KR20080013926A - High-molecular compounds and high-molecular luminescent devices made by 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

High-Molecular Compounds and High-Molecular Luminescent Devices Made by Using the Same

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

High molecular weight light emitting materials and charge transport materials are soluble in a solvent, and have been studied in various ways in that an organic layer in a light emitting device can be formed 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 and charge transport materials (International Publication No. 99/54385).

However, the device performance of the device using the polymer compound as a light emitting material, a charge transporting material, or the like was not practically satisfactory.

For example, the polymer LED using the polymer compound has not yet been practically satisfactory in device performance such as light emission efficiency and color tone of light emission.

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 for an electronic device.

That is, the present invention provides a polymer compound comprising at least one of the residues of the compound represented by the following formula (I).

In the formula, the A ring, the B ring and the C ring each independently represent an aromatic ring or a non-aromatic ring which may have a substituent, and 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, z represents 0 or 1, and A and B rings other than Z ₅ constituting each ring each other The atoms of may be shared, and at least one of the A ring, the B ring and the C ring is a non-aromatic ring.

Best Mode for Carrying Out the Invention

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

As an aromatic ring, what contains 4n + 2 (pi) electrons in a ring structure is mentioned. Specifically, Aromatic hydrocarbon ring, such as a benzene ring and a cyclodecane pentaene ring; Aromatic heterocycles, such as a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a pyrimidine ring, and a pyridazine ring, are mentioned.

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, a cycloheptene ring, a cycloheptadiene ring, a cycloheptatriene ring and a cyclo Octane ring, cyclooctene ring, cyclooctadiene ring, cyclooctatriene ring, cyclooctatetraene ring, cyclononane ring, cyclononene ring, cyclononane diene ring, cyclononane triene ring, cyclodecane ring, cyclodecene ring, Cyclodecane diene ring, cyclodecane triene ring, cyclodecane tetraene ring, cyclododecane ring, cyclododecene ring, cyclododecane diene ring, cyclododecane triene ring, cyclododecane tetraene ring, cyclododecane penta ring Alicyclic type, such as an cyclic ring, a cyclo undecane ring, a cyclo undecene ring, a cyclo undecane diene ring, a cyclo undecane triene ring, a cyclo undecane tetraene ring, a cyclo undecane pentaene ring, and a cyclo undecane hexaene ring .; Non-aromatic heterocycles, such as a pyran ring and a thiopyran ring, are mentioned.

When an aromatic ring or a non-aromatic ring has a substituent, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, and aryl. Alkynyl group, substituted amino group, substituted silyl group, fluorine atom, acyl group, acyloxy group, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group and nitro group, and alkyl group, alkoxy group , Aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkylthio group are more preferable.

Here, the alkyl group may be any one of straight chain, branched or cyclic, and usually has 1 to 20 carbon atoms, preferably 3 to 20, and specific examples thereof include methyl group, ethyl group, propyl group, i-propyl group and butyl group. , i-butyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group , Lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, and the like, and pentyl group, isoamyl group, hexyl group, octyl group , 2-ethylhexyl group, decyl group, and 3,7-dimethyloctyl group are preferable.

The alkoxy group may be either linear, branched or cyclic, having usually 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms, and specific examples thereof include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, Butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3 , 7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group, methoxymethyloxy group, 2-methoxyethyloxy group etc. are mentioned, A pentyloxy group, a hexyloxy group, an octyloxy group, 2-ethylhexyloxy group, a decyloxy group, and a 3,7- dimethyl octyloxy group are preferable.

The alkylthio group may be either linear, branched or cyclic, having usually 1 to 20 carbon atoms, preferably 3 to 20 carbon atoms, and specific examples thereof include methylthio group, ethylthio group, propylthio group and i-propyl. Thio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group , A decylthio group, a 3,7-dimethyloctylthio group, a laurylthio group, a trifluoromethylthio group, and the like, and a pentylthio group, hexylthio group, octylthio group, 2-ethylhexylthio group, The decylthio group and the 3,7-dimethyloctylthio group are preferable.

