CN101184789B - High-molecular compound and high-molecular luminescent device using the same - Google Patents

Abstract

High-molecular compounds characterized by having at least one residue of a compound represented by the general formula (1): (1) wherein A, B and C are each independently an optionally substituted aromatic or nonaromatic ring; Z1, Z2, Z3, Z4, and Z5 are each independently C-(Q)z or a nitrogen atom; Q is a substituent or hydrogen; z is 0 or 1; A and B may own a ring-constituent atom jointly in addition to Z5; and one or two of A, B and C are nonaromatic rings.

Description

Polymer compound and polymer light-emitting device using it

technical field

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

Background technique

High-molecular-weight light-emitting materials and charge-transporting materials have been studied in various ways because they are soluble in solvents and can form an organic layer of a light-emitting device by a coating method. Polyfluorenes are known as polymer compounds that can be used in electronic devices such as polymer light-emitting devices (polymer LEDs) as light-emitting materials or charge transport materials (International Publication No. 99/54385). the

However, the device performance of a device using the above-mentioned polymer compound as a light-emitting material, a charge transport material, etc. is not always at a practically satisfactory level. the

For example, polymer LEDs using the above-mentioned polymer compounds are not yet at a practically satisfactory level in terms of device performance such as luminous efficiency and luminous color tone. the

Contents of the invention

An object of the present invention is to provide a polymer compound capable of providing an electronic device having excellent device performance when used as a material of an electronic device. the

That is, the present invention provides a polymer compound containing at least one residue of a compound represented by the following formula (1). the

(式1) 

(Formula 1)

[In the formula, Ring A, Ring B, and Ring C independently represent an aromatic ring or a non-aromatic ring that may have a substituent, and Z ₁ , Z ₂ , Z ₃ , Z ₄ , and Z ₅ independently represent C -(Q)z or a nitrogen atom, Q represents a substituent or a hydrogen atom, z represents 0 or 1, and the A ring and the B ring can also share atoms other than Z ₅ constituting their respective rings, the A ring, the B ring and the C ring One or more and two or less rings are non-aromatic rings. ]

Detailed ways

In formula (1), ring A, ring B, and ring C each independently represent an aromatic ring or a non-aromatic ring which may have a substituent. the

Examples of the aromatic ring include those containing 4n+2 π electrons in the ring structure. Specifically, aromatic hydrocarbons such as benzene rings and cyclodepentacene rings; aromatic heterocycles such as furan rings, thiophene rings, pyrroles, pyridine rings, pyrimidine rings, and pyridazine rings are mentioned. the

Examples of the non-aromatic ring include a cyclopentane ring, a cyclopentene ring, a cyclopentadiene ring, a cyclohexane ring, a cyclohexene ring, a cyclohexadiene ring, a cycloheptane ring, and a cycloheptene ring. , cycloheptadiene ring, cycloheptatriene ring, cyclooctane ring, cyclooctene ring, cyclooctadiene ring, cyclooctatriene ring, cyclooctene tetraene ring, cyclononane ring, cyclononene ring , cyclononadiene ring, cyclononatriene ring, cyclodecane ring, cyclodecene ring, cyclodecadiene ring, cyclodecatriene ring, cyclodecatetraene ring, cyclododecane ring, cyclododeca Alkene ring, cyclododecanadiene ring, cyclododecanetriene ring, cyclododecanetraene ring, cyclododecanpentaene ring, cycloundecane ring, cycloundecene ring, cycloundeca Alicyclic rings such as alkanadiene ring, cycloundecanetriene ring, cycloundecanetetraene ring, cycloundecanepentaene ring, cycloundecane hexaene ring; pyran ring, thiopyran ring, etc. non-aromatic heterocycle. the

When the aromatic ring or non-aromatic ring has a substituent, examples of the substituent include alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, aryl Alkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, fluorine atom, acyl group, acyloxy group, amido group, imide group, monovalent heterocyclic ring group, carboxyl group, substituted carboxyl group, cyano group and nitro group, more preferably alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, arylalkoxy group, arylalkylthio group. the

Here, the alkyl group may be linear, branched or cyclic, and generally has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include methyl, ethyl, Propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 3, 7-Dimethyloctyl, lauryl, trifluoromethyl, pentafluoroethyl, perfluorobutyl, perfluorohexyl, perfluorooctyl, etc., preferably pentyl, isopentyl, hexyl, octyl, 2 - ethylhexyl, decyl, 3,7-dimethyloctyl. the

The alkoxy group may be linear, branched or cyclic, and generally has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include methoxy and ethoxy. , propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyl Oxygen, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy, trifluoromethoxy, pentafluoroethoxy, perfluorobutoxy, perfluorohexyl, perfluorobutoxy Fluorooctyl, methoxymethyloxy, 2-methoxyethyloxy, etc., preferably pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, 3, 7-Dimethyloctyloxy. the

The alkylthio group may be linear, branched or cyclic, and generally has about 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples thereof include methylthio and ethylthio , propylthio, isopropylthio, butylthio, isobutylthio, tert-butylthio, pentylthio, hexylthio, cyclohexylthio, heptylthio, octylthio, 2-ethylhexyl Sulfuryl, nonylthio, decylthio, 3,7-dimethyloctylthio, laurylthio, trifluoromethylthio, etc., preferably pentylthio, hexylthio, octylthio, 2- Ethylhexylthio, decylthio, 3,7-dimethyloctylthio. the

An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and includes a substance having a condensed ring, and a substance in which two or more independent benzene rings or fused rings are bonded directly or through a group such as a vinylidene group. The carbon number of the aryl group is usually about 6 to 60, preferably 7 to 48. Specific examples thereof include phenyl, C ₁ to C ₁₂ alkoxyphenyl (C ₁ to C ₁₂ means that the carbon number is 1 to 12. Same below.), C ₁ ~C ₁₂ alkylphenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, pentafluorophenyl, etc., preferably C ₁ -C ₁₂ alkoxyphenyl, C ₁ -C ₁₂ alkylphenyl. Specific examples of the C ₁ -C ₁₂ alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, and pentyloxy. , hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy, etc. .

基、甲基乙基苯基、异丙基苯基、丁基苯基、异丁基苯基、叔丁基苯基、戊基苯基、异戊基苯基、己基苯基、庚基苯基、辛基苯基、壬基苯基、癸基苯基、十二烷基苯基等。  Specific examples of C ₁ -C ₁₂ alkylphenyl groups include methylphenyl, ethylphenyl, dimethylphenyl, propylphenyl,

base, methylethylphenyl, isopropylphenyl, butylphenyl, isobutylphenyl, tert-butylphenyl, pentylphenyl, isopentylphenyl, hexylphenyl, heptylphenyl Base, octylphenyl, nonylphenyl, decylphenyl, dodecylphenyl, etc.

The carbon number of the aryloxy group is usually about 6 to 60, preferably 7 to 48. Specific examples thereof include phenoxy, C ₁ to C ₁₂ alkoxyphenoxy, C ₁ to C ₁₂ alkylbenzene Oxy, 1-naphthyloxy, 2-naphthyloxy, pentafluorophenyloxy, etc., preferably C ₁ -C ₁₂ alkoxyphenoxy, C ₁ -C ₁₂ alkylphenoxy.

Specific examples of the C ₁ -C ₁₂ alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, and pentyloxy. , hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy, etc. .

Specific examples of C ₁ -C ₁₂ alkylphenoxy groups include methylphenoxy, ethylphenoxy, dimethylphenoxy, propylphenoxy, 1,3,5-tris Methylphenoxy, methylethylphenoxy, isopropylphenoxy, butylphenoxy, isobutylphenoxy, tert-butylphenoxy, pentylphenoxy, isopentyl Phenoxy, hexylphenoxy, heptylphenoxy, octylphenoxy, nonylphenoxy, decylphenoxy, dodecylphenoxy and the like.

The carbon number of the arylthio group is usually 3 to 60, and specific examples thereof include phenylthio, C ₁ to C ₁₂ alkoxyphenylthio, C ₁ to C ₁₂ alkylphenylthio, 1-naphthylthio, 2-naphthylthio, pentafluorophenylthio, etc., preferably C ₁ -C ₁₂ alkoxyphenylthio, C ₁ -C ₁₂ alkylphenylthio.

The carbon number of the aralkyl group is usually about 7 to 60, preferably 7 to 48. Specific examples thereof include phenyl-C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxyphenyl-C ₁ ~C ₁₂ alkyl, C ₁ ~C ₁₂ alkylphenyl-C ₁ ~C ₁₂ alkyl, 1-naphthyl-C ₁ ~C ₁₂ alkyl, 2-naphthyl-C ₁ ~C ₁₂ alkyl, etc. , preferably C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl.

The carbon number of the arylalkoxy group is usually about 7 to 60, preferably 7 to 48 carbon atoms. Specific examples thereof include phenylmethoxy, phenylethoxy, phenylbutoxy, phenyl Pentyloxy, phenylhexyloxy, phenylheptyloxy, phenyloctyloxy, etc. phenyl-C ₁ ~C ₁₂ alkoxy, C ₁ ~C ₁₂ alkoxyphenyl-C ₁ ~C ₁₂ Alkoxy, C ₁ ~C ₁₂ alkylphenyl-C ₁ ~C ₁₂ alkoxy, 1-naphthyl-C ₁ ~C ₁₂ alkoxy, 2-naphthyl-C ₁ ~C ₁₂ alkoxy etc., preferably C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkoxy.

The carbon number of the aralkylthio group is usually about 7 to 60, preferably 7 to 48, and specific examples thereof include phenyl-C ₁ -C ₁₂ alkylthio, C ₁ -C ₁₂ alkoxy phenyl-C ₁ ～C ₁₂ alkylthio, C ₁ ～C ₁₂ alkylphenyl-C ₁ ～C ₁₂ alkylthio, 1-naphthyl-C ₁ ～C ₁₂ alkylthio, 2 -Naphthyl-C ₁ ~C ₁₂ alkylthio, etc., preferably C ₁ ~C ₁₂ alkoxyphenyl-C ₁ ~C ₁₂ alkylthio, C ₁ ~C ₁₂ alkylphenyl-C ₁ ~ C ₁₂ alkylthio.

The carbon number of the arylalkenyl group is usually about 8 to 60, and specific examples thereof include phenyl-C ₂ -C ₁₂ alkenyl, C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl, C ₁ ~C ₁₂ alkylphenyl-C ₂ ~C ₁₂ alkenyl, 1-naphthyl-C ₂ ~C ₁₂ alkenyl, 2-naphthyl-C ₂ ~C ₁₂ alkenyl group, etc., preferably C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkenyl.

The carbon number of the arylalkynyl group is usually about 8 to 60. Specific examples thereof include phenyl to C ₂ to C ₁₂ alkynyl, C ₁ to C ₁₂ alkoxyphenyl-C ₂ to C ₁₂ alkynyl C ₁ -C ₁₂ alkylphenyl-C ₂ -C ₁₂ alkynyl, 1-naphthyl-C ₂ -C ₁₂ alkynyl, 2-naphthyl-C ₂ -C ₁₂ alkynyl, etc., preferably C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkynyl, C ₁ -C ₁₂ alkylphenyl-C ₂ -C ₁₂ alkynyl.

As the substituted amino group, an amino group substituted by one or two groups selected from an alkyl group, an aryl group, an aralkyl group or a monovalent heterocyclic group, the alkyl group, an aryl group, an aralkyl group or A monovalent heterocyclic group may also be a substituent. The carbon number of the substituted amino group, not including the carbon number of the substituent, is usually about 1 to 60, preferably 2 to 48 carbons. the

Specifically, methylamino, dimethylamino, ethylamino, diethylamino, propylamino, dipropylamino, isopropylamino, diisopropylamino, butylamino, isopropylamino, Butylamino, tert-butylamino, pentylalkyl, hexylamino, cyclohexylamino, heptylamino, octylamino, 2-ethylhexylamino, nonylamino, decylamino, 3,7-dimethyl Octylamino, laurylamino, cyclopentylamino, dicyclopentylamino, cyclohexylamino, dicyclohexylamino, pyrrolidinyl, piperidinyl, bistrifluoromethylaminophenylamino, biphenyl Amino, C ₁ -C ₁₂ alkoxyphenylamino, di(C ₁ -C ₁₂ alkoxyphenyl)amino, di(C ₁ -C ₁₂ alkylphenyl)amino, 1-naphthylamino, 2 -Naphthylamino, pentafluorophenylamino, pyridylamino, pyridazinylamino, pyrimidinylamino, pyrazinylamino, triazylaminophenyl-C ₁ ~C ₁₂ alkylamino, C ₁ ~C ₁₂ alkoxy phenyl-C ₁ ～C ₁₂ alkylamino, C ₁ ～C ₁₂ alkylphenyl-C ₁ ～C ₁₂ alkylamino, di(C ₁ ～C ₁₂ alkoxyphenyl-C ₁ ～C ₁₂ Alkyl)amino, di(C ₁ ~C ₁₂ alkylphenyl-C ₁ ~C ₁₂ alkyl)amino, 1-naphthyl-C ₁ ~C ₁₂ alkylamino, 2-naphthyl-C ₁ ~C ₁₂ Alkylamino, etc.

Examples of the substituted silyl group include silyl groups substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an aralkyl group or a monovalent heterocyclic group. The carbon number of the substituted silyl group is usually about 1 to 60, preferably 3 to 48 carbon atoms. Furthermore, the alkyl group, aryl group, aralkyl group or monovalent heterocyclic group may have a substituent. the

Specifically, trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, dimethylisopropylsilyl, diethylisopropylsilyl, diethylsilyl Propylsilyl, tert-Butylsilyldimethylsilyl, Amyldimethylsilyl, Hexyldimethylsilyl, Heptyldimethylsilyl, Octyldimethylsilyl base, 2-ethylhexyldimethylsilyl, nonyldimethylsilyl, decyldimethylsilyl, 3,7-dimethyloctyl-dimethylsilyl, lauryl Dimethylsilyl group, phenyl-C ₁ ~C ₁₂ alkylsilyl group, C ₁ ~C ₁₂ alkoxyphenyl-C ₁ ~C ₁₂ alkylsilyl group, C ₁ ~C ₁₂ alkane phenyl-C ₁ ～C ₁₂ alkylsilyl, 1-naphthyl-C ₁ ～C ₁₂ alkylsilyl, 2-naphthyl-C ₁ ～C ₁₂ alkylsilyl, phenyl- C ₁ ~C ₁₂ alkyldimethylsilyl, triphenylsilyl, tri-p-xylylsilyl, tribenzylsilyl, biphenylmethylsilyl, tert-butyl Biphenylsilyl group, dimethylphenylsilyl group and the like.

