an electric field is applied. Any function can be used as long as it can form a layer having a function of being injected, a function of transferring injected charges, and a function of providing a field of recombination of holes and electrons and emitting light. . A light emitting material other than the light emitting element material of the present invention may be used for the light emitting layer. For example, benzoxazole derivative, benzimidazole derivative, benzothiazole derivative, styrylbenzene derivative, polyphenyl derivative, diphenylbutadiene derivative, tetraphenylbutadiene derivative, naphthalimide derivative, coumarin derivative, perylene derivative, perinone derivative, oxadiazole derivative, aldazine Derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives,
Pyrrolopyridine derivatives, thiadiazolopyridine derivatives,
Examples thereof include cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidin compounds, various metal complexes represented by 8-quinolinol derivatives and rare earth complexes, and polymer compounds such as polythiophene, polyphenylene, and polyphenylenevinylene.

The thickness of the light emitting layer is not particularly limited, but is generally preferably 1 nm to 5 μm, and preferably 5 nm to 5 μm.
1 μm is more preferable, and 10 nm to 500 nm is particularly preferable. The method for forming the light emitting layer is not particularly limited, but includes resistance heating evaporation, electron beam, sputtering, molecular lamination, coating (spin coating, casting, dip coating, etc.), LB, etc. A method is used, preferably a resistance heating evaporation or coating method.

The material of the hole injection layer and the hole transport layer has a function of injecting holes from the anode, a function of transporting holes, or a function of blocking electrons injected from the cathode. Anything is acceptable. Specific examples thereof include, in addition to the light emitting device material of the present invention, a carbazole derivative, a triazole derivative, an oxazole derivative, an oxadiazole derivative, an imidazole derivative, a polyarylalkane derivative, a pyrazoline derivative, a pyrazolone derivative, a phenylenediamine derivative, and an arylamine. Derivatives, amino-substituted chalcone derivatives, styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives,
Silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline copolymers, thiophene oligomers, polythiophenes, etc. Conductive polymer oligomers and the like can be mentioned.

The thickness of the hole injection layer and the hole transport layer is not particularly limited, but is usually preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and more preferably 10 nm to 5 μm.
00 nm is particularly preferred. The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. Good.

The hole injecting layer and the hole transporting layer may be formed by a vacuum deposition method, an LB method, or a method in which a hole injecting and transporting agent is dissolved or dispersed in a solvent and coated (spin coating, casting, Dip coating method) is used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. Examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, and poly ( N-vinylcarbazole), hydrocarbon resins, ketone resins, phenoxy resins, polyamides, ethyl cellulose, vinyl acetate, ABS resins, polyurethanes, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, silicone resins, and the like.

The material of the electron injection layer and the electron transport layer has a function of injecting electrons from a cathode, a function of transporting electrons, or a function of blocking holes injected from an anode. I just need. Specific examples thereof include, in addition to the light emitting device material of the present invention, a triazole derivative, an oxazole derivative, an oxadiazole derivative, a fluorenone derivative, an anthraquinodimethane derivative, an anthrone derivative, a diphenylquinone derivative, a thiopyrandioxide derivative, and a carbodiimide. Derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands Various metal complexes typified by metal complexes are listed.

The thickness of the electron injection layer and the electron transport layer is not particularly limited, but is usually preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and more preferably 10 nm to 5 μm.
00 nm is particularly preferred. The electron injection layer and the electron transport layer may have a single-layer structure composed of one or more of the above-mentioned materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. Examples of the method for forming the electron injecting layer and the electron transporting layer include a vacuum deposition method, an LB method, and a method of dissolving or dispersing an electron injecting and transporting agent in a solvent and coating (spin coating, casting, dip coating, etc.) and the like. Is used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. As the resin component, for example, those exemplified in the case of the hole injection / transport layer can be applied.

As the material of the protective layer, any material may be used as long as it has a function of preventing the element that promotes element deterioration such as moisture and oxygen from entering the element. Specific examples thereof include In, Sn, Pb, Au, Cu, Ag, Al, and T.
i, metal such as Ni, MgO, SiO, SiO ₂ , Al ₂ O
_{3, GeO, NiO, CaO,} BaO, Fe 2 O 3, Y 2 O
_3, a metal oxide such as TiO _2, MgF _2, LiF, Al
Metal fluorides such as F ₃ and CaF ₂ , polyethylene, polypropylene, polymethyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, and a mixture of chlorotrifluoroethylene and dichlorodifluoroethylene. Polymer, copolymer obtained by copolymerizing a monomer mixture containing tetrafluoroethylene and at least one comonomer, fluorinated copolymer having a cyclic structure in the copolymer main chain, water absorption of 1% or more Sex substance,
A moisture-proof substance having a water absorption of 0.1% or less can be used.