An aryl group is an atomic group remove | excluding one hydrogen atom from an aromatic hydrocarbon, and the thing which has a condensed ring, and the thing which two or more independent benzene rings or condensed rings couple | bonded directly or through groups, such as vinylene, is included. The aryl group is usually about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms, and specific examples thereof include a phenyl group and a C ₁ to C ₁₂ alkoxyphenyl group (C ₁ to C ₁₂ represent carbon atoms 1 to 12, which are the same below), C ₁ to C ₁₂ alkylphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, pentafluorophenyl group and the like are exemplified, and C ₁ to C ₁₂ Alkoxyphenyl groups and C ₁ to C ₁₂ alkylphenyl groups are preferred.

C ₁ to C ₁₂ alkoxy, specifically methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, Heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like.

As the C ₁ to C ₁₂ alkylphenyl group, specifically, methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, i-propylphenyl group, butylphenyl group, i-butylphenyl group, t-butylphenyl group, pentyl A phenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group, etc. are illustrated.

The aryloxy group has usually 6 to 60 carbon atoms, preferably 7 to 48, and specific examples thereof include phenoxy group, C ₁ to C ₁₂ alkoxyphenoxy group, C ₁ to C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2 -naphthyloxy group, and a phenyl oxy example pentafluorophenyl, a C ₁ to C ₁₂ alkoxy phenoxy group, C ₁ to C ₁₂ alkylphenoxy group are preferable.

C ₁ to C ₁₂ alkoxy, specifically methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, Heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like.

As the C ₁ to C ₁₂ alkyl phenoxy group, specifically methyl phenoxy group, ethyl phenoxy group, dimethyl phenoxy group, propylphenoxy group, 1,3,5-trimethylphenoxy group, methylethylphenoxy group, i-propylphenoxy group, Butylphenoxy, i-butylphenoxy, t-butylphenoxy, pentylphenoxy, isoamylphenoxy, hexylphenoxy, heptylphenoxy, octylphenoxy, nonylphenoxy, decylphenoxy, and dodecylphenoxy This is illustrated.

The arylthio group usually has about 3 to 60 carbon atoms, and specific examples thereof include a phenylthio group, a C ₁ to C ₁₂ alkoxyphenylthio group, a C ₁ to C ₁₂ alkylphenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group. , there is illustrated the like coming phenylthio pentafluorophenyl, coming C ₁ to C ₁₂ alkoxyphenyl-T, is preferably a C ₁ to C ₁₂ alkyl phenylthio group.

The arylalkyl group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms, and specific examples thereof include phenyl-C ₁ to C ₁₂ alkyl groups, C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkyl groups, and C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkyl groups, 1-naphthyl-C ₁ to C ₁₂ alkyl groups, 2-naphthyl-C ₁ to C ₁₂ alkyl groups and the like are exemplified, and C ₁ to C ₁₂ alkoxyphenyl-C ₁ to a C ₁₂ alkyl group, C ₁ to C ₁₂ alkyl, phenyl -C ₁ to C ₁₂ alkyl group are preferable.

The arylalkoxy group is usually about 7 to 60 carbon atoms, preferably 7 to 48, and specific examples thereof include phenylmethoxy group, phenylethoxy group, phenylbutoxy group, phenylpentyloxy group, phenylhexyloxy group, phenylheptyloxy group, to ₁ -C phenyl such as phenyl oxide tilok time C ₁₂ alkoxy group, C ₁ to C ₁₂ alkoxyphenyl--C ₁ to C ₁₂ alkoxy group, C ₁ to C ₁₂ alkyl, phenyl -C ₁ to C ₁₂ alkoxy group, 1 Naphthyl-C ₁ to C ₁₂ alkoxy groups, 2-naphthyl-C ₁ to C ₁₂ alkoxy groups, and the like, and C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkoxy groups, C ₁ to C ₁₂ alkyls Phenyl-C ₁ to C ₁₂ alkoxy groups are preferred.