The acyl group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, benzoyl, trifluoro Acetyl, pentafluorobenzoyl, etc. the

The carbon number of the acyloxy group is usually about 2 to 20, preferably 2 to 18, and specific examples thereof include acetyloxy, propionyloxy, butyryloxy, isobutyryloxy, and neobutyryloxy. Valeryloxy, benzoyloxy, trifluoroacetoxy, pentafluorobenzoyloxy, etc. the

The carbon number of the amide group is usually about 2 to 20, preferably 2 to 18, and specific examples thereof include formamide, acetamide, propionamide, butyramide, benzamide, trisamide, Fluoroacetamide, pentafluorobenzamide, diformamide, diacetamide, dipropionamide, dibutyramide, dibenzamide, bistrifluoroacetamide, dipentafluorobenzyl Amide, etc. the

Examples of the imide group include residues obtained by removing a hydrogen atom bonded to the nitrogen atom of an imide compound, and have a carbon number of about 4 to 20. Specifically, the groups shown below are exemplified. . the

The monovalent heterocyclic group refers to an atomic group remaining after removing one hydrogen atom from a heterocyclic compound, and the carbon number is usually about 4-60, preferably 4-20. In addition, the carbon number of the substituent is not included in the carbon number of the heterocyclic group. The term "heterocyclic compound" herein refers to an organic compound having a cyclic structure in which the elements constituting the ring are not only carbon atoms but also contain heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, and boron in the ring. Specifically, the following configurations can be given. the

In the above formula, R independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an arylalkoxy group, an arylalkylthio group, Aryl alkenyl group, aryl alkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amido group, imide group, monovalent hetero Cyclic, carboxyl, substituted carboxyl or cyano. the

Among them, thienyl, C ₁ ~C ₁₂ alkylthienyl, pyrrolyl, furyl, pyridyl, C ₁ ~C ₁₂ alkylpyridyl, piperidyl, quinolinyl, isoquinolyl, etc. are preferred, and more Preferred are thienyl, C ₁ -C ₁₂ alkylthienyl, pyridyl, and C ₁ -C ₁₂ alkylpyridyl.

The substituted carboxyl group refers to a carboxyl group substituted by an alkyl group, an aryl group, an aralkyl group or a monovalent heterocyclic group, and generally has about 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms. Specific examples thereof include: Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, cyclohexyl Oxycarbonyl, Heptyloxycarbonyl, Octyloxycarbonyl, 2-Ethylhexyloxycarbonyl, Nonyloxycarbonyl, Decyloxycarbonyl, 3,-Dimethyloctyloxycarbonyl, Dodecyloxycarbonyl , trifluoromethoxycarbonyl, pentafluoroethoxycarbonyl, perfluorobutoxycarbonyl, perfluorohexyloxycarbonyl, perfluorooctyloxycarbonyl, phenoxycarbonyl, naphthyloxycarbonyl, pyridyloxycarbonyl wait. Furthermore, the alkyl group, aryl group, aralkyl group or monovalent heterocyclic group may have a substituent. The carbon number of the substituent is not included in the carbon number of the substituted carboxyl group. the

In the above formula (1), Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ each independently represent C-(Q)z or a nitrogen atom, Q represents a substituent or a hydrogen atom, and z represents 0 or 1.

Examples of substituents for Q include alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio, aryl chain Alkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, fluorine atom, acyl group, acyloxy group, amido group, imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group and nitro group, etc. , and its definition, specific examples, etc. are the same as those described above. the

The A ring and the B ring may share atoms of rings other than Z ₅ constituting the respective rings, and one or more of the A ring, B ring, and C ring are non-aromatic rings. The case where the A ring and the B ring share one ring atom except _Z5 is preferred. In addition, it is preferable that there is one non-aromatic ring.

In addition, the polymer compound of the present invention preferably contains a repeating unit represented by the following formulas (1-1) to (1-3) as a repeating unit. the

Formula (1-1) Formula (1-2) Formula (1-3)

[In the formula, Ring A, Ring B, and Ring C independently represent an aromatic ring or a non-aromatic ring that may have a substituent, and Z ₁ , Z ₂ , Z ₃ , Z ₄ , and Z ₅ independently represent C -(Q)z or a nitrogen atom, Q represents a substituent or a hydrogen atom, z represents 0 or 1, ring A and ring B may share atoms other than Z ₅ , and may be one of the substituents of each ring The rings are combined to form a ring, and one or more of the rings without a connecting bond among the A ring, B ring, and C ring are non-aromatic rings. ]

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

etc. and examples where they have substituents. the

Specific examples of the repeating unit represented by formula (1-2) include

etc. and examples where they have substituents. the

Specific examples of the repeating unit represented by formula (1-3) include

etc. and examples where they have substituents. the

Among the repeating units represented by the above formulas (1-1) to (1-3), for the atoms constituting the A ring, the B ring, and the C ring (the so-called "atoms constituting the ring" means the atoms forming the skeleton of the ring) In other words, atoms such as nitrogen, oxygen, sulfur, silicon, and selenium may be included in addition to carbon atoms, but from the viewpoint of adjusting charge transport properties, it is preferable that all the atoms constituting the A ring, B ring, and C ring are carbon atoms. the

From the viewpoint of improving the solubility of the polymer compound, adjusting the emission wavelength, and adjusting the charge transport property, it is preferable that any one of the A ring, B ring, and C ring has a substituent. the

In addition, from the viewpoint of charge transportability, the repeating unit of the structure represented by the above formulas (1-1) and (1-2) is preferable, and from the viewpoint of easiness of synthesis, it is more preferable to have the repeating units represented by the above formula (1-1) ) represents the structure. the

In addition, the above formula (1-1) is more preferably the following formula (2-1). the

Formula (2-1)

[wherein, R ₁ and R ₂ independently represent a substituent, D ring represents a non-aromatic ring that may also have a substituent, a represents an integer of 0 to 2, b represents an integer of 0 to 3, and in R ₁ and When a plurality of R ₂ are present, they may be the same or different, and R ₁ and R ₂ may be combined to form a ring. In addition, R ₁ and/or R ₂ may combine with D ring to form a ring, and Q and z have the same meanings as above. ]

The repeating unit including the above formula (2-1) is preferably a repeating unit represented by the following formula (3-1). the

Formula (3-1)

[In the formula, R ₁ , R ₂ , D ring, Q, z, a, and b have the same meanings as above. ]

Among the repeating units represented by the formula (3-1), the following formulas (4-1), (4-2), (4-3) and (4-4) are more preferable from the viewpoint of adjusting the charge transport property. Represents the repeating unit. the

Formula (4-1) Formula (4-2)

Formula (4-3) Formula (4-4)

[In the formula, R _1a , R _1b , R _2a to R _2c and R _3a to R _3g represent substituents. In formulas (4-1) to (4-3), R _2c and R _3g may combine with each other to form a ring. In formula (4-4), R _2c and R _3g may combine with each other to form a ring. ]

Examples of the rings bonded to each other include aromatic rings, non-aromatic rings, and the like, and specific examples thereof are the same as those described above. the

And, the unit of formula (4-1)～(4-3) is included in the case of z=1 in formula (3-1), the unit of formula (4-4) is included in formula (3-1) In the case of z=0. the

Specific examples of the repeating unit represented by the above formula (4-1) include

Specific examples of the repeating unit represented by the above formula (4-2) include

Specific examples of the repeating unit represented by the above formula (4-3) include

Specific examples of the repeating unit represented by the above formula (4-4) include

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

Belong to the above formula (1-1), (1-2), (1-3), (2-1), (3-1), (4-1), (4-2), (4-3 ) and (4-4) the total number of repeating units of the structure represented by the polymer compound of the present invention is usually 1 mol% to 100 mol% of the total number of all repeating units, preferably 5 mol% to 100 mol% . the

From the viewpoint of changing the emission wavelength, the viewpoint of improving luminous efficiency, the viewpoint of improving heat resistance, etc., the polymer compound of the present invention is preferably in addition to the above-mentioned formula (1-1), (1-2), (1-3 ), (2-1), (3-1), (4-1), (4-2), (4-3) and (4-4) in addition to the repeating units represented by one or more of these Copolymers of other repeating units. the

As above-mentioned formula (1-1), (1-2), (1-3), (2-1), (3-1), (4-1), (4-2), (4-3 ) and (4-4), the repeating unit is preferably a repeating unit represented by the following formula (5), formula (6), formula (7) or formula (8). the

-Ar ₁ - (5)

-(Ar ₂ -X ₁ ) _ff -Ar ₃ - (6)

-Ar ₄ -X ₂ - (7)

-X ₃ - (8)

In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. X ₁ , X ₂ and X ₃ each independently represent -CR ₉ =CR ₁₀ -, -C≡C-, -N(R ₁₁ )- or -(SiR ₁₂ R ₁₃ ) _m -. R ₉ and R ₁₀ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, or a cyano group. R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, an aralkyl group or a substituted amino group. ff represents an integer of 1 or 2. m represents the integer of 1-12. When there are multiple R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₂ , they may be the same or different.

The arylene group mentioned here is an atomic group after removing two hydrogen atoms from an aromatic hydrocarbon, including an atomic group with a condensed ring, and two or more independent benzene rings or fused rings directly or through groups such as vinylidene groups bonded atoms. The arylene group may also have a substituent. the

Examples of substituents include alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio, arylalkenyl , arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, imide group, monovalent heterocyclic group, carboxyl group, Substitute carboxyl, cyano. the

The carbon number of the part except the substituent in an arylene group is about 6-60 normally, Preferably it is 6-20. In addition, the total carbon number of the arylene group including the substituent is usually about 6 to 100. the

Examples of the arylene group include phenylene (for example, formulas 1 to 3 in the figure below), naphthalenediyl (formulas 4 to 13 in the figure below), anthracene diyl groups (formulas 14 to 19 in the figure below), biphenyl Diyl (formula 20-25 in the figure below), fluorene diyl (formula 36-38 in the figure below), terphenyldiyl (formula 26-28 in the figure below), fused ring compound base (formula 29 in the figure below) ~35), styrene diyl groups (formulas A to D in the figure below), distyryl diyl groups (formulas E and F in the figure below), etc. Among them, phenylene, biphenylene, fluorenediyl, and stilylenediyl are preferable. the

In addition, the divalent heterocyclic group in Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ refers to an atomic group remaining after removing two hydrogen atoms from a heterocyclic compound, and this group may have a substituent. The term "heterocyclic compound" as used herein refers to an organic compound having a ring structure in which the elements constituting the ring are not only carbon atoms, but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic are included in the ring. Among divalent heterocyclic groups, aromatic heterocyclic groups are preferred.

Examples of substituents include alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio, arylalkenyl , arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, imide group, monovalent heterocyclic group, carboxyl group, Substitute carboxyl, cyano. the

The number of carbon atoms of the part excluding the substituent in the divalent heterocyclic group is usually about 3 to 60. In addition, the total carbon number including the substituent of the divalent heterocyclic group is usually about 3-100. the

As a divalent heterocyclic group, the following groups are mentioned, for example. the

As heteroatoms, divalent heterocyclic groups including nitrogen: pyridinediyl (formula 39-44 in the figure below), diazaphenylene (formula 45-48 in the figure below), quinoline diyl (formula 45-48 in the figure below), quinoline diyl ( Formula 49～63), quinoxaline dibase (formula 64～68 in the figure below), acridine dibase (formula 69～72 in the figure below), bipyridine dibase (formula 73～75 in the figure below), phenanthrene Arborindiyl (formula 76-78 in the figure below) and the like. the

A group having a fluorene structure containing silicon, nitrogen, selenium, etc. as a heteroatom (formulas 79 to 93 in the figure below). the

Five-membered ring heterocyclic groups containing silicon, nitrogen, sulfur, selenium, etc. as heteroatoms: Examples include (formulas 94 to 98 in the diagram below). the

Five-membered ring condensed heterocyclic groups containing silicon, nitrogen, selenium, etc. as heteroatoms: Examples include (formulas 99 to 100, 102 to 110 in the diagram below). the

A five-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom, which is combined at the α position of the heteroatom to form a dimer or oligomer: can be listed (formula 111 in the figure below) ~112). the

A five-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom, and a group bonded to a phenyl group at the α-position of the heteroatom: (Formulas 113 to 119 in the diagram below). the

Groups substituted with phenyl, furyl, and thienyl groups on five-membered ring heterocyclic groups containing oxygen, nitrogen, sulfur, etc. as heteroatoms: Examples include (formulas 120 to 125 in the diagram below). the

In addition, the divalent group having a metal complex structure among Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ means that two hydrogens are removed from the organic ligand of the metal complex having an organic ligand. The divalent group remaining after the atom.

The carbon number of the organic ligand is usually about 4 to 60, for example, 8-hydroxyquinoline and its derivatives, benzoquinoline and its derivatives, 2-phenylpyridine and its derivatives, 2- Phenylbenzothiazole and its derivatives, 2-phenylbenzoxazole and its derivatives, porphyrin and its derivatives, etc. the

In addition, examples of the central metal of the complex include aluminum, zinc, beryllium, iridium, platinum, gold, europium, terbium, and the like. the

Examples of the metal complex having an organic ligand include low-molecular fluorescent materials, metal complexes known as phosphorescent materials, triplet light-emitting complexes, and the like. the

Specifically, the following (126-132) can be illustrated as a divalent group which has a metal complex structure. the

In the above formulas 1 to 132, R independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an arylalkoxy group, an aryl group Alkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imide residue, amido group, imide group , a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. In addition, the carbon atoms contained in the groups of formulas 1 to 132 may be substituted by nitrogen atoms, oxygen atoms or sulfur atoms, and the hydrogen atoms may be substituted by fluorine atoms. the

In addition, among the repeating units represented by the above-mentioned formulas (5), (6), (7), and (8), the following formulas (9), (10), (11), (12), and (13) or a repeating unit represented by formula (14). the

[ _wherein , R represents alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio, arylalkenyl , arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, imide group, monovalent heterocyclic group, carboxyl group , substituted carboxyl or cyano. n represents an integer of 0-4. When a plurality of R ₁₄ are present, they may be the same or different. ]

[wherein, R ₁₅ and R ₁₆ independently represent alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio , aryl alkenyl, aryl alkynyl, amino, substituted amino, silyl, substituted silyl, halogen atom, acyl, acyloxy, imine residue, amido, imide, monovalent Heterocyclyl, carboxyl, substituted carboxyl or cyano. o and p each independently represent the integer of 0-3. When there are a plurality of R ₁₅ and R ₁₆ , they may be the same or different. ]

[wherein, R ₁₇ and R ₂₀ independently represent alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio , aryl alkenyl, aryl alkynyl, amino, substituted amino, silyl, substituted silyl, halogen atom, acyl, acyloxy, imine residue, amido, imide, monovalent Heterocyclyl, carboxyl, substituted carboxyl or cyano. q and r each independently represent the integer of 0-4. R ₁₈ and R ₁₉ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, or a cyano group. When there are a plurality of R ₁₇ and R ₂₀ , they may be the same or different. ]

[ _wherein , R represents alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio, arylalkenyl , arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, imide group, monovalent heterocyclic group, carboxyl group , substituted carboxyl or cyano. s represents an integer of 0-2. Ar ₁₃ and Ar ₁₄ each independently represent an arylene group, a divalent heterocyclic group, or a divalent group having a metal complex structure. ss and tt each independently represent 0 or 1. X ₄ represents O, S, SO, SO ₂ , Se or Te. When a plurality of R ₂₁ are present, they may be the same or different. ]

[wherein, R ₂₂ and R ₂₅ independently represent alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio , aryl alkenyl, aryl alkynyl, amino, substituted amino, silyl, substituted silyl, halogen atom, acyl, acyloxy, imine residue, amido, imide, monovalent Heterocyclyl, carboxyl, substituted carboxyl or cyano. t and u each independently represent the integer of 0-4. X ₅ represents O, S, SO, SO ₂ , Se, Te, NR ₂₄ or SiR ₂₅ R ₂₆ . X ₆ and X ₇ each independently represent N or CR ₂₇ . R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ each independently represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a monovalent heterocyclic group. When there are a plurality of R ₂₂ , R ₂₃ and R ₂₇ , they may be the same or different. ]

Examples of the central five-membered ring of the repeating unit represented by formula (11) include thiadiazole, oxadiazole, triazole, thiophene, furan, silole and the like. the

[wherein, R ₂₈ and R ₃₃ independently represent alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio , aryl alkenyl, aryl alkynyl, amino, substituted amino, silyl, substituted silyl, halogen atom, acyl, acyloxy, imine residue, amido, imide, monovalent Heterocyclyl, carboxyl, substituted carboxyl or cyano. v and w each independently represent the integer of 0-4. R ₂₉ , R ₃₀ , R ₃₁ and R ₃₆ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. Ar ₅ represents an arylene group, a divalent heterocyclic group, or a divalent group having a metal complex structure. When a plurality of R ₂₈ and R ₃₃ exist, they may be the same or different. ]

In addition, among the repeating units represented by the above formula (6), the repeating unit represented by the following formula (15) is preferable from the viewpoint of changing the emission wavelength, improving the luminous efficiency, and improving heat resistance. the

[In the formula, Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ each independently represent an arylene group or a divalent heterocyclic group. Ar ₁₀ , Ar ₁₁ and Ar ₁₂ each independently represent an aryl group or a monovalent heterocyclic group. Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ and Ar ₁₀ may also have a substituent. x and y each independently represent 0 or 1. 0≦x+y≦1. ]

Specific examples of the repeating unit represented by the above formula (15) include those represented by the following (Formulas 133 to 140). the

In the above formula, R is the same as in the above formulas 1 to 132. the

In order to improve the solubility in solvents, it is preferable to have one or more substituents other than hydrogen atoms, and the less symmetrical the shape of the repeating unit containing the substituents, the better. the

In the above formula, in the substituent R containing an alkyl group, it is preferable to contain one or more cyclic or branched alkyl groups in order to improve the solubility of the polymer compound in a solvent. the

In addition, when R in the above formula contains an aryl group or a heterocyclic group in a part thereof, they may further have one or more substituents. the

Among the repeating units represented by the above formula (15), it is preferable that Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ each independently represent an arylene group, and Ar ₁₀ , Ar ₁₁ and Ar ₁₂ each independently represent an aryl group.