The method for forming the protective layer is not particularly limited. For example, a vacuum deposition method, a sputtering method, a reactive sputtering method, an MBE (molecular beam epitaxy) method,
Cluster ion beam method, ion plating method,
Plasma polymerization (high frequency excitation ion plating), plasma CVD, laser CVD, thermal CVD
Method, gas source CVD method, and coating method can be applied.

[0101]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. Example 1 A solution prepared by dissolving 40 mg of a compound shown in Table 1 below in 3 ml of 1,2-dichloroethane was spin-coated (about 40 nm in film thickness) on a washed ITO substrate.
Tris (8-hydroxyquinolinato) aluminum (A
lq) was vacuum deposited to a film thickness of about 60 nm (8
× 10 ^-6 to 1 × 10 ^-5 Torr). A mask (a mask having a light-emitting area of 5 mm × 5 mm) patterned on an organic thin film is provided, and magnesium: silver = 1 in a vapor deposition apparatus.
After 0: 1 was co-evaporated at 250 nm, silver was evaporated at 300 nm (8 × 10 ⁻⁶ to 1 × 10 ⁻⁵ Torr) to produce light-emitting elements (samples 101 to 113). The light emission characteristics were measured as follows.

Source measure unit 2 manufactured by Toyo Technica
Using a 400 type, a DC constant voltage is applied to the EL element using ITO as an anode and magnesium: silver as a cathode to emit light, and the luminance thereof is measured by a luminance meter BM-8 manufactured by Topcon Corporation, and the emission wavelength is measured by a spectrum analyzer PMA manufactured by Hamamatsu Photonics. -11
It measured using. In addition, the fabricated device was heated at 60 ° C. and 20 ° C.
The relative luminance (luminance after lapse of time assuming that the luminance immediately after device production was 100, expressed as a relative value (drive voltage: 15 V)) was evaluated after leaving the device for 3 hours under the condition of% RH and emitting light. Table 1 shows the results.

[0103]

[Table 1]

[0104]

Embedded image

From the results shown in Table 1, it is found that the light-emitting devices of the present invention (samples 105 to 113) using the light-emitting device materials of the present invention have the following characteristics.
It can be seen that the minimum driving voltage is low and high-luminance light emission is possible. In addition, it can be seen that the decrease in luminance after storage at high temperature is small and the durability is excellent.

Example 2 Compound 37 shown in Table 2 below
mg, compound A (electron transporting agent) 1 represented by the following structural formula
2 mg and 3 mg of a compound B (light emitting material) represented by the following structural formula were dissolved in 3 ml of 1,2-dichloroethane,
Light-emitting elements were manufactured by the same manufacturing method as in Example 1 (Samples 201 to 206). Table 2 shows the evaluation results of the emission characteristics.

[0107]

[Table 2]

[0108]

Embedded image

From the results shown in Table 2, the light-emitting elements of the present invention (samples 204 to 206) in which the light-emitting element material of the present invention is used as a host material and doped with a light-emitting material and an electron transporting agent have a low minimum driving voltage, and It can be seen that high-luminance light emission is possible. In addition, it can be seen that the decrease in luminance after storage at high temperature is small and the durability is excellent.

Example 3 Compound 40 shown in Table 3 below
mg, blue light emitting material B 10.0 m represented by the following structural formula
g, 2.0 mg of green light-emitting material G, 0.5 mg of red light-emitting material R1, 0.5 mg of R2, and 12.0 mg of compound A used in Example 2 were dissolved in 3 ml of 1,2-dichloroethane and washed on an ITO substrate. Was spin coated. The thickness of the formed organic thin film was about 110 nm. Mask patterned on organic thin film (light emitting area is 5mm × 5
mm), and magnesium: silver = 10: 1 is co-deposited at 50 nm in a vapor deposition apparatus.
m was vapor-deposited to produce a light-emitting element (samples 301 to 30).
3). Table 3 shows the evaluation results of the emission characteristics.