The arylalkylthio group has usually 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms, and specific examples thereof include a phenyl-C ₁ to C ₁₂ alkylthio group and a C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkylthio group. , C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkylthio group, 1-naphthyl-C ₁ to C ₁₂ alkylthio group, 2-naphthyl-C ₁ to C ₁₂ alkylthio group and the like are exemplified, C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkylthio groups and C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkylthio groups are preferred.

The arylalkenyl group usually has about 8 to 60 carbon atoms, and specific examples thereof include a phenyl-C ₂ to C ₁₂ alkenyl group, a C ₁ to C ₁₂ alkoxyphenyl-C ₂ to C ₁₂ alkenyl group, and a C ₁ to C ₁₂ alkyl group. -C ₂ to C ₁₂ alkenyl groups, 1-naphthyl-C ₂ to C ₁₂ alkenyl groups, 2-naphthyl-C ₂ to C ₁₂ alkenyl groups and the like are exemplified, and C ₁ to C ₁₂ alkoxyphenyl-C ₂ to C ₁₂ alkenyl groups, C ₂ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkenyl groups are preferred.

The arylalkynyl group usually has about 8 to 60 carbon atoms, and specific examples thereof include a phenyl-C ₂ to C ₁₂ alkynyl group, C ₁ to C ₁₂ alkoxyphenyl-C ₂ to C ₁₂ alkynyl group, and C ₁ to C ₁₂ alkylphenyl- C ₂ to C ₁₂ alkynyl group, 1-naphthyl-C ₂ to C ₁₂ alkynyl group, 2-naphthyl-C ₂ to C ₁₂ alkynyl group and the like are exemplified, and C ₁ to C ₁₂ alkoxyphenyl-C ₂ to C ₁₂ alkynyl group, C ₁ to C ₁₂ alkylphenyl-C ₂ to C ₁₂ alkynyl group is preferable.

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. . Carbon number of a substituted amino group is about 1-60 normally, Preferably it is 2-48, without including carbon number of the said substituent.

Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, i-propylamino group, diisopropylamino group, butylamino group, i-butylamino group, t-butylamino group, pentylamino group, hexyl Amino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicysi Chlohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ to C ₁₂ alkoxyphenylamino group, di (C ₁ to C ₁₂ alkoxyphenyl) amino group, di (C ₁ to C ₁₂ alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, Pyridazinylamino group, pyrimidylamino group, pyrazylamino group, triazylamino group, phenyl-C ₁ to C ₁₂ alkylamino group, C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkylamino group, C ₁ to C ₁₂ alkylphenyl -C ₁ to C ₁₂ alkylamino group, di (C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkyl) amino group, di (C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkyl) amino group, 1-naph Yl-C ₁ to C ₁₂ alkylamino groups, 2-naphthyl-C ₁ to C ₁₂ alkylamino groups, and the like.

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

Specifically, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, t-butylsilyldimethylsilyl group, Pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group , Lauryldimethylsilyl group, phenyl-C ₁ to C ₁₂ alkylsilyl group, C ₁ to C ₁₂ alkoxyphenyl-C ₁ to C ₁₂ alkylsilyl group, C ₁ to C ₁₂ alkylphenyl-C ₁ to C ₁₂ alkylsilyl Groups, 1-naphthyl-C ₁ to C ₁₂ alkylsilyl groups, 2-naphthyl-C ₁ to C ₁₂ alkylsilyl groups, phenyl-C ₁ to C ₁₂ alkyldimethylsilyl groups, triphenylsilyl groups, tri-p -Xylyl silyl group, tribenzyl silyl group, diphenyl methyl silyl group, t-butyl diphenyl silyl group, dimethylphenyl silyl group, etc. are illustrated.

The acyl group has usually 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms, and specific examples thereof include an acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, trifluoroacetyl group and pentafluoro Robenzoyl group etc. are illustrated.

The acyloxy group has usually 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms, and specific examples thereof include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, benzoyloxy group and tri Fluoroacetyloxy group, pentafluorobenzoyloxy group, etc. are illustrated.