Ar ₆ , Ar ₇ , and Ar ₈ are each independently preferably unsubstituted phenylene, unsubstituted biphenyl, unsubstituted naphthylene, or unsubstituted anthracendiyl.

Ar ₁₀ , Ar ₁₁ , and Ar ₁₂ are each independently preferably an aryl group having three or more substituents from the viewpoint of solubility, luminous efficiency, and stability, and more preferably Ar ₁₀ , Ar ₁₁ , and Ar ₁₂ have A phenyl group having three or more substituents, a naphthyl group having three or more substituents, or an anthracenyl group having three or more substituents, and Ar ₁₀ , Ar ₁₁ and Ar ₁₂ are more preferably phenyl groups having three or more substituents.

Among them, Ar ₁₀ , Ar ₁₁ and Ar ₁₂ are each independently preferably represented by the following formula (15-1).

[wherein, Re, Rf and Rg independently represent alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio , arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, siloxy, substituted siloxy, monovalent heterocyclic group or halogen atom. ]

Among the repeating units represented by the above formula (15), Ar ₇ is preferably the following formula (15-2) or (15-3).

[Here, the benzene rings contained in the structures represented by (15-2) and (15-3) may each independently have one to four substituents. These substituents may be the same or different. In addition, a plurality of substituents may be linked to form a ring. In addition, another aromatic hydrocarbon ring or heterocyclic ring may be bonded adjacent to the benzene ring. ]

As the repeating unit represented by the above-mentioned formula (15), examples represented by the following (formulas 141 to 142) can be given as particularly preferable specific examples. the

[wherein, Re to Rg are as described above. ]

In the above formulas, Re to Rg are the same as those in the above formulas 1 to 132. In order to improve the solubility in solvents, it is preferable to have one or more substituents other than hydrogen atoms, and the less symmetrical the shape of the repeating unit containing the substituents, the better. the

Among the substituents in which R contains an alkyl chain in the above formula, it is preferable to contain one or more cyclic or branched alkyl chains in order to improve the solubility of the polymer compound in a solvent. the

In addition, in the above formula, when R partially contains an aryl group or a heterocyclic group, these may further have one or more substituents. the

In addition, the polymer compound of the present invention may also contain the above-mentioned formula (1-1), (1-2), (1-3) and formula (5) ~ A repeating unit other than the repeating unit represented by formula (15). In addition, these repeating units or other repeating units may be connected by non-conjugated units, and these non-conjugated moieties may be contained in the repeating units. As a combination structure, the structure shown below, the structure which combined two or more of the structures shown below, etc. can be illustrated. 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. the

Among the polymer compounds of the present invention, preferred are compounds consisting only of repeating units represented by the above formula (1-1); and/or compounds consisting only of repeating units represented by (1-2); and/or compounds consisting only of ( 1-3) The compound composed of the repeating unit represented by the above-mentioned formula (1-1) and/or (1-2) and/or (1-3) is preferably substantially combined with the above-mentioned formula (5) to (15 ) compound consisting of one or more repeating units represented by ). the

In addition, the polymer compound of the present invention may be a random, block or graft copolymer, or may be a polymer having an intermediate structure thereof, for example, a random copolymer having a block property. From the viewpoint of obtaining a high-molecular light-emitting body with a high quantum yield of fluorescence or phosphorescence, a block random copolymer or a block or graft copolymer is more preferable than a complete random copolymer. It also includes the case where the main chain has a branch and has three or more terminal parts, or a dendritic substance. the

In addition, when the terminal group of the polymer compound of the present invention remains as it is, the luminescent characteristics or lifetime of the device may be reduced, so it can be protected with a stable group. A structure having a conjugated bond continuous to the conjugated structure of the main chain is preferred, for example, a structure in which an aryl group or a heterocyclic group is bonded via a carbon-carbon bond can be exemplified. Specifically, substituents described in Formula 10 of JP-A-9-45478 and the like can be exemplified. the

In the polymer compound of the present invention, preferably at least one of its molecular chain ends is selected from monovalent heterocyclic groups, monovalent aromatic amine groups, monovalent groups derived from heterocyclic coordination metal complexes, and aromatic Aromatic terminal groups in the group. The aromatic terminal group may be one type, or two or more types. From the viewpoint of fluorescence characteristics or device characteristics, it is preferable that there are substantially no terminal groups other than aromatic terminal groups. Here, the molecular chain terminal refers to the aromatic terminal group present at the terminal of the polymer compound by the production method of the present invention; it belongs to the leaving group of the monomer used in polymerization, and exists at the time of polymerization without leaving. A leaving group at the end of a polymer compound; a hydrogen atom that is bonded to an aromatic terminal group without being bonded to a leaving group derived from a monomer present at the end of a polymer compound. Among these molecular chain terminals, the leaving group that is a leaving group of a monomer used in polymerization and does not leave during polymerization but exists at the end of a polymer compound is produced, for example, using a monomer having a halogen atom as a raw material. In the case of the polymer compound of the present invention, if the halogen remains at the terminal of the polymer compound, the fluorescence characteristics and the like tend to decrease, so it is preferable that substantially no leaving group of the monomer remains at the terminal. the

In a polymer compound, at least one of its molecular chain ends is selected from a monovalent heterocyclic group, a monovalent aromatic amine group, a monovalent group or a chemical formula derived from a heterocyclic coordination metal complex By blocking the aromatic terminal group in the aryl group of 90 or more, various properties can be expected to be imparted to the polymer compound. Specifically, the effect of prolonging the time required for the brightness of the device to decrease; the effect of improving charge injection, charge transport, and luminescent characteristics; the effect of improving compatibility or interaction between copolymers; anchoring (anchor) -like) effects, etc. the

Examples of the monovalent aromatic amine group include a structure in which one of the two bonds in the structure of the formula (15) is blocked with R. the

As a monovalent group derived from a heterocyclic coordination metal complex, one of the two bonds in the above-mentioned divalent group having a metal complex structure is sealed with R blocked structure. the

Among the aromatic terminal groups possessed by the polymer compound of the present invention, the aryl group having a chemical formula weight of 90 or more usually has about 6 to 60 carbon atoms. The chemical formula weight of the aryl group referred to here refers to the sum of values obtained by multiplying the atomic number of each element by the atomic weight for each element in the chemical formula when the aryl group is expressed in a chemical formula. the

Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a group having a fluorene structure, a condensed ring compound group, and the like. the

As the phenyl group to block the end, for example,

As the naphthyl end-blocked, for example, can be cited

As the anthracenyl group, for example,

As a group containing a fluorene structure, for example,

As the condensed ring compound group, for example, can be cited

As the terminal group for improving the charge injection and charge transport properties, a monovalent heterocyclic group, a monovalent aromatic amine group, and a condensed ring compound group are preferable, and a monovalent heterocyclic group and a condensed ring compound group are more preferable. the

As the terminal group for improving luminescent properties, naphthyl, anthracenyl, condensed ring compound groups, and monovalent groups derived from heterocyclic coordination metal complexes are preferable. the

As the terminal group having the effect of prolonging the time required for the brightness of the device to decrease, an aryl group having a substituent is preferable, and a phenyl group having 1 to 3 alkyl groups is preferable. the

An aryl group having a substituent is preferable as the terminal group having the effect of improving compatibility or interaction between polymer compounds. In addition, by using a phenyl group substituted with an alkyl group having 6 or more carbon atoms, an anchoring effect can be exerted. The so-called anchoring effect means that the terminal group plays an anchoring role on the aggregate of the polymer and improves the interaction effect. the

As a group for improving device characteristics, the following structures are preferable. the

R in the formula can exemplify the above-mentioned R. the

The polystyrene-equivalent number average molecular weight of the polymer compound of the present invention is usually about 10 ³ to 10 ⁸ , preferably about 10 ⁴ to 10 ⁶ . In addition, the polystyrene-equivalent weight average molecular weight is 10 ³ to 10 ⁸ , preferably 10 ⁴ to 5×10 ⁶ .

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

Compared with the corresponding polyfluorene derivatives, the polymer compound of the present invention can emit light at a shorter wavelength. the

Next, the production method of the polymer compound of the present invention will be described. the

Among the polymer compounds of the present invention, for example, compounds having repeating units represented by formulas (1-1), (1-2), and (1-3) can be obtained by using the following formula (16-1 ), (16-2) and (16-3)

Formula (16-1) Formula (16-2) Formula (16-3)

[In the formula, ring A, ring B, ring C, and Z ₁ to Z ₅ are as described above. Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y ₆ each independently represent a substituent involved in polymerization. ]

The indicated compound is produced by polymerization. the

Among the compounds represented by the formula (16-1), the compound represented by the formula (17-1) is preferable. the

Formula (17-1)

[In the formula, R ₁ , R ₂ , a, b, ring D, Q, z, Y ₁ and Y ₂ represent the same meanings as above. ]

Among the compounds represented by formula (17-1), structures represented by formulas (18-1), (18-2), (18-3) and (18-4) are more preferable. the

Formula (18-1) Formula (18-2)

Formula (18-3) Formula (18-4)

In addition, among the compounds represented by the formula (16-2), the compound represented by the formula (17-2) is preferable. the

Formula (17-2)

[In the formula, ring B, ring C, Z ₂ , Z ₃ , Z ₄ , Y ₃ and Y ₄ have the same meanings as above. Z ₆ , Z ₇ and Z ₈ each independently represent C-(Q) _z or a nitrogen atom. Z _1a , Z _5a and Z ₉ each independently represent a carbon atom. Q and z represent the same meaning as above. R ₄ represents a substituent. e represents an integer of 0-2. When there are a plurality of R ₄ , they may be the same or different, and R ₄ may be combined to form a ring. ]

In addition, among the compounds represented by the formula (16-3), the compound represented by the formula (17-3) is preferable. the

Formula (17-3)

[In the formula, ring A, ring B, Z ₁ , Z ₄ , Z ₅ , Y ₅ and Y ₆ have the same meanings as above. Z ₁₀ , Z ₁₁ , Z ₁₂ and Z ₁₃ each independently represent C-(Q) _z or a nitrogen atom. Z _2a and Z _3a each independently represent a carbon atom. Q and z represent the same meaning as above. R ₅ represents a substituent. f represents an integer of 0-2. When there are a plurality of R ₅ , they may be the same or different, and R ₅ may be combined to form a ring. ]

In the production method of the present invention, examples of substituents involved in polymerization include halogen atoms, alkylsulfonate groups, arylsulfonate groups, aralkylsulfonate groups, borate groups, sulfonium methyl , phosphonium methyl, phosphate methyl, monohalomethyl, -B(OH) ₂ , formyl, cyano, vinyl, etc.

Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of increasing the degree of polymerization, bromine atoms and iodine atoms are preferable. the

As the alkylsulfonate group, mesylate group, ethanesulfonate group, trifluoromethanesulfonate group, etc. can be exemplified, and as the arylsulfonate group, benzenesulfonate group, p- As the tosylate group and the like, examples of the arylsulfonate group include benzylsulfonate group and the like. the

As boric acid ester group, the group represented by the following formula can be illustrated. the

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

As a sulfonium methyl group, the group represented by the following formula can be illustrated. the

-CH ₂ S ⁺ Me ₂ X ^- , -CH ₂ S ⁺ Ph ₂ X ^- ,

(X represents a halogen atom, Ph represents a phenyl group.)

As a phosphonium methyl group, the group represented by the following formula can be illustrated. the

-CH ₂ P ⁺ Ph ₃ X ^- (X represents a halogen atom.)

As the phosphate methyl group, groups represented by the following formulas can be exemplified. the

-CH ₂ PO(OR') ₂ (X represents a halogen atom, R' represents an alkyl group, an aryl group, or an aralkyl group.)

Examples of the monohalomethyl group include fluoromethyl, chloromethyl, bromomethyl and iodomethyl. the

Preferred substituents as substituents involved in polymerization vary depending on the type of polymerization reaction, but for example, in the case of using a zero-valent nickel complex such as Yamamoto coupling reaction, halogen atoms, alkylsulfonic acid Ester group, arylsulfonate group or aralkylsulfonate group. In addition, when a nickel catalyst or a palladium catalyst is used such as Suzuki coupling reaction, alkylsulfonate group, halogen atom, borate group, -B(OH) ₂ and the like can be mentioned.