[0111]

[Table 3]

[0112]

Embedded image

From the results shown in Table 3, the light emitting devices of the present invention (samples 302 and 303) using the light emitting device material of the present invention showed that
It can be seen that low-voltage driving and high-luminance light emission are possible as compared with the light-emitting element using the comparative compound (sample 301). In the light-emitting element using the comparative compound, the generation of dark spots was remarkably observed, whereas the light-emitting element of the present invention showed good planar light emission. Further, it can be seen that good white light emission is possible when the light-emitting element material of the present invention is used in combination with blue, green and red light-emitting materials.

[0114]

According to the present invention, it is possible to provide a light-emitting element material which is capable of driving at a low voltage and emits light with high luminance, has excellent durability, and a light-emitting element using the same. In particular, good light-emitting characteristics can be obtained even by a coating method with low luminance, and a light-emitting element can be advantageously manufactured in terms of manufacturing cost and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 26/06 C08F 26/06 4J100 C08G 63/685 C08G 63/685 5F041 65/00 65/00 69/32 69/32 H01L 33/00 H01L 33/00 A H05B 33/14 H05B 33/14 BF term (reference) 3K007 AB00 AB02 AB03 AB06 AB18 CA01 CA05 CB01 DA00 DB03 EB00 FA01 4C034 DM01 4J001 DA01 DB01 DC16 DC24 EB37 EC55 EC69 FB03 FC03 JA20 4J005 BA00 4J029 AA04 AB07 AC01 AC02 AE04 BB13A CH01 DA13 4J100 AB07P AM21P AQ06P BA04P BA31P BC43P BC49P BC53P BC65P BC73P BC79P BC83P CA01 CA04 DA61 JA32 5F041 AA03 CA36 CA88 CA36 CA45

Claims (9)

[Claims] 1. A light emitting device material comprising a polymer having a partial structure represented by the following general formula (I). Embedded image 2. A light emitting device material comprising a polymer containing at least one repeating unit represented by the following general formula (II). Embedded image (In the general formula (II), R _2c , R _2d and R _2e each independently represent a substituent. 2p, 2q and 2r each represent 0.
Represents an integer of from 4 to 4. 2p, 2q and 2r are each 2
In the above case, R _2c , R _2d and R _2e may be the same or different from each other. L ₂ represents a single bond or a divalent linking group. R ₂₁ represents a hydrogen atom, an alkyl group or an aryl group. m ₂ represents an integer of 1 or more. ) 3. A light emitting device material comprising a polymer containing at least one repeating unit represented by the following general formula (III). Embedded image (In the general formula (III), R _3e is, .R _3c represents a hydrogen atom or a substituent, R _3d and R _{3 f} are, .3P and 3r independently represents a substituent represents an integer of 0 to 4 3q is 0-3
Represents an integer. When each of 3p, 3q, and 3r is 2 or more, R _3c , R _3d, and R _3f may be the same or different from each other. L ₃ is a single bond or 2
Represents a valent linking group. R ₃₁ represents a hydrogen atom, an alkyl group or an aryl group. m ₃ represents an integer of 1 or more. ) 4. A light emitting device material comprising a polymer containing at least one repeating unit represented by the following general formula (IV). Embedded image In (formula (IV), R _4e is .R _4c represents a hydrogen atom or a substituent, R _4d and R _{4 f} is .4P and 4q each independently represent a substituent, 0-3 respectively integers Represents 4
r represents an integer of 0 to 4. When each of 4p, 4q, and 4r is 2 or more, R _4c , R _4d, and R _4f may be the same or different from each other. L ₄ represents a single bond or a divalent linking group. m ₄ represents an integer of 1 or more. ) 5. The formula (II) wherein m ₂ is from 6 to 1
The light emitting device material according to claim 2, wherein the material is 00000. 6. m ₃ in the general formula (III) is 6 to 1
The light emitting device material according to claim 3, wherein the material is 00000. 7. The formula (IV) wherein m ₄ is from 6 to 1
The light emitting device material according to claim 4, wherein the material is 00000. 8. A light-emitting element having a light-emitting layer or a plurality of organic compound thin layers including the light-emitting layer between a pair of electrodes, wherein at least one of the light-emitting elements is made of the light-emitting element material according to any one of claims 1 to 7. A light-emitting element comprising: 9. A light-emitting element having a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer between a pair of electrodes, wherein at least one of the light-emitting element materials according to any one of claims 1 to 7 is used. A light-emitting element, which is a layer formed by coating.