The amide group is usually about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms, and specific examples thereof include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, Pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group, ditrifluoroacetamide group, dipentafluorobenzamide group, etc. This is illustrated.

As an acid imide group, the residue obtained except the hydrogen atom couple | bonded with the nitrogen atom from the acid imide is mentioned, A carbon number is about 4-20, Specifically, the group etc. shown below are illustrated.

The monovalent heterocyclic group refers to the remaining atomic groups excluding one hydrogen atom from the heterocyclic compound, and the carbon number is usually about 4 to 60, preferably 4 to 20. In addition, carbon number of a substituent does not contain carbon number of a heterocyclic group. Here, a heterocyclic compound means that in the organic compound which has a cyclic structure, the element which comprises a ring contains not only a carbon atom but hetero atoms, such as oxygen, sulfur, nitrogen, phosphorus, and boron, in a ring. Specifically, the following structure is illustrated.

In the above formula, each R independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, or aryl An alkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group.

Among them, thienyl group, C ₁ to C ₁₂ alkylthienyl group, pyrrolyl group, furyl group, pyridyl group, C ₁ to C ₁₂ alkylpyridyl group, piperidyl group, quinolyl group, isoquinolyl group and the like are preferable, Thienyl group, C ₁ to C ₁₂ alkylthienyl group, pyridyl group, and C ₁ to C ₁₂ alkylpyridyl group are more preferable.

The substituted carboxyl group refers to a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and usually has 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms, and specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group and a proton. Poxycarbonyl group, i-propoxycarbonyl group, butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyl Oxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxy Carbonyl group, perfluorooctyloxycarbonyl group, phenoxycarbonyl group, naph When the like group, a pyridyloxy group. In addition, the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The carbon number of the substituent does not include the carbon number of the substituted carboxyl group.

In Formula (I), 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 Indicates.

Substituents for Q include alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkoxy, arylalkylthio, arylalkenyl, arylalkynyl, substituted amino and substituted silyl A group, a fluorine atom, an acyl group, an acyloxy group, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group, and a nitro group, etc. are mentioned, The definition, the specific example, etc. are mentioned above. Is the same as

The A ring and the B ring may share atoms of rings other than Z ₅ constituting each ring, and at least one of A ring, B ring and C ring is a non-aromatic ring.

Preferably ring A and ring B is Z ₅ It is a case where the atom of one ring is shared other than this. Moreover, the case where one non-aromatic ring is one is preferable.

Moreover, it is preferable that the high molecular compound of this invention contains the repeating unit represented by following formula (Ia)-Ic as a repeating unit.

In the formula, the A ring, the B ring and the C ring each independently represent an aromatic ring or a non-aromatic ring which may have a substituent, and 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, z represents 0 or 1, and the A and B rings may share atoms of a ring other than Z ₅ ; In addition, the substituents of each ring may be bonded to each other to further form a ring, and at least one of the rings having no bonding hand among the A ring, the B ring, and the C ring is a non-aromatic ring.

As a specific example of the repeating unit represented by general formula (Ia),

Etc. and these have a substituent.

As a specific example of the repeating unit represented by general formula (Ib),

Etc. and these have a substituent.

As a specific example of the repeating unit represented by general formula (Ic),

Etc. and these have a substituent.

In the repeating units represented by the above formulas (Ia) to (Ic), the atoms constituting the A ring, the B ring, and the C ring (the term `` atomic constituting the ring '' refers to an atom forming a skeleton of the ring) include nitrogen and oxygen in addition to carbon atoms. Although it may contain atoms, such as sulfur, silicon, and selenium, it is preferable that all the atoms which comprise A ring, B ring, and C ring are carbon atoms from a viewpoint of adjusting charge transport property.

It is preferable that any one of A ring, B ring, and C ring has a substituent from the viewpoint of improving the solubility of a high molecular compound, the viewpoint of adjusting the light emission wavelength, and the viewpoint of adjusting charge transport property.

In addition, from the viewpoint of charge transportability, a repeating unit having a structure represented by the formulas (Ia) and (Ib) is preferable, and a structure represented by the formula (Ia) is more preferable in view of ease of synthesis.