In particular, the polymer compound having the repeating unit of formula (4-1) can use the polymer compound having the repeating unit of formula (4-2) to (4-4) on activated carbon loaded with palladium, platinum , rhodium, ruthenium or a mixture of their noble metal catalyst hydrogenation. the

On the contrary, the macromolecular compound having the repeating unit of formula (4-2)～(4-4) can have the polymer compound of repeating unit of formula (4-1) in 2,3-dichloro-5,6- Dicyano-1,4-benzoquinone (DDQ), obtained by oxidation with tetrabutylammonium bromide under alkaline conditions. the

In addition, when the polymer compound of the present invention has a repeating unit other than formula (1-1) or formula (1-2) or formula (1-3), as long as the formula (1-1) or formula ( 1-2) or compounds having repeating units other than formula (1-3) having two substituents participating in polymerization may coexist and polymerize. the

In addition to the compound represented by the above formula (16-1), (16-2) or (16-3), a compound represented by any of the following formulas (19) to (22) can also be used as a raw material. the

Y ₇ -Ar ₁ -Y ₈ (19)

Y ₉ -(Ar ₂ -X ₁ ) _ff -Ar ₃ -Y ₁₀ (20)

Y ₁₁ -Ar ₄ -X ₂ -Y ₁₂ (21)

Y ₁₃ -X ₃ -Y ₁₄ (22)

[wherein, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , ff, X ₁ , X ₂ and X ₃ are the same as above. Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Y ₁₃ , and Y ₁₄ each independently represent a polymerizable substituent. ]

In addition to the unit represented by the above formula (1-1), (1-2) or (1-3), it is also possible to produce one or more units of (5), (6), (7) or (8) in this order. Unit polymer compound. the

In addition, as a repeating unit other than the repeating unit represented by the above formula (1-1), (1-2) or (1-3), a compound having two substituents corresponding to the above formula (15) participating in polymerization , Compounds represented by the following formula (15-7) can be mentioned. the

[wherein, Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ , Ar ₁₀ , Ar ₁₁ , Ar ₁₂ , x and y are the same as above. _Y15 and _Y16 each independently represent a substituent involved in polymerization. ]

Compounds represented by formula (15-8) or formula (15-9) are more preferred. the

Formula (15-8) Formula (15-9)

[wherein, Re to Rg are as described above. Y ₁₇ , Y ₁₈ , Y ₁₉ , and Y ₂₀ each independently represent a substituent involved in polymerization. ]

Specifically, the production method of the present invention can be carried out by dissolving a compound having a plurality of substituents involved in polycondensation as a monomer in an organic solvent, for example, using a base or a suitable catalyst at a temperature above the melting point and below the boiling point of the organic solvent. For example, "Organic Reactions", Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965; "Organic Syntheses", Collective Volume VI, pp. 407-411, John Wiley & Sons, Inc., 1988; Chem.Rev., Vol. 95, pp. 2475 (1995); J.Organomet.Chem., pp. 576, p. 147 (1999); known methods described in Makromol. Chem., Macromol. Symp., vol. 12, p. 229 (1987). the

In the production method of the polymer compound of the present invention, as a method of polymerizing it, substitutions involving the polymerization of the compounds represented by the above formulas (16-1) to (16-3) and (22) to (25) may be carried out. The bases are correspondingly produced using known polymerization reactions. the

When the polymer compound of the present invention forms a double bond during polymerization, for example, the method described in JP-A-5-202355 can be used. That is, polymerization using the Wittig reaction of a compound having a formyl group and a compound having a phosphonium methyl group, or a compound having a formyl group and a phosphonium methyl group; polymerization using a Heck reaction of a compound having a vinyl group and a compound having a halogen atom ; Polymerization using the dehydrohalogenation method of compounds having 2 or more monohalogenated methyl groups; Polymerization using the sulfonium salt decomposition method of compounds having 2 or more sulfonium methyl groups; Utilizing compounds with formyl groups Methods such as polymerization using Knoevenagel reaction of compounds having cyano groups; methods such as polymerization using McMurry reactions of compounds having 2 or more formyl groups. the

When the polymer compound of the present invention forms a triple bond in the main chain by polymerization, for example, Heck reaction and Sonogashira reaction can be utilized. the

In addition, in the case where no double bond or triple bond is formed, 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) complex can be exemplified. ; The method of polymerization using an oxidizing agent such as FeCl ₃ ; the method of electrochemically oxidative polymerization; or the method of decomposing an intermediate polymer with an appropriate leaving group, etc.

Among them, the method of polymerization by Wittig reaction, the polymerization by Heck reaction, the polymerization by Knoevenagel reaction, the method of polymerization by Suzuki coupling reaction, the method of polymerization by Grignard reaction, and the method of polymerization by nickel 0 valence complex are preferable because of the ease of structural control. method of compound polymerization. the

In the production method of the present invention, in the compound represented by the formula (16-1), (16-2) or (16-3) alone or in the compound selected from the compounds represented by the formula (19) to (22) When polymerizing at least one of the following production methods, that is, Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y 7 , Y ₈ , Y ₉ , Y ₁₀ , _{Y 11 ,} Y ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ , Y ₁₈ , Y ₁₉ , and Y ₂₀ are each independently a halogen atom, an alkylsulfonate group, an arylsulfonate group or an aralkylsulfonate group Ester group, polycondensation in the presence of nickel zero-valent complex.

Examples of raw material compounds include dihalogenated compounds, bis(alkylsulfonate) compounds, bis(arylsulfonate) compounds, bis(arylalkylsulfonate) compounds, and halogen-alkylsulfonate compounds. , Halogen-arylsulfonate compound, halogen-aralkylsulfonate compound, alkylsulfonate-arylsulfonate compound, alkylsulfonate-aralkylsulfonate compound, arylsulfonate Ester-aralkylsulfonate compounds. the

In addition, in the production method of the present invention, when the compound represented by the formula (16-1), (16-2) or (16-3) is used alone or in combination with a compound selected from the compounds represented by the formulas (19) to (22), When at least one of the compounds is polymerized, the production method of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ is preferable. , Y ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ , Y ₁₈ , Y ₁₉ , and Y ₂₀ are each independently a halogen atom, an alkylsulfonate group, an arylsulfonate group, an aralkyl group Sulfonate group, -B(OH) ₂ or borate group, the total number of moles of halogen atom, alkylsulfonate group, arylsulfonate group and aralkylsulfonate group and -B The ratio of the total number of moles of (OH) ₂ and borate groups is substantially 1 (usually K/J is in the range of 0.7 to 1.2), and polycondensation is performed using a nickel or palladium catalyst.

Specific combinations of raw material compounds include dihalogenated compounds, bis(alkylsulfonate) compounds, bis(arylsulfonate) compounds, or bis(arylalkylsulfonate) compounds and diboronic acid compounds or A combination of diboronate compounds. the

In addition, halogen-boric acid compounds, halogen-boric acid ester compounds, arylsulfonate-boric acid compounds, alkylsulfonate-boric acid ester compounds, arylsulfonate-boric acid compounds, arylsulfonic acid Ester-boronate compounds, aralkylsulfonate-boronic acid compounds, aralkylsulfonate-boronic acid compounds, aralkylsulfonate-boronic acid ester compounds. the

The organic solvent varies depending on the compound used or the reaction, but in general, in order to suppress side reactions, the solvent used is preferably deoxidized sufficiently and the reaction is carried out in an inert atmosphere. In addition, it is preferable to perform dehydration treatment in the same manner. However, in the case of a reaction in a two-phase system with water such as a Suzuki coupling reaction, it is not limited thereto. the

Examples of solvents include saturated hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane; unsaturated hydrocarbons such as benzene, toluene, ethylbenzene, and xylene; carbon tetrachloride, chloroform, and methylene chloride , chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane and other halogenated saturated hydrocarbons; chlorobenzene, dichlorobenzene, trichlorobenzene, etc. Halogenated unsaturated hydrocarbons; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, tert-butanol; carboxylic acids such as formic acid, acetic acid, propionic acid; dimethyl ether, diethyl ether, methyl tert-butyl ether , tetrahydrofuran, tetrahydropyran, dioxane and other ethers; trimethylamine, triethylamine, N, N, N', N'-tetramethylethylenediamine, pyridine and other amines; N, N For amides such as dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, and N-methylmorpholine oxide, a single solvent or a mixed solvent thereof can be used. Among them, ethers are preferable, and tetrahydrofuran and diethyl ether are more preferable. the

For the reaction, a base or a suitable catalyst is appropriately added. They can be selected according to the reaction used. The base or catalyst is preferably sufficiently dissolved in the solvent used for the reaction. As a method of mixing the base or the catalyst, it can be exemplified that the reaction liquid is stirred under an inert atmosphere such as argon or nitrogen, and slowly adding a solution of the base or the catalyst; The method of adding the reaction solution. the

When the polymer compound of the present invention is used in polymer LEDs, etc., since its purity affects the performance of elements such as light emitting characteristics, it is preferable to distill, sublimate, recrystallize, etc. the monomer before polymerization. Polymerization after refining. In addition, after polymerization, it is preferable to carry out purification treatment such as reprecipitation purification and separation by chromatography. the

(16-1) to (16-3), (17-1) to (17-3), and (18-1) to (18-4) useful as raw materials for the polymer compound of the present invention can be obtained by It is obtained by brominating a compound having a structure in which Y ₁ to Y ₆ of the above formula is substituted with hydrogen atoms.

In particular, the compound of the structure of formula (18-1) can also be carried by palladium, platinum, rhodium, ruthenium or Mixed catalyst hydrogenation of their precious metals obtained. the

On the contrary, the compound having the structure of formula (18-2)～(18-4) can be obtained by the compound having the structure of formula (18-1) in 2,3-dichloro-5,6-dicyano-1 , 4-Benzoquinone (DDQ), obtained by oxidation with tetrabutylammonium bromide under basic conditions. the

Next, the polymer LED of the present invention will be described. the

The polymer LED of the present invention is characterized in that it has an organic layer between electrodes composed of an anode and a cathode, and the organic layer contains the polymer compound of the present invention. the

The organic layer may be any of a light emitting layer, a hole transport layer, an electron transport layer, etc., but the organic layer is preferably a light emitting layer. the

Here, the light-emitting layer refers to a layer having a function of emitting light, the so-called hole-transporting layer refers to a layer having a function of transporting holes, and the term “electron-transporting layer” refers to a layer having a function of transporting electrons. Furthermore, the electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. A light-emitting layer, a hole transport layer, and an electron transport layer can be independently used in two or more layers. the

When the organic layer is a light-emitting layer, the light-emitting layer as the organic layer may further contain a hole transport material, an electron transport material, or a light-emitting material. Here, the term "luminescent material" refers to a material that exhibits fluorescence and/or phosphorescence. the

When the polymer compound of the present invention is mixed with a hole transport material, the mixing ratio of the hole transport material is 1 wt % to 80 wt %, preferably 5 wt % to 60 wt %, based on the entire mixture. When mixing the polymer compound of the present invention with the electron transport material, the mixing ratio of the electron transport material is 1 wt % to 80 wt %, preferably 5 wt % to 60 wt %, based on the entire mixture. In addition, when the polymer compound of the present invention is mixed with a luminescent material, the mixing ratio of the luminescent material is 1 wt % to 80 wt %, preferably 5 wt % to 60 wt %, based on the entire mixture. When mixing the polymer compound of the present invention with a luminescent material, a hole transport material, and/or an electron transport material, the mixing ratio of the luminescent material is 1 wt % to 50 wt %, preferably 5 wt % to 5 wt %, based on the entire mixture. 40wt%, the total of hole transport material and electron transport material is 1wt%-50wt%, preferably 5wt%-40wt%, the content of the polymer compound of the present invention is 99wt%-20wt%. the

As the hole transport material, electron transport material, and light-emitting material to be mixed, known low-molecular compounds, triplet light-emitting complexes, or high-molecular compounds can be used, but high-molecular compounds are preferably used. Examples of hole-transporting materials, electron-transporting materials, and light-emitting materials of polymer compounds include WO99/139692, WO99/48160, GB2340304A, WO00/53656, WO01/19834, WO00/55927, GB2348316, WO00/46321, WO00/ 06665, WO99/54943, WO99/54385, US5777070, WO98/06773, WO97/05184, WO00/35987, WO00/53655, WO01/34722, WO99/24526, WO00/22027, WO00/22026, WO98/27136, US WO98/21262, US5741921, WO97/09394, WO96/29356, WO96/10617, EP0707020, WO95/07955, JP2001-181618, JP2001-123156, JP2001-3045, JP2000-351967, 2000-303066, TKP 2000-299189, TKP 2000-252065, TKP 2000-136379, TKP 2000-104057, TKP 2000-80167, TKP 10-324870, TKP 10-114891, TKP 9- Polyfluorene, its derivatives and copolymers, polyarylene, its derivatives and copolymers, polyarylene vinylene, its derivatives and copolymers, and aromatic amines disclosed in 111233, JP-A-9-45478, etc. (co)polymers and their derivatives. the

As fluorescent materials of low molecular weight compounds, for example, pigments such as naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethines, xanthenes, coumarins, and cyanines, 8 - Metal complexes of hydroxyquinoline or derivatives thereof, aromatic amines, tetraphenylcyclopentadiene or derivatives thereof, tetraphenylbutadiene or derivatives thereof, and the like. the

Specifically, for example, known materials such as those described in JP-A No. 57-51781 and the same publication No. 59-194393 can be used. the

Examples of triplet light-emitting complexes include Ir(ppy)3 and _Btp2Ir (acac) with iridium as the central metal, PtOEP with platinum as the central metal, Eu(TTA)3phen with europium as the central metal, etc. wait.

As a triplet light-emitting complex, specifically, for example, it is described in Nature, (1998), 395, 151, Appl. Phys. Lett. (1999), 75 (1), 4, Proc. SPIE-Int. Soc. Opt.Eng.(2001), 4105(Organic Light-Emitting Materials and Devices IV), 119, J.Am.Chem.Soc., (2001), 123, 4304, Appl.Phys.Lett.(1997), 71 (18), 2596, Syn.Met., (1998), 94(1), 103, Syn.Met., (1999), 99(2), 1361, Adv.Mater., (1999), 11(10 ), 852, Jpn.J.Appl.Phys., 34, 1883 (1995) et al. the

The composition of the present invention contains at least one material selected from the group consisting of a hole transport material, an electron transport material, and a luminescent material, and the polymer compound of the present invention, and can be used as a luminescent material or a charge transport material. the

The content ratio of at least one material selected from the group consisting of a hole transport material, an electron transport material, and a light emitting material to the polymer compound of the present invention can be determined according to the application. the

As another embodiment of the present invention, a polymer composition containing two or more polymer compounds of the present invention can be exemplified. the

The optimum value of the film thickness of the light emitting layer included in the polymer LED of the present invention differs depending on the material used, and it may be selected so that the driving voltage and luminous efficiency become appropriate values. For example, it is 1 nm to 1 μm, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm. the

As a method of forming the light emitting layer, for example, a method of forming a film from a solution can be exemplified. In the production of polymer LEDs, by using the polymer compound of the present invention, not only when a film is formed from a solution, the solvent can be dried and removed after coating the solution, but also when a charge transport material or a light emitting material is mixed The same method can also be applied in the case of , which is very advantageous in terms of manufacturing. the

As a method of forming a film from a solution, spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, etc. can be used. Coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, offset printing method, inkjet printing method and other coating methods. Printing methods such as screen printing, flexographic printing, offset printing, and inkjet printing are preferable from the viewpoint of easy pattern formation and separate application of multiple colors. the

The ink composition of the present invention can be used as a solution used in printing methods and the like. the

The ink composition of the present invention only needs to contain at least one polymer compound of the present invention and a solvent. In addition to the polymer compound of the present invention, it may also contain a hole transport material, an electron transport material, a luminescent material, a stabilizer, etc. additive. the

The ink composition of the present invention is liquid at the time of device fabrication, and typically refers to a material that is liquid at normal pressure (ie, 1 atmosphere) and 25°C. the

In addition, the ink composition of the present invention does not necessarily need to be colored. the

The ratio of the polymer compound of the present invention in the ink composition is usually 20 wt% to 100 wt%, preferably 40 wt% to 100 wt%, based on the total weight of the ink composition after removing the solvent. the

In addition, the proportion of the solvent in the ink composition is 1 wt % to 99.9 wt %, preferably 60 wt % to 99.9 wt %, more preferably 90 wt % to 99.8 wt %, based on the total weight of the ink composition. the

Although the viscosity of the ink composition (solution) varies depending on the printing method, when the solution is passed through the discharge device such as the inkjet printing method, in order to prevent clogging or flight deflection at the time of discharge, the viscosity is preferably at 25°C. It is in the range of 1 to 20 mPa·s. the

Examples of solvents used in the ink composition of the present invention include chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene, and other chlorine solvents; tetrahydrofuran, dioxane and other ether solvents; toluene, xylene and other aromatic hydrocarbon solvents; cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane Aliphatic hydrocarbon-based solvents such as alkane, n-nonane, and n-decane; ketone-based solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ester-based solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Glycol, Ethylene Glycol Monobutyl Ether, Ethylene Glycol Monoethyl Ether, Ethylene Glycol Monomethyl Ether, Dimethoxyethane, Propylene Glycol, Diethoxymethane, Triethylene Glycol Monoethyl Ether, Glycerin, 1,2- Polyols such as hexanediol and their derivatives; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; sulfone solvents such as dimethyl sulfoxide; N-methyl-2-pyrrolidone, N, N-dimethylformamide and other amide solvents. In addition, among these solvents, it is preferable to contain one or more organic solvents having a structure including at least one benzene ring and having a melting point of 0°C or lower and a boiling point of 100°C or higher. the

、正丙基苯、异丙基苯、正丁基苯、异丁基苯、仲丁基苯、苯甲醚、乙氧基苯、1-甲基萘、环己烷、环己酮、环己基苯、联二环己烷、环己烯基环己酮、正庚基环己烷、正己基环己烷、甲基苯甲酸酯、2-丙基环己酮、2-庚酮、3-庚酮、4-庚酮、2-辛酮、2-壬酮、2-癸酮、二环己基酮，更优选含有二甲苯、苯甲醚、

、环己基苯、联二环己烷甲基苯甲酸酯当中的至少一种。  As the type of solvent, from the viewpoints of solubility of the polymer compound of the present invention in an organic solvent, uniformity during film formation, viscosity characteristics, etc., aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ester solvents, Ketone solvents, preferably toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene,

, n-propylbenzene, cumene, n-butylbenzene, isobutylbenzene, sec-butylbenzene, anisole, ethoxybenzene, 1-methylnaphthalene, cyclohexane, cyclohexanone, cyclohexanone Hexylbenzene, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, methyl benzoate, 2-propylcyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2-decanone, dicyclohexyl ketone, more preferably containing xylene, anisole,

, cyclohexylbenzene, and dicyclohexyl methyl benzoate at least one.

The types of solvents in the ink composition are preferably 2 or more types, more preferably 2 to 3 types, and even more preferably 2 types from the viewpoint of film-forming properties and device characteristics. the

When two types of solvents are contained in the ink composition, one of the solvents may be in a solid state at 25°C. From the viewpoint of film-forming properties, it is preferable that one solvent has a boiling point of 180° C. or higher, the other solvent has a boiling point of 180° C. or lower, more preferably one solvent has a boiling point of 200° C. or higher, and the other solvent has a boiling point of 200° C. or higher. The first solvent is a solvent with a boiling point below 180°C. In addition, from the viewpoint of viscosity, it is preferable to dissolve 0.2 wt% or more of the polymer compound of the present invention in both of the two solvents at 60°C, and it is preferable to dissolve it in one of the two solvents at 25°C. 0.2 wt% or more of the polymer compound of the present invention. the

When the ink composition contains three solvents, one or two of them may be in a solid state at 25°C. From the viewpoint of film-forming properties, at least one of the three solvents is preferably a solvent having a boiling point of 180° C. or higher, at least one of the solvents is a solvent having a boiling point of 180° C. or lower, more preferably at least one of the three solvents The solvents have a boiling point of not less than 200°C and not more than 300°C, and at least one solvent has a boiling point of not more than 180°C. In addition, from the viewpoint of viscosity, it is preferable to dissolve 0.2 wt % or more of the polymer compound of the present invention in two of the three solvents at 60° C., preferably in one of the three solvents, 0.2 wt% or more of the polymer compound of the present invention is dissolved at 25°C. the

When the ink composition contains two or more solvents, from the viewpoint of viscosity and film-forming properties, the solvent with the highest boiling point is preferably 40 to 90 wt%, more preferably 50 to 90 wt%, based on the weight of all solvents in the ink composition %, more preferably 65 to 85 wt%. the

及甲基苯甲酸酯构成的组合物。  As the ink composition of the present invention, a composition composed of anisole and bicyclohexane, a composition composed of anisole and cyclohexylbenzene, a composition composed of xylene Compositions composed of dicyclohexyl and bicyclohexane, compositions composed of xylene and cyclohexylbenzene, compositions composed of

and methyl benzoate compositions.

Among the additives that may be contained in the ink composition of the present invention, examples of hole transport materials include polyvinylcarbazole or its derivatives, polysilane or its derivatives, and aromatic amines in the side chain or main chain. Polysiloxane derivatives, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or its derivatives, polythiophene or its derivatives, polypyrrole or its derivatives, poly(p-phenylenevinylene) or derivatives thereof, or poly(2,5-thienylenevinylene) or derivatives thereof. the

Examples of electron transport materials include oxadiazole derivatives, anthraquinone dimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinone or derivatives thereof, tetracyanoanthraquinone di Methane or its derivatives, fluorene derivatives, diphenyldicyanoethylene or its derivatives, phenoquinone derivatives or metal complexes of 8-hydroxyquinoline or its derivatives, polyquinoline or its derivatives substances, polyquinoxaline or its derivatives, polyfluorene or its derivatives. the

Examples of light-emitting materials include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine-based, xanthene-based, coumarin-based, cyanine-based pigments, 8-hydroxyquinoline or Metal complexes of its derivatives, aromatic amines, tetraphenylcyclopentadiene or its derivatives, or tetraphenylbutadiene or its derivatives, etc. the

The ink composition (solution) of the present invention may contain additives for adjusting viscosity and/or surface tension in addition to the polymer compound of the present invention. As the additive, a high-molecular-weight high-molecular-weight compound (thickener) or weak solvent for increasing the viscosity, a low-molecular-weight compound for reducing the viscosity, a surfactant for reducing the surface tension, etc. may be used in combination appropriately. Can. the

As the above-mentioned high-molecular-weight polymer compound, it is sufficient that it is soluble in a solvent similarly to the polymer compound of the present invention, and does not hinder light emission or charge transport. For example, high-molecular-weight polystyrene, polymethyl methacrylate, or a substance having a large molecular weight among the high-molecular compounds of the present invention can be used. The weight average molecular weight is preferably at least 500,000, more preferably at least 1 million. the

Weak solvents can also be used as thickeners. That is, the viscosity can be increased by adding a small amount of weak solvent to the solid content in the solution. When adding a weak solvent for this purpose, the type and amount of the solvent may be selected within a range in which the solid content in the solution does not precipitate. the

In addition, in order to improve storage stability, the ink composition (solution) of the present invention may contain an antioxidant in addition to the polymer compound of the present invention. As the antioxidant, as long as it is soluble in a solvent like the polymer compound of the present invention and does not interfere with light emission or charge transport, examples include phenolic antioxidants, phosphorus antioxidants, and the like. the

From the viewpoint of the solubility of the polymer compound of the present invention in a solvent, the difference between the solubility parameter of the solvent and the solubility parameter of the polymer compound is preferably 10 or less, more preferably 7 or less. the

The solubility parameter of the solvent and the solubility parameter of the polymer compound of the present invention can be obtained by the method described in "Solvent Handbook (Kodansha, 1976)". the

Examples of the polymer LED of the present invention include polymer LEDs in which an electron transport layer is provided between the cathode and the luminescent layer, polymer LEDs in which a hole transport layer is provided between the anode and the luminescent layer, and polymer LEDs in which the cathode and the luminescent layer are provided. Polymer LEDs and the like in which an electron transport layer is provided between layers and a hole transport layer is provided between the anode and the light emitting layer. the

For example, the following structures a) to d) can be specifically illustrated. the

a) anode/luminescent layer/cathode

b) anode/hole transport layer/emissive layer/cathode

c) anode/luminescent layer/electron transport layer/cathode

d) Anode/hole transport layer/luminescent layer/electron transport layer/cathode

(Here, / means that each layer is stacked adjacently. The same applies below.)

The polymer LED of the present invention also includes an LED containing the polymer compound of the present invention in a hole transport layer and/or an electron transport layer. the

When the polymer compound of the present invention is used in the hole transport layer, the polymer compound of the present invention is preferably a polymer compound containing a hole transport group. Copolymers, copolymers with stilbene, etc. the

In addition, when the polymer compound of the present invention is used in the electron transport layer, the polymer compound of the present invention is preferably a polymer compound containing an electron transport group, and specific examples thereof include dioxane Copolymers of azoles, copolymers with triazoles, copolymers with quinoline, copolymers with quinoxaline, copolymers with benzothiadiazole, etc. the

When the polymer LED of the present invention has a hole-transporting layer, examples of the hole-transporting material used include polyvinylcarbazole or its derivatives, polysilane or its derivatives, side chain or main chain Polysiloxane derivatives with aromatic amines, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or its derivatives, polythiophene or its derivatives , polypyrrole or derivatives thereof, poly(p-phenylenevinylene) or derivatives thereof, or poly(2,5-thienylenevinylene) or derivatives thereof. the

Specifically, examples of the hole transport material include JP-A-63-70257, JP-A-63-175860, JP-2-135359, JP-2-135361, and 2 -Materials described in Gazette No. 209988, the same Gazette No. 3-37992, the same Gazette No. 3-152184, etc. the

Among them, as the hole-transporting material used in the hole-transporting layer, polyvinylcarbazole or its derivatives, polysilane or its derivatives, those having an aromatic amine compound group in the side chain or the main chain are preferable. Polysiloxane derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, poly(p-phenylenevinylene) or derivatives thereof or poly(2,5-thienylenevinylene) or Polymer hole transport materials such as derivatives thereof are more preferably polyvinylcarbazole or derivatives thereof, polysilane or derivatives thereof, and polysiloxane derivatives having aromatic amines in side chains or main chains. the

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

The polymer binder to be mixed is preferably one that does not significantly hinder charge transport, and one that does not strongly absorb visible light can be preferably used. Examples of the polymer binder include poly(N-vinylcarbazole), polyaniline or derivatives thereof, polythiophene or derivatives thereof, poly(p-phenylene vinylene) or derivatives thereof, Poly(2,5-thienylenevinylene) or its derivatives, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane wait. the

Polyvinylcarbazole or its derivatives can be obtained, for example, from vinyl monomers by cationic polymerization or radical polymerization. the

Examples of polysilanes or derivatives thereof include compounds described in Chem. Rev. Vol. 89, p. 1359 (1989), British Patent No. GB2300196, and the like. As the synthesis method, the methods described therein can also be used, but the Kipping method is particularly preferably used. the

Since polysiloxane or its derivative has substantially no hole transport property in the siloxane skeleton structure, it is preferable to use a substance having the structure of the above-mentioned low-molecular hole transport material in the side chain or the main chain. In particular, a substance having a hole-transporting aromatic amine in a side chain or a main chain can be exemplified. the

The method of forming a film of the hole transport layer is not particularly limited, but if it is a low-molecular hole transport material, a method of forming a film from a mixed solution thereof and a polymer binder can be exemplified. In addition, if it is a polymeric hole transport material, a method of forming a film from a solution can be exemplified. the

The solvent used for film formation from a solution is not particularly limited as long as it dissolves the hole transport material. Examples of the solvent include chlorine-based solvents such as chloroform, dichloromethane, 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; , butyl acetate, ethyl cellosolve acetate and other ester solvents. the

As a method of forming a film from a solution, spin coating method, casting method, micro gravure coating method, gravure coating method, rod coating method, roll coating method, wire rod coating method, dip coating method, etc. Coating method, spray coating method, screen printing method, flexographic printing method, offset printing method, inkjet printing method and other coating methods. the

As the film thickness of the hole transport layer, the optimum value varies depending on the material used, and it is sufficient to select such that the driving voltage and luminous efficiency become moderate values. However, at least a thickness that does not cause pinholes is required. When thick, the driving voltage of the element becomes high, which is not preferable. Therefore, the film thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm. the

When the polymer LED of the present invention has an electron transport layer, known materials can be used as the electron transport material used, and oxadiazole derivatives, anthraquinone dimethane or derivatives thereof, benzoquinone or its derivatives can be exemplified. Derivatives, naphthoquinone or its derivatives, anthraquinone or its derivatives, tetracyanoanthraquinone dimethane or its derivatives, fluorene derivatives, diphenyldicyanoethylene or its derivatives, diphenoquinone Derivatives or metal complexes of 8-hydroxyquinoline or its derivatives, polyquinoline or its derivatives, polyquinoxaline or its derivatives, polyfluorene or its derivatives, etc. the

Specifically, JP-A-63-70257, JP-A-63-175860, JP-2-135359, JP-2-135361, JP-2-209988, and Materials described in Publication No. 3-37992, the same Publication No. 3-152184, and the like. the

Among them, metal complexes of oxadiazole derivatives, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinone or derivatives thereof, or 8-hydroxyquinoline or derivatives thereof, polyquinoline or Its derivatives, polyquinoxaline or its derivatives, polyfluorene or its derivatives, etc., more preferably 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4 -Oxadiazoles, benzoquinones, anthraquinones, tris(8-quinolinolate)aluminum, polyquinolines. the

The film-forming method as the electron-transporting layer is not particularly limited, but if it is a low-molecular-weight electron-transporting material, a vacuum evaporation method from a powder or a film-forming method from a solution or a molten state can be exemplified. For conveying materials, a method of forming a film from a solution or a molten state can be exemplified. When forming a film from a solution or a molten state, the above-mentioned polymer binder may be used in combination. the

The solvent used for film formation from a solution is not particularly limited as long as it dissolves the electron transport material and/or the polymer binder. Examples of the solvent include chlorine-based solvents such as chloroform, dichloromethane, 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; , butyl acetate, ethyl cellosolve acetate and other ester solvents. the

As a film-forming method from a solution or a molten state, spin coating, casting, microgravure coating, gravure coating, rod coating, roll coating, wire-wound bar coating, dipping, etc., can be used. Coating method, spray coating method, screen printing method, flexographic printing method, offset printing method, inkjet printing method and other coating methods. the

As the film thickness of the electron transport layer, the optimum value differs depending on the material used, as long as the driving voltage and luminous efficiency can be selected in such a way as to achieve an appropriate value, but at least a thickness that does not cause pinholes is required, and when it is too thick , the driving voltage of the element becomes high, which is not ideal. 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. the

In addition, among the charge transport layers provided adjacent to the electrodes, the layer that has the function of improving the efficiency of injecting charges from the electrodes and has the effect of lowering the driving voltage of the device is sometimes generally referred to as a charge injection layer (hole injection layer). layer, electron injection layer). the

In addition, in order to improve the adhesion with the electrode or improve the charge injection from the electrode, the above-mentioned charge injection layer or an insulating layer with a film thickness of 2 nm or less may be provided adjacent to the electrode. In addition, in order to improve the adhesion of the interface or prevent A thin buffer layer may also be inserted at the interface of the charge transport layer or the light emitting layer by mixing or the like. the

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. the

The polymer compound of the present invention can also be made into an organic semiconductor thin film and used as a polymer field effect transistor. As a structure of a polymer field effect transistor, generally, a source and a drain are provided in contact with an active layer made of a polymer, and then a gate is provided with an insulating layer in contact with the active layer. the

Polymer field effect transistors are usually formed on a support substrate. The material of the supporting substrate is not particularly limited as long as it does not interfere with the characteristics of the field effect transistor, and a glass substrate, a flexible film substrate, or a plastic substrate can be used. the