Moreover, it is more preferable that said Formula (Ia) is following Formula (IIa).

In the formula, R ₁ And R ₂ each independently represent a substituent, the D ring represents a non-aromatic ring which may have a substituent, a represents an integer of 0 to 2, b represents an integer of 0 to 3, and R ₁ and R ₂ are When a plurality of each exists, they may be the same or different, R ₁ and R ₂ may be bonded to each other to form a ring, R ₁ And / or R ₂ may be bonded to a D ring to form a ring, and Q and z represent the same meaning as described above.

It is preferable that the repeating unit containing the said Formula (IIa) is a repeating unit represented by following formula (IIIa).

In formula, R <_1> , R <_2> , D ring, Q, z, a, and b show the same meaning as the above.

Among the repeating units represented by the formula (IIIa), those represented by the following formulas (IVa), (IVb), (IVc) and (IVd) are more preferable from the viewpoint of adjusting the charge transportability.

In the formula, R _1a , R _1b , R _2a to R _2c , and R _3a to R _3g represent a substituent, and in Formulas IVa to IVc, R _2c and R _3g may combine with each other to form a ring. In IVd, R _2c and R _3e may combine with each other to form a ring.

Examples of the ring formed by bonding to each other include an aromatic ring and a non-aromatic ring, and the specific examples thereof are the same as described above.

In addition, the units of Formulas IVa to IVc are included when z = 1 in Formula IIIa, and the units of Formula IVd are included when z = 0 in Formula IIIa.

As a specific example of the repeating unit represented by the said general formula (IVa),

Can be mentioned.

As a specific example of the repeating unit represented by the said general formula (IVb),

Can be mentioned.

As a specific example of the repeating unit represented by the said general formula (IVc),

Can be mentioned.

As a specific example of the repeating unit represented by the said general formula (IVd),

Can be mentioned.

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

The sum total of the repeating unit which is a structure represented by the said Formula (Ia), (Ib), (Ic), (IIa), (IIIa), (IVa), (IVb), (IVc), and (IVd) is 1 mol% or more to 100 mol of the sum total of all the repeating units which the high molecular compound of this invention has. It is% or less, and it is preferable that they are 5 mol% or more and 100 mol% or less.

The polymer compound of the present invention is represented by the above formulas Ia, Ib, Ic, IIa, IIIa, IVa, IVb, IVc and IVd from the viewpoint of changing the emission wavelength, increasing the luminous efficiency, improving the heat resistance, and the like. In addition to the repeating unit used, the copolymer containing 1 or more types of other repeating units is preferable.

As a repeating unit other than the repeating unit represented by the said Formula (Ia), (Ib), (Ic), (IIa), (IIIa), (IVa), (IVb), (IVc), and (IVd), the repeating unit represented by following formula (V), formula (VI), formula (VII) or formula (VIII) is preferable. .

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 arylalkyl group or a substituted amino group. ff represents an integer of 1 or 2. m represents the integer of 1-12. When a plurality of R ₉ , R ₁₀ , R ₁₁ , R _12, and R ₁₃ are each present, they may be the same or different.

Here, an arylene group is an atomic group remove | excluding two hydrogen atoms from an aromatic hydrocarbon, and the thing which has a condensed ring, and the thing which two or more independent benzene rings or condensed rings couple | bonded directly or through groups, such as vinylene, is included. The arylene group may have a substituent.

Examples of the substituent include alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, Substituted silyl groups, halogen atoms, acyl groups, acyloxy groups, imine residues, amide groups, acid imide groups, monovalent heterocyclic groups, carboxyl groups, substituted carboxyl groups, and cyano groups.

Carbon number of the part except a substituent in an arylene group is about 6-60 normally, Preferably it is 6-20. In addition, the total carbon number containing the substituent of an arylene group is about 6-100 normally.