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

When forming the active layer, it is very advantageous in terms of production to use a polymer soluble in an organic solvent, and thus it is preferable. As a film-forming method from a solution in which a polymer is dissolved in an organic solvent, spin coating, casting, microgravure coating, gravure coating, rod coating, roll coating, wire winding, etc., can be used. Coating methods such as bar coating, dip coating, spray coating, screen printing, flexographic printing, offset printing, and inkjet printing. the

It is preferably a sealed polymer field effect transistor formed by sealing the polymer field effect transistor after it is manufactured. In this way, the polymer field effect transistor can be blocked from the atmosphere, and the deterioration of the characteristics of the polymer field effect transistor can be suppressed. the

Examples of sealing methods include a method of covering with UV curable resin, thermosetting resin, or inorganic SiONx film, and a method of bonding glass plates or films with UV curable resin, thermosetting resin, and the like. In order to effectively block the atmosphere from the atmosphere, it is preferable to carry out the steps up to sealing without exposing the polymer field effect transistor to the atmosphere (for example, in a dry nitrogen atmosphere, in a vacuum, etc.). the

In the present invention, examples of polymer LEDs provided with a charge injection layer (electron injection layer, hole injection layer) include polymer LEDs provided with a charge injection layer adjacent to a cathode, and polymer LEDs provided with a charge injection layer adjacent to an anode. Polymer LED with charge injection layer. the

For example, the following structures e)-p) are specifically mentioned. the

e) Anode/Charge Injection Layer/Emitting Layer/Cathode

f) anode/luminescent 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/emissive layer/charge injection layer/cathode

j) anode/charge injection layer/hole transport layer/emissive layer/charge injection layer/cathode

k) anode/charge injection layer/emissive layer/electron transport layer/cathode

l) anode/luminescent layer/electron transport layer/charge injection layer/cathode

m) anode/charge injection layer/light-emitting layer/electron transport layer/charge injection layer/cathode

n) anode/charge injection layer/hole transport layer/light emitting layer/electron transport layer/cathode

o) anode/hole transport layer/light emitting layer/electron transport layer/charge injection layer/cathode

p) anode/charge injection layer/hole transport layer/light emitting layer/electron transport layer/charge injection layer/cathode

As a specific example of the charge injection layer, a layer containing a conductive polymer can be exemplified; it is provided between the anode and the hole transport layer, and contains an intermediate layer having an anode material and a hole transport material contained in the hole transport layer. A layer of a material having an ionization potential of a value of ; a layer of a material having an electron affinity of an intermediate value between the cathode material and the electron transport material contained in the electron transport layer, etc., provided between the cathode and the electron transport layer. the

When the above-mentioned charge injection layer is a layer containing a conductive polymer, the conductivity of the conductive polymer is preferably not less than 10 ⁻⁵ S/cm and not more than 10 ³ . In order to reduce the leakage current between light-emitting pixels, more It is preferably 10 ^-5 S/cm or more and 10 ² or less, more preferably 10 ^-5 S/cm or more and 10 ¹ or less.

When the above-mentioned charge injection layer is a layer containing a conductive polymer, the conductivity of the conductive polymer is preferably not less than 10 ⁻⁵ S/cm and not more than 10 ³ S/cm. In order to reduce leakage between light-emitting pixels, The current is more preferably from 10 ^-5 S/cm to 10 ² S/cm, and still more preferably from 10 ^-5 S/cm to 10 ¹ S/cm.

Generally, the conductive polymer is doped with an appropriate amount of ions so that the electrical conductivity of the conductive polymer is not less than 10 ⁻⁵ S/cm and not more than 10 ³ .

The type of ions to be doped is an anion in the case of a hole injection layer, and a cation in the case of an electron injection layer. Examples of anions include polystyrenesulfonate ions, alkylbenzenesulfonate ions, and camphorsulfonate ions, and examples of cations include lithium ions, sodium ions, potassium ions, and tetrabutylammonium ions. wait. the

The film thickness of the charge injection layer is, for example, 1 nm to 100 nm, preferably 2 nm to 50 nm. the

The material used for the charge injection layer may be appropriately selected according to its relationship with the electrode or the material of the adjacent layer, and polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives can be exemplified. , polyphenylene vinylene and its derivatives, polythiophene vinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, containing aromatics in the main chain or side chain Conductive polymers such as polymers with an amine structure, metal phthalocyanines (copper phthalocyanines, etc.), carbon, etc. the

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. Examples of polymer LEDs provided with an insulating layer with a film thickness of 2 nm or less include polymer LEDs provided with an insulating layer with a film thickness of 2 nm or less adjacent to the cathode, and polymer LEDs provided with an insulating layer with a film thickness of 2 nm or less adjacent to the anode. Polymer LED below the insulating layer. the

Specifically, the following structures q) to ab) can be mentioned. the

q) anode/insulating layer/luminescent layer/cathode with film thickness below 2nm

r) anode/luminescent layer/insulating layer/cathode with film thickness below 2nm

s) Anode/insulating layer with film thickness below 2nm/luminescent layer/insulating layer with film thickness below 2nm/cathode

t) anode/insulating layer with film thickness below 2nm/hole transport layer/luminescent layer/cathode

u) Anode/hole transport layer/luminescent layer/insulating layer with film thickness below 2nm/cathode

v) Anode/insulating layer with film thickness below 2nm/hole transport layer/light-emitting layer/insulating layer with film thickness below 2nm/cathode

w) anode/insulating layer with film thickness below 2nm/luminescent layer/electron transport layer/cathode

x) Anode/luminescent layer/electron transport layer/insulating layer with film thickness below 2nm/cathode

y) Anode/insulating layer with film thickness below 2nm/luminescent layer/electron transport layer/insulating layer with film thickness below 2nm/cathode

z) Anode/insulating layer with film thickness below 2nm/hole transport layer/luminescent layer/electron transport layer/cathode

aa) anode/hole transport layer/luminescent layer/electron transport layer/insulating layer with film thickness below 2nm/cathode

ab) Anode/insulating layer with a film thickness of less than 2nm/hole transport layer/luminescent layer/electron transport layer/insulating layer with a film thickness of less than 2nm/cathode

The substrate on which the polymer LED of the present invention is formed can be any substrate that does not change when electrodes and organic layers are formed, and examples thereof include glass, plastic, polymer films, silicon substrates, and the like. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent. the

Generally, at least one of the anode and the cathode of the polymer LED of the present invention is transparent or translucent. The anode side is preferably transparent or translucent. the

As the material of the anode, a conductive metal oxide film, a semitransparent metal thin film, or the like can be used. Specifically, indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO) as a composite of these, films made of conductive glass made of indium zinc oxide (NESA, etc.), Gold, platinum, silver, copper, etc., preferably ITO, indium zinc oxide, tin oxide. Examples of the production method include a vacuum vapor deposition method, a sputtering method, an ion plating method, a coating method, and the like. In addition, as the anode, an organic transparent conductive film such as polyaniline or its derivatives, polythiophene or its derivatives, or the like can also be used. the

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

In addition, on the anode, in order to make charge injection easier, a layer composed of phthalocyanine derivatives, conductive polymers, carbon, etc. can also be provided; or a layer composed of metal oxides or metal fluorides, organic insulating materials, etc. A layer with an average film thickness of 2 nm or less. the

As the cathode material used in the polymer LED of the present invention, a material having a small work function is preferable. Examples include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium and other metals; and their Alloys of two or more of them; or alloys of more than one of them with gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin; graphite or graphite interlayer compounds, etc. . Examples of alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys. The cathode may also have a laminated structure of two or more layers. the

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

As a method for producing the cathode, a vacuum vapor deposition method, a sputtering method, a lamination method of thermocompression bonding a metal thin film, or the like can be used. In addition, between the cathode and the organic layer, a layer made of conductive polymers, or a layer made of metal oxides or metal fluorides, organic insulating materials, etc., with an average film thickness of 2 nm or less may be provided. After completion, a protective layer to protect the polymer LED can also be installed. In order to use the polymer LED stably for a long time, it is preferable to install a protective layer and/or a protective cover to protect the element from external influences. the

As the protective layer, polymer compounds, metal oxides, metal fluorides, metal borides, and the like can be used. In addition, a glass plate, a plastic plate whose surface has been subjected to a low water permeability treatment, etc. can be used as a protective cover, and a method of sealing the cover by bonding a thermosetting resin or a photosetting resin to the element substrate is preferably used. If spacers are used to maintain space, it is easy to prevent damage to components. If an inert gas such as nitrogen or argon is injected into this space, the oxidation of the cathode can be prevented. In addition, by installing a desiccant such as barium oxide in this space, it is possible to easily prevent the moisture absorbed in the manufacturing process from damaging the element. . Among them, any one or more methods are preferably employed. the

The polymer LED of the present invention can be used in planar light sources, segmented display devices, dot matrix display devices, and liquid crystal display devices (such as backlights of liquid crystal display devices). the

In order to obtain planar light emission using the polymer LED of the present invention, it is only necessary to arrange planar anodes and cathodes so as to overlap each other. In addition, in order to obtain pattern-like light emission, there is a method of providing a mask with a pattern-like window on the surface of the above-mentioned planar light-emitting element, and a method of forming an organic layer of a non-light-emitting part extremely thick so that it does not emit light substantially. method, a method of patterning either one or both electrodes of the anode or the cathode. By forming a pattern by any of these methods and disposing certain electrodes independently on/off, a segmented display element capable of displaying numerals, letters, simple signs, etc. can be obtained. In addition, in order to form a dot matrix device, both the anode and the cathode may be arranged in stripes and orthogonally arranged. Partial color display and multi-color display can be realized by coating a plurality of polymer phosphors with different luminescent colors, or by using color filters or fluorescence conversion filters. The dot matrix element can be driven passively, or combined with TFT etc. for active driving. These display elements can be used as display devices such as computers, televisions, portable terminals, mobile phones, navigators, and video camera viewfinders. the

In addition, the above-mentioned planar light-emitting element is self-luminous and thin, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar light source for illumination. In addition, if a flexible substrate is used, it can also be used as a curved light source or a display device. the

Hereinafter, examples are given to explain the present invention in more detail, but the present invention is not limited to them. the

(number average molecular weight and weight average molecular weight) 

Here, the number average molecular weight and weight average molecular weight were calculated|required for the number average molecular weight and weight average molecular weight of polystyrene conversion by GPC (manufactured by Shimadzu Corporation: LC-10Avp). The polymer to be measured was dissolved in tetrahydrofuran to a concentration of about 0.5% by weight, and 50 μL was injected into the GPC. Tetrahydrofuran was used as the mobile phase of GPC at a flow rate of 0.6 mL/min. As a column, two pieces of TSKgel SuperHM-H (manufactured by Toso) and one piece of TSKgel SuperH2000 (manufactured by Toso) were connected in series. As a detector, a differential refractive index detector (manufactured by Shimadzu Corporation: RID-10A) was used. the

(Fluorescence Spectroscopy)

The measurement of the fluorescence spectrum was carried out in the following manner. Thin films of the polymer were produced by spin coating a 0.8 wt% solution of the polymer on quartz. The thin film was excited at a wavelength of 350 nm, and the fluorescence spectrum was measured using a fluorescence spectrophotometer (Fluorolog manufactured by Horiba, Ltd.). In order to obtain the relative fluorescence intensity in the thin film, the fluorescence spectrum plotted by the wavenumber was integrated in the spectral measurement range using the Raman line intensity of water as a standard, and measured using a spectrophotometer (Cary5E manufactured by Varian). The value obtained by dividing the absorbance at the excitation wavelength was obtained. the

(HPLC determination)

Measuring instrument: Agilent 1100LC

Measuring conditions: L-Column ODS, 5μm, 2.1mm×150mm;

Liquid A: Acetonitrile, Liquid B: THF

Gradient

Liquid B:

0% (60min.) → 10% up/min → 100% (10min),

Sample concentration: 5.0mg/mL (THF solution),

Injection volume: 1μL

Detection wavelength: 350nm

Synthesis example 1

(Synthesis of 1-bromo-4-tert-butyl-2,6-dimethylbenzene) 

Under an inert atmosphere, 225 g of acetic acid was added to a 500 ml three-necked flask, and 5-tert-butyl-m-xylene was added. Next, after adding 31.2 g of bromine, it was made to react at 15-20 degreeC for 3 hours. the

The reaction solution was added to 500 ml of water, and the precipitate was filtered. It was washed twice with 250 ml of water to obtain 34.2 g of a white solid. the

<Synthesis of N,N'-diphenyl-N,N'-bis(4-tert-butyl-2,6-dimethylphenyl)-1,4-phenylenediamine>

Under an inert atmosphere, 36 ml of degassed dehydrated toluene was added to a 100 ml three-necked flask, and 0.63 g of tri(tert-butyl)phosphine was added. Next, add 0.41 g of tris(dibenzylideneacetone) dipalladium, 9.6 g of 1-bromo-4-tert-butyl-2,6-dimethylbenzene, 5.2 g of sodium tert-butoxide, N,N'- After 4.7 g of diphenyl-1,4-phenylenediamine was reacted at 100° C. for 3 hours. the

The reaction solution was added to 300 ml of saturated brine, and extracted with 300 ml of chloroform heated to about 50°C. After the solvent was distilled off, 100 ml of toluene was added, the mixture was heated until the solid was dissolved, and after standing to cool, the precipitate was filtered to obtain 9.9 g of a white solid. the

<Synthesis of N,N'-bis(4-bromophenyl)-N,N'-bis(4-tert-butyl-2,6-dimethylphenyl)-1,4-phenylenediamine>

Under an inert atmosphere, add dehydrated N,N-dimethylformamide 350ml to a 100ml three-necked flask, after dissolving N'-diphenyl-N,N'-bis(4-tert-butyl-2,6 After 5.2 g of -dimethylphenyl)-1,4-phenylenediamine, add N-bromosuccinimide 3.5 g/N, N-dimethylformamide solution dropwise in an ice bath, and make it react for a day and night . the

150 ml of water was added to the reaction liquid, and the deposited precipitate was filtered and washed twice with 50 ml of methanol to obtain 4.4 g of a white solid. the

¹ H-NMR (300MHz/THF-d8)

δ(ppm)=1.3[s, 18H], 2.0[s, 12H], 6.6~6.7[d, 4H], 6.8~6.9[br, 4H], 7.1[s, 4H], 7.2~7.3[d, 4H]

MS(FD ⁺ )M ⁺ 738

Synthesis example 2

<Synthesis of N, N'-diphenyl-N, N'-bis(4-tert-butyl-2,6-dimethylphenyl)-benzidine>

Under an inert atmosphere, 1660 ml of dehydrated toluene was added to a 300 ml three-necked flask, and 275.0 g of N,N'-diphenylbenzidine and 449.0 g of 4-tert-butyl-2,6-dimethylbromobenzene were added. Next, 7.48 g of tris(dibenzylideneacetone)dipalladium and 196.4 g of sodium tert-butoxide were added, and then 5.0 g of tris(tert-butyl)phosphine was added. Then, it was made to react at 105 degreeC for 7 hours. the

2,000 ml of toluene was added to the reaction liquid, filtered through cerite, and the filtrate was washed three times with 1,000 ml of water, and concentrated to 700 ml. To this was added 1600 ml of a toluene/methanol (1:1) solution, and the precipitated crystals were filtered and washed with methanol. 479.4 g of a white solid were obtained. the

<Synthesis of N,N'-bis(4-bromophenyl)-N,N'-bis(4-tert-butyl-2,6-dimethylphenyl)-benzidine>

Under an inert atmosphere, after dissolving 472.8 g of the above-mentioned N, N'-diphenyl-N, N'-bis(4-tert-butyl-2,6-dimethylphenyl)-benzidine in 4730 g of chloroform 281.8 g of N-bromosuccinimide was divided into 12 parts and added in 1 hour under shading and ice bathing, and reacted for 3 hours. the

1439 ml of chloroform was added to the reaction liquid, followed by filtration, and the chloroform solution of the filtrate was washed with 2159 ml of 5% sodium thiosulfate, and the toluene was distilled off to obtain white crystals. The obtained white crystals were recrystallized from toluene/methanol to obtain 678.7 g of white crystals. the

MS (APCI (+)): (M+H) ⁺ 815.2

Embodiment 1<The synthesis of compound B>

<Synthesis of Compound A>

(Compound A)

31 ml of ion-exchanged water was added to the reaction vessel, and 29 g (727 mmol) of sodium hydroxide was added little by little while stirring to completely dissolve it. The system was replaced with argon, and 30 ml of toluene and 5.0 g (24 mmol) of 1,2,3,10b-tetrahydrofluoranthene were added, stirred and dissolved. Next, 2.3 g (7.3 mmol) of tetrabutylammonium bromide and 9.4 g (48 mmol) of octyl bromide were added, and it was made to react at 40 degreeC for 3 hours. The organic layer was extracted with toluene and water, and dried over sodium sulfate. After distilling off the solvent, it was purified by silica gel chromatography using hexane as a developing solvent to obtain 6.45 g of pale yellow crystals. the

MS (APCI (+)): 318 ([M+H] ⁺ )

¹ H-NMR (300MHz/CDCl ₃ ) δ7.69(1H,d), 7.50(1H,d), 7.40(1H,d), 7.34～7.22(3H,m), 7.03(1H,d), 3.07 ～2.96(1H, m), 2.77～2.70(1H, m), 2.37～2.18(2H, m), 1.95～1.74(3H, m), 1.27～1.04(11H, m), 0.84～0.69(5H, m)

(Synthesis of compound B)

(compound B)

5.8 g (18 mmol) of compound A and 115 ml of a mixed solvent of acetic acid:dichloromethane = 1:1 were added to a reaction vessel replaced with argon, and stirred and dissolved at room temperature. Next, 14 g (36 mmol) of benzyltrimethylammonium tribromide was added, and zinc chloride was added with stirring until benzyltrimethylammonium tribromide was completely dissolved. While following the reaction with HPCL, benzyltrimethylammonium tribromide and zinc chloride were added as appropriate. After the reaction, the organic layer was extracted with chloroform and water, washed twice with water, and then neutralized with potassium carbonate aqueous solution. After drying over sodium sulfate, the solvent was distilled off, purified by silica gel chromatography using hexane as a developing solvent, and then recrystallized from a mixed solvent of ethanol:hexane = 10:1 to obtain 5.08 g of compound B as a white powder. the

MS (APPI (+)): 476 (M ⁺ )

¹ H-NMR (300MHz/CDCl ₃ ) δ7.53～7.43(4H, m), 7.33(1H, d), 2.90～2.84(2H, m), 2.33～2.22(2H, m), 2.05～1.96( 1H, m), 1.83～1.64(2H, m), 1.32～1.05(13H, m), 0.85～0.81(3H, m)

Example 2

(Synthesis of polymer compound 1)

Compound B (0.1 g) and 2,2'-bipyridine (0.089 g) were dissolved in 19 mL of dehydrated tetrahydrofuran, and bis(1,5-cyclooctadiene)nickel was added to the solution under a nitrogen atmosphere (0) {Ni(COD) ₂ } (0.156g), heated up to 60°C, and reacted for 3 hours. The reaction solution was cooled to room temperature, added dropwise to a mixed solution of 25% ammonia water 1 mL/methanol 19 mL/ion-exchanged water 19 mL, stirred for 1 hour, and the precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 1) was 0.08 g. In addition, the polystyrene-equivalent number average molecular weight was 2.9×10 ⁴ , and the weight average molecular weight was 6.1×10 ⁴ .

Example 3

<Synthesis of Polymer Compound 2>

Compound B (0.557g), N, N'-bis(4-bromophenyl)-N,N'-bis(4-tert-butyl-2,6-dimethylphenyl)-1,4- After dissolving phenylenediamine (0.096 g) and 2,2'-bipyridine (0.548 g) in 140 mL of dehydrated tetrahydrofuran, the inside of the system was replaced with nitrogen by bubbling argon. After heating up to 60°C, bis(1,5-dichlorooctadiene)nickel(0){Ni(COD) ₂ }(0.965g) was added to the solution under nitrogen atmosphere, stirred and reacted for 3 hours. The reaction solution was cooled to room temperature, added dropwise to a mixed solution of 25% ammonia 5mL/methanol 140mL/ion-exchanged water 140mL, stirred for 1 hour, and the precipitate was filtered, dried under reduced pressure, and dissolved in toluene 40ml. After dissolution, 1.6 g of diatomaceous earth (radiolite) was added, stirred for 30 minutes, and insoluble matter was filtered. The resulting filtrate was purified by passing through an alumina column. Then, 80 mL of 5.2% aqueous hydrochloric acid was added, and after stirring for 3 hours, the aqueous layer was removed. Then, 80 mL of 4% ammonia water was added, and the aqueous layer was removed after stirring for 2 hours. Next, about 80 mL of ion-exchanged water was added to the organic layer, and after stirring for 1 hour, the aqueous layer was removed. Thereafter, the organic layer was poured into 160 ml of methanol, stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 2) was 0.33 g. In addition, the polystyrene-equivalent number average molecular weight and weight average molecular weight were Mn=1.6×10 ⁴ and Mw=8.7×10 ⁴ , respectively.

Example 4

<Synthesis of Polymer Compound 3>

Compound B (0.433g), N, N'-bis(4-bromophenyl)-N,N'-bis(4-tert-butyl-2,6-dimethylphenyl)-benzidine (0.318 g) After dissolving 2,2'-bipyridine (0.548 g) in 140 mL of dehydrated tetrahydrofuran, the inside of the system was replaced with nitrogen by bubbling argon. After heating up to 60°C, bis(1,5-dichlorooctadiene)nickel(0){Ni(COD) ₂ }(0.965g) was added to the solution under nitrogen atmosphere, stirred and reacted for 3 hours. The reaction solution was cooled to room temperature, added dropwise to a mixed solution of 25% ammonia 5mL/methanol 140mL/ion-exchanged water 140mL, stirred for 1 hour, and the precipitate was filtered, dried under reduced pressure, and dissolved in toluene 40ml. After dissolution, 1.6 g of diatomaceous earth was added, stirred for 30 minutes, and insoluble matter was filtered. The resulting filtrate was purified by passing through an alumina column. Then, 80 mL of 5.2% aqueous hydrochloric acid was added, and after stirring for 3 hours, the aqueous layer was removed. Then, 80 mL of 4% ammonia water was added, and the aqueous layer was removed after stirring for 2 hours. Next, about 80 mL of ion-exchanged water was added to the organic layer, and after stirring for 1 hour, the aqueous layer was removed. Thereafter, the organic layer was poured into 160 ml of methanol, stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 3) was 0.46 g. In addition, the polystyrene-equivalent number average molecular weight and weight average molecular weight were Mn=1.0×10 ⁴ and Mw=6.1×10 ⁴ , respectively.

Example 5

<Synthesis of Polymer Compound 4>

Compound B (0.588g), N, N'-bis(4-bromophenyl)-N,N'-bis(4-tert-butyl-2,6-dimethylphenyl)-benzidine (0.053 g) After dissolving 2,2'-bipyridine (0.548 g) in 140 mL of dehydrated tetrahydrofuran, the inside of the system was replaced with nitrogen by bubbling argon. After heating up to 60°C, bis(1,5-cyclooctadiene)nickel(0){Ni(COD) ₂ }(0.965g) was added to the solution under a nitrogen atmosphere, stirred, and reacted for 3 hours. The reaction solution was cooled to room temperature, added dropwise to a mixed solution of 25% ammonia 5mL/methanol 140mL/ion-exchanged water 140mL, stirred for 1 hour, and the precipitate was filtered, dried under reduced pressure, and dissolved in toluene 40ml. After dissolution, 1.6 g of diatomaceous earth was added, stirred for 30 minutes, and insoluble matter was filtered. The resulting filtrate was purified by passing through an alumina column. Then, 80 mL of 5.2% aqueous hydrochloric acid was added, and after stirring for 3 hours, the aqueous layer was removed. Then, 80 mL of 4% ammonia water was added, and the aqueous layer was removed after stirring for 2 hours. Next, about 80 mL of ion-exchanged water was added to the organic layer, and after stirring for 1 hour, the aqueous layer was removed. Thereafter, the organic layer was poured into 160 ml of methanol, stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 4) was 0.31 g. In addition, the polystyrene-equivalent number average molecular weight and weight average molecular weight were Mn=2.5×10 ⁴ and Mw=1.2×10 ⁵ , respectively.

Embodiment 6<The production and performance of EL element>

(preparation of solution)

The polymer compound 2 obtained in the above description was dissolved in toluene to prepare a toluene solution having a polymer concentration of 1.8% by weight. the

(Production of EL elements) 

A suspension of poly(3,4)ethylenedioxythiophene/polystyrenesulfonic acid (manufactured by Bayer, BaytronP AI4083) was used on a glass substrate on which an ITO film was attached to a thickness of 150 nm by sputtering. The liquid filtered with a 0.2 μm membrane filter was formed into a thin film with a thickness of 70 nm by a spin coater, and dried on a hot plate at 200° C. for 10 minutes. Then, using the toluene solution obtained in the above operation, a film was formed with a spin coater at a rotation speed of 3400 rpm. The film thickness after film formation was about 95 nm. Next, after drying this under reduced pressure at 80° C. for 1 hour, about 4 nm of lithium fluoride was deposited, about 5 nm of calcium was deposited as a cathode, and about 80 nm of aluminum was deposited to produce an EL element. Then, after the degree of vacuum reached 1×10 ^-4 Pa or less, vapor deposition of the metal was started.

(Performance of EL element)

By applying a voltage to the obtained device, EL emission having a peak at 455 nm was obtained from the device. When the EL emission color is represented by the CIE color coordinate value, x=0.150, y=0.128, showing a very good blue color. The intensity of EL light emission is basically proportional to the current density. In addition, this element can be seen to start emitting light from 5.2V. The luminous efficiency increased monotonously in the range of the measured applied voltage (0 V to 12 V), and the value at 12 V showed a relatively high efficiency of 1.02 cd/m ² .

Embodiment 7<The production and performance of EL element>

(preparation of solution)

Polymer Compound 4 obtained in the above description was dissolved in toluene at a ratio of 90% by weight and Polymer Compound 3 at a ratio of 10% by weight to prepare a toluene solution having a polymer concentration of 1.8% by weight. the

(Production of EL elements) 

An EL element was produced in exactly the same manner as described in Example 6, except that the toluene solution obtained in the above operation was used. Furthermore, the rotational speed of the polymer solution in the spin coater was 3300 rpm, and the film thickness of the polymer film after film formation was 95 nm. the

(Performance of EL element)

By applying a voltage to the obtained device, EL emission having a peak at 425 nm was obtained from the device. When the EL emission color is represented by the CIE color coordinate value, x=0.155, y=0.072, showing a very good blue color. The intensity of EL light emission is basically proportional to the current density. In addition, this element can be seen to start emitting light from 5.5V. The luminous efficiency increased monotonously in the range of the measured applied voltage (0 V to 12 V), and the value at 12 V showed a relatively high efficiency of 0.22 cd/m ² .

Embodiment 8<The production and performance of EL element>

(preparation of solution)

The polymer compound 4 obtained in the above description was dissolved in toluene to prepare a toluene solution having a polymer concentration of 1.8% by weight. the

(Production of EL elements) 

An EL element was produced in exactly the same manner as described in Example 6, except that the toluene solution obtained in the above operation was used. Furthermore, the rotational speed of the polymer solution in the spin coater was 2500 rpm, and the film thickness of the polymer film after film formation was 90 nm. the

(Performance of EL element)

By applying a voltage to the obtained device, EL emission having a peak at 425 nm was obtained from the device. When the EL emission color is represented by the CIE color coordinate value, x=0.155, y=0.074, showing a very good blue color. The intensity of EL light emission is basically proportional to the current density. In addition, this device can be seen to start emitting light from 5.8V. The luminous efficiency increased monotonously in the measured applied voltage range (0V to 12V), and the value at 12V showed a relatively high efficiency of 0.57cd/m ² .

Embodiment 9<The synthesis of compound D>

(Synthesis of Compound C)

(compound C)

31 ml of ion-exchanged water was added to the reaction container, and 29 g (727 mmol) of sodium hydroxide was added little by little while stirring to completely dissolve it. The system was replaced with argon, and 30 ml of toluene and 5.0 g (24 mmol) of 1,2,3,10b-tetrahydrofluoranthene were added, stirred and dissolved. Next, 2.3 g (7.3 mmol) of tetrabutylammonium bromide and 9.4 g (48 mmol) of 2-ethylhexyl bromide were added, and it was made to react at 40 degreeC for 3 hours. The organic layer was extracted with toluene and water, and dried over sodium sulfate. After distilling off the solvent, it was purified by silica gel chromatography using hexane as a developing solvent to obtain 6.88 g of a yellow oil. the

MS (APPI (+)): 318 ([M+H] ⁺ )

¹ H-NMR (300MHz/CDCl ₃ ) δ7.69(1H,d), 7.50(1H,d), 7.40(1H,d), 7.33～7.22(3H,m), 7.02(1H,d), 3.07 ～2.96(1H, m), 2.79～2.71(1H, m), 2.36～2.22(2H, m), 2.10～1.99(1H, m), 1.93～1.76(2H, m), 1.24～1.15(1H, m), 0.88～0.37(9H, m)

(Synthesis of compound D)

(compound D)

6.8 g (21 mmol) of compound C, 6.7 g (49 mmol) of zinc chloride, and 134 ml of a mixed solvent of acetic acid:dichloromethane=1:1 were added to a reaction vessel replaced with argon, and stirred at room temperature. Next, 18 g (47 mmol) of benzyltrimethylammonium tribromide was dissolved in 150 ml of methylene chloride and added dropwise. After completion of the dropwise addition, the reaction was carried out at room temperature for 2 hours, followed by the reaction at 40° C. and 50° C. for 30 minutes each, and the reaction was stopped by adding chloroform and 5% aqueous sodium bisulfite solution. The organic layer was extracted with chloroform and water, washed twice with water, and then neutralized with an aqueous potassium carbonate solution. After drying over sodium sulfate, the solvent was distilled off and purified three times by silica gel chromatography using hexane as a developing solvent to obtain 1.73 g of Compound D as a yellow oil (slowly crystallized into white when left standing at room temperature). the

MS(APPI(+))476(M ⁺ )

¹ H-NMR (300MHz/CDCl ₃ ) δ7.52～7.42(4H, m), 7.33(1H, d), 3.00～2.80(2H, m), 2.40～2.20(2H, m), 2.02～1.89( 2H, m), 1.75～1.70(1H, m), 1.31～1.15(2H, m), 0.96～0.39(8H, m)

Example 10

<Synthesis of Polymer Compound 5>

Under a nitrogen atmosphere, Compound D (0.476 g) and 2,2'-bipyridine (0.422 g) were dissolved in 72 mL of dehydrated tetrahydrofuran, followed by stirring to dissolve. Bis(1,5-dichlorooctadiene) nickel (0) {Ni(COD) ₂ } (0.743 g) was added to this solution, stirred, and reacted at 60 degreeC for 3 hours. The reaction solution was cooled to room temperature, added dropwise to a mixed solution of 25% ammonia 4mL/methanol 72mL/ion-exchanged water 72mL, stirred for 1 hour, and the precipitate was filtered, dried under reduced pressure, and dissolved in toluene 20ml. After dissolution, 1.6 g of diatomaceous earth was added, stirred for 30 minutes, and insoluble matter was filtered. The resulting filtrate was purified by passing through an alumina column. Then, 40 mL of 5.2% aqueous hydrochloric acid was added, and after stirring for 3 hours, the aqueous layer was removed. Then, 40 mL of 4% ammonia water was added, and the aqueous layer was removed after stirring for 2 hours. Next, about 40 mL of ion-exchanged water was added to the organic layer, and after stirring for 1 hour, the aqueous layer was removed. Thereafter, the organic layer was poured into 80 ml of methanol, stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 5) was 0.17 g. In addition, the polystyrene-equivalent number average molecular weight and weight average molecular weight were Mn=1.1×10 ⁵ and Mw=3.2×10 ⁵ , respectively.

Comparative example 1

<Synthesis of polymer compound 6>

0.22g (0.40mmol) of 2,7-dibromo-9,9-dioctylfluorene, N,N'-bis(4-bromophenyl)-N,N'-bis(4-tert-butyl- After adding 0.20g (0.27mmol) of 2,6-dimethylphenyl)-1,4-phenylenediamine and 0.24g (1.5mmol) of 2,2'-bipyridine into the reaction vessel, replace the reaction system with nitrogen . Tetrahydrofuran (dehydration solvent) previously degassed by bubbling argon gas was added thereto. Then, 0.42 g (1.5 mmol) of bis(1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and it was made to react at 60 degreeC for 3 hours. Also, the reaction was carried out in a nitrogen atmosphere. After the reaction, the solution was cooled, poured into a mixed solution of 25% ammonia water 10 mL/methanol 120 mL/ion-exchanged water 50 mL, and stirred for about 1 hour. The resulting precipitate was then recovered by filtration. After the precipitate was washed with ethanol, it was dried under reduced pressure for 2 hours. Then, this precipitate was dissolved in 50 ml of toluene, 50 mL of 1N hydrochloric acid was added, stirred for 1 hour, the water layer was removed, 4% ammonia water 50 mL was added to the organic layer, and the water layer was removed after stirring for 1 hour. The organic layer was added dropwise to 120 mL of methanol, stirred for 1 hour, and the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 40 mL of toluene. Thereafter, it was purified by passing through an alumina column (amount of alumina: 20 g), and the recovered toluene solution was added dropwise to 120 mL of methanol, stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained polymer compound 6 was 0.094 g. the

Polystyrene-equivalent number average molecular weight of polymer compound 6 was 2.0×10 ⁴ , and polystyrene-equivalent weight average molecular weight was 1.1×10 ⁵ .

Comparative example 2 <Production and performance of EL element> 

(preparation of solution)

The polymer compound 6 obtained in the above description was dissolved in chloroform to prepare a chloroform solution having a polymer concentration of 1.8% by weight. the

(Production of EL elements) 

On a glass substrate on which an ITO film was adhered to a thickness of 150 nm by sputtering, a solution of poly(ethylenedioxythiophene)/polystyrenesulfonic acid (manufactured by Bayer, BaytronP) was used to coat the glass substrate with a spin coater. A film was formed with a thickness of 50 nm, and dried on a hot plate at 200° C. for 10 minutes. Then, using the chloroform solution prepared above, a spin coater was used to form a film at a rotational speed of 2500 rpm. The film thickness is about 100 nm. Next, after drying this under reduced pressure at 80° C. for 1 hour, about 4 nm of LiF was deposited as a cathode buffer layer, about 5 nm of calcium was deposited as a cathode, and about 80 nm of aluminum was deposited to fabricate an EL element. Then, after the degree of vacuum reached 1×10 ^-4 Pa or less, vapor deposition of the metal was started.

(Performance of EL element)

By applying a voltage to the obtained device, EL emission having a peak at 448 nm was obtained. When the EL emission color is represented by the C.I.E. color coordinate value, then x=0.155, y=0.133. The element exhibited the maximum luminous efficiency at about 10V, which was 0.14 cd/A. the

When the polymer compound of the present invention is used as a material of an electronic device, it can provide an electronic device having excellent device performance. the

The polymer compound of the present invention generally emits fluorescence or phosphorescence in a solid state, and can be used as a polymer luminescent body (a high-molecular-weight light-emitting material). the

In addition, the polymer compound has excellent charge transport performance, and can be suitably used as a polymer LED material or a charge transport material. A polymer LED using this polymer light-emitting body is a high-performance polymer LED that can be driven at low voltage and with high efficiency. Therefore, the polymer LED can be ideally used in devices such as backlights of liquid crystal displays, curved or planar light sources for illumination, segmented display elements, and dot-matrix flat panel displays. the

In addition, the polymer compound of the present invention can also be used as a material for conductive thin films such as dyes for lasers, materials for organic solar cells, organic semiconductors for organic transistors, conductive thin films, and organic semiconductor thin films. the

In addition, it can also be used as a light-emitting thin film material that emits fluorescence or phosphorescence. the

Claims (25)

1. A polymer compound characterized in that it contains a repeating unit represented by the following formula (2-1),

Formula (2-1) In the formula, R ₁ and R ₂ independently represent a substituent, D ring represents a non-aromatic ring that may also have a substituent, a represents an integer of 0 to 2, b represents an integer of 0 to 3, and in R ₁ and R When there are _two or more of them, they may be the same or different, and _R1 and _R2 may be combined to form a ring; _R1 and/or _R2 may be combined with D ring to form a ring, Q represents a substituent or a hydrogen atom, and z represents 0 or 1. 2. The polymer compound according to claim 1, wherein the repeating unit represented by the above formula (2-1) is a repeating unit represented by the following formula (3-1),

Formula (3-1) In the formula, R ₁ , R ₂ , ring D, Q, z, a and b have the same meanings as above. 3. The polymer compound according to claim 2, characterized in that, the repeating unit represented by the above formula (3-1) is the following formula (4-1), (4-2), (4-3) or the repeating unit represented by (4-4),

Formula (4-1) Formula (4-2)

Formula (4-3) Formula (4-4) In the formula, R _1a , R _1b , R _2a to R _2c and R _3a to R _3g each independently represent a hydrogen atom or a substituent. In formulas (4-1) to (4-3), R _2c and R _3g are combined to form a ring, and in formula (4-4), R _2c and R _3e may be combined to form a ring. 4. The macromolecular compound according to claim 1, further comprising a repeating unit represented by the following formula (5), formula (6), formula (7) or formula (8), -Ar ₁ - (5) -(Ar ₂ -X ₁ ) _ff -Ar ₃ - (6) -Ar ₄ -X ₂ - (7) -X ₃ - (8) In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure, and X ₁ , X ₂ and X ₃ independently represent means -CR ₉ ＝CR ₁₀ -, -C≡C-, -N(R ₁₁ )- or -(SiR ₁₂ R ₁₃ ) _m -, R ₉ and R ₁₀ independently represent a hydrogen atom, an alkyl group, an aromatic radical, monovalent heterocyclic group, carboxyl, substituted carboxyl group or cyano group, R ₁₁ , R ₁₂ and R ₁₃ independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, an aralkyl group or a substituted amino group, ff represents 1 or 2, m represents an integer of 1 to 12, and when R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are present in plural, they may be the same or different. 5. The polymer compound according to claim 1, further comprising a repeating unit represented by the following formula (9), (10), (11), (12), (13) or (14),

In the _formula , R represents alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio, arylalkenyl, Arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, imide group, monovalent heterocyclic group, carboxyl group, Substituting carboxyl, cyano or nitro, n represents an integer from 0 to 4, and in the case of multiple _R14 , they can be the same or different;

In the formula, R ₁₅ and R ₁₆ independently represent alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio, Arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halogen atom, acyl, acyloxy, imine residue, amido, imide, monovalent Heterocyclic group, carboxyl group, substituted carboxyl group, cyano group or nitro group, o and p independently represent integers from 0 to 3, and when there are multiple _R15 and _R16 , they can be the same or different;

In the formula, R ₁₇ and R ₂₀ independently represent alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio, Arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halogen atom, acyl, acyloxy, imine residue, amido, imide, monovalent Heterocyclyl, carboxyl, substituted carboxyl, cyano or nitro, q and r each independently represent an integer of 0 to 4, _R18 and _R19 each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent hetero Cyclic group, carboxyl group, substituted carboxyl group or cyano group, in the case of multiple R ₁₇ and R ₂₀ , they can be the same or different;

In the _formula , R represents alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio, arylalkenyl, Arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, imide group, monovalent heterocyclic group, carboxyl group, Substituting carboxyl, cyano or nitro, s represents an integer of 0-2. Ar ₁₃ and Ar ₁₄ each independently represent an arylene group, a divalent heterocyclic group, or a divalent group having a metal complex structure, ss and tt each independently represent 0 or 1, X ₄ represents O, S, SO, SO ₂ , Se or Te, where multiple R ₂₁ are present, which may be the same or different,

In the formula, R ₂₂ and R ₂₃ independently represent alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio, Arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halogen atom, acyl, acyloxy, imine residue, amido, imide, monovalent Heterocyclic group, carboxyl group, substituted carboxyl group, cyano group or nitro group, t and u each independently represent an integer from 0 to 4, X5 represents O, S, SO ₂ , Se, Te, NR ₂₄ or SiR ₂₅ R ₂₆ , X ₆ and X ₇ each independently represent N or CR ₂₇ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ each independently represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a monovalent heterocyclic group, and in the presence of multiple In the case of R ₂₅ , R ₂₆ and R ₂₇ , they may be the same or different,

In the formula, R ₂₈ and R ₃₃ independently represent alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio, Arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halogen atom, acyl, acyloxy, imine residue, amido, imide, monovalent Heterocyclic group, carboxyl group, substituted carboxyl group, cyano group or nitro group, v and w each independently represent an integer from 0 to 4, R ₂₉ , R ₃₀ , R ₃₁ and R ₃₂ each independently represent a hydrogen atom, an alkyl group, an aromatic group, 1-valent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group, Ar ₅ represents an arylene group, a 2-valent heterocyclic group or a 2-valent group with a metal complex structure, when there are multiple R ₂₈ and R ₃₃ , they can be the same or different. 6. The polymer compound according to claim 1, further comprising a repeating unit represented by the following formula (15),

In the formula, Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ each independently represent an arylene group or a divalent heterocyclic group, Ar ₁₀ , Ar ₁₁ and Ar ₁₂ each independently represent an aryl group or a monovalent heterocyclic group, Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ and Ar ₁₀ may have a substituent, x and y each independently represent 0 or 1, and 0≦x+y≦1. 7. A method for producing a polymer compound according to any one of claims 1 to 6, characterized in that, as a raw material, at least a compound represented by the following formula (17-1) is used to polymerize,

In the formula, R ₁ , R ₂ , a, b, ring D, Q, and z represent the same meanings as Q and z in claim 1 above, and Y ₁ and Y ₂ each independently represent a substituent participating in polymerization. 8. The production method according to claim 7, wherein the compound represented by the above formula (17-1) is the following formula (18-1), (18-2), (18-3) or ( 18-4) the compound represented, Formula (18-1) Formula (18-2) Formula (18-3) Formula (18-4) In the formula, R _1a , R _1b , R _2a to R _2c and R _3a to R _3g independently represent a hydrogen atom or a substituent, and in formulas (18-1) to (18-3), R _2c and R _3g can be combined with each other To form a ring, R _2c and R _3g in the formula (18-4) can combine with each other to form a ring, and Y ₁ and Y ₂ represent the same meaning as above. 9. The production method according to claim 7, wherein, in addition to the compound represented by the above-mentioned formula (17-1), a compound represented by any one of the following formulas (19) to (22) is used as a raw material Aggregated using, Y ₇ -Ar ₁ -Y ₈ (19) Y ₉ -(Ar ₂ -X ₁ ) _ff -Ar ₃ -Y ₁₀ (20) Y ₁₁ -Ar ₄ -X ₂ -Y ₁₂ (21) Y ₁₃ -X ₃ -Y ₁₄ (22) In the formula, Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ each independently represent an arylene group, a divalent heterocyclic group, or a divalent group having a metal complex structure, and X ₁ , X ₂ , and X ₃ each independently means -CR ₉ ＝CR ₁₀ -, -C≡C-, -N(R ₁₁ )- or -(SiR ₁₂ R ₁₃ ) _m -, R ₉ and R ₁₀ independently represent a hydrogen atom, an alkyl group, an aromatic radical, monovalent heterocyclic group, carboxyl, substituted carboxyl group or cyano group, R ₁₁ , R ₁₂ and R ₁₃ independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, an aralkyl group or a substituted amino group, ff represents 1 or 2, m represents an integer of 1 to 12, and when there are multiple R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ , they may be the same or different, and Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Y ₁₃ , and Y ₁₄ each independently represent a substituent involved in polymerization. 10. The production method according to claim 7, wherein the compound represented by formula (17-1) is used alone or with at least one compound selected from compounds represented by formula (19) to (22) During the polymerization, Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Y ₁₃ and Y ₁₄ are independently Halogen atoms, alkyl sulfonate groups, aryl sulfonate groups or aralkyl sulfonate groups are polycondensed in the presence of nickel zero-valent complexes. 11. The production method according to claim 7, wherein the compound represented by formula (17-1) is used alone or with at least one selected from the compounds represented by formula (19) to (22) During the polymerization, Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Y ₁₃ and Y ₁₄ are independently Halogen atom, alkylsulfonate group, arylsulfonate group, aralkylsulfonate group, -B(OH) ₂ or borate group, halogen atom, alkylsulfonate group, arylsulfonate group The ratio of the total number of moles of ester groups and aralkylsulfonate groups to the total number of moles of -B(OH) ₂ and borate groups is substantially 1, and polycondensation is performed using a nickel or palladium catalyst. 12. A compound represented by formula (18-2), formula (18-3) or formula (18-4) of claim 8 above. 13. A composition characterized by comprising at least one material selected from the group consisting of hole transport materials, electron transport materials, and luminescent materials, and the polymer compound according to any one of claims 1 to 6. 14. An ink composition comprising the polymer compound according to any one of claims 1 to 6 and a solvent. 15. The ink composition according to claim 14, wherein the viscosity is 1 to 20 mPa·s at 25°C. 16. A light emitting film containing the polymer compound according to any one of claims 1 to 6. 17. A conductive film containing the polymer compound according to any one of claims 1 to 6. 18. An organic semiconductor thin film containing the polymer compound according to any one of claims 1 to 6. 19. A polymer light-emitting device, characterized by having an organic layer between electrodes composed of an anode and a cathode, and the organic layer contains the polymer compound according to any one of claims 1 to 6. 20. The polymer light-emitting element according to claim 19, wherein the organic layer is a light-emitting layer. 21. The polymer light-emitting device according to claim 20, wherein the light-emitting layer further contains a hole-transporting material, an electron-transporting material, or a light-emitting material. 22. A planar light source comprising the polymer light-emitting device according to any one of claims 19-21. 23. A segmented display device, characterized by comprising the polymer light-emitting element according to any one of claims 19-21. 24. A dot-matrix display device, characterized by comprising the polymer light-emitting element according to any one of claims 19-21. 25. A liquid crystal display device comprising the polymer light emitting element according to any one of claims 19 to 21.