Examples of the arylene group include a phenylene group (for example, formulas 1 to 3), a naphthalenediyl group (formulas 4 to 13), anthracene-diyl group (formulas 14 to 19), and a biphenyl-didiary (formulas 20 to 20). 25), fluorene-diyl group (formulas 36 to 38), terphenyl-diyl group (formulas 26 to 28), condensed cyclic compound groups (formula 29 to 35), stilbene-diyl (formulas A to D), distilbene-diyl (formulas E, F) and the like are exemplified. Especially, a phenylene group, a biphenylene group, a fluorene- diyl group, and a stilbene- diyl group are preferable.

In addition, the bivalent heterocyclic group in Ar <_1> , Ar <_2> , Ar <_3>, and Ar <_4> means the atomic group which removed two hydrogen atoms from the heterocyclic compound, and the said group may have a substituent. Here, a heterocyclic compound means that in the organic compound which has a cyclic structure, the element which comprises a ring contains not only a carbon atom but hetero atoms, such as oxygen, sulfur, nitrogen, phosphorus, boron, arsenic, in a ring. Of the divalent heterocyclic groups, aromatic heterocyclic groups are preferable.

Examples of the substituent include alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, Substituted silyl groups, halogen atoms, acyl groups, acyloxy groups, imine residues, amide groups, acid imide groups, monovalent heterocyclic groups, carboxyl groups, substituted carboxyl groups, and cyano groups.

Carbon number of the part except the substituent in a bivalent heterocyclic group is about 3-60 normally. In addition, the total carbon number containing the substituent of a bivalent heterocyclic group is about 3-100 normally.

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

Divalent heterocyclic group containing nitrogen as a hetero atom: pyridine-diyl group (formulas 39 to 44), diazaphenylene group (formulas 45 to 48), quinolindiyl group (formulas 49 to 63), and quinoxalindi Diary (Formula 64-68), acridinediyl group (Formula 69-72), bipyridyldiyl group (Formula 73-75), phenanthrolinediyl group (Formula 76-78), and the like;

Groups containing silicon, nitrogen, selenium, and the like as hetero atoms, and having a fluorene structure (formulas 79-93);

5-membered ring heterocyclic groups including silicon, nitrogen, sulfur, selenium, etc. as a hetero atom (formulas 94-98);

5-membered ring condensed heterocyclic group containing silicon, nitrogen, selenium, etc. as a hetero atom (formulas 99 to 100, 102 to 110);

A 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom, and a group bonded at the α position of the hetero atom to form a dimer or oligomer (formulas 111 to 112);

A 5-membered ring heterocyclic group including silicon, nitrogen, sulfur, selenium, etc. as a hetero atom, and a group bonded to a phenyl group at the α position of the hetero atom (Formulas 113 to 119);

Examples of the hetero atom include groups in which a phenyl group, a furyl group, and a thienyl group are substituted with a 5-membered ring condensed heterocyclic group containing oxygen, nitrogen, sulfur, and the like (formulas 120 to 125).

In addition, the divalent group which has a metal complex structure in Ar <_1> , Ar <_2> , Ar <_3>, and Ar <_4> is a divalent group remaining except two hydrogen atoms from the organic ligand of the metal complex which has an organic ligand.

The carbon number of the organic ligand is usually about 4 to 60, for example 8-quinolinol and its derivatives, benzoquinolinol and its derivatives, 2-phenyl-pyridine and its derivatives, 2-phenyl-benzothiazole and Derivatives thereof, 2-phenyl-benzoxazole and derivatives thereof, porphyrins and derivatives thereof, and the like.

Moreover, as a center metal of the said complex, aluminum, zinc, beryllium, iridium, platinum, gold, europium, terbium, etc. are mentioned, for example.

As a metal complex which has an organic ligand, a low molecular fluorescent material, a metal complex known as a phosphorescent material, a triplet light emission complex, etc. are mentioned.

As a bivalent group which has a metal complex structure, the following general formula (126-132) is illustrated specifically.

In Chemical Formulas 1 to 132, R each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, or an arylalke Neyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group Indicates. In addition, the carbon atoms of the groups of Formulas 1 to 132 may be substituted with a nitrogen atom, an oxygen atom, or a sulfur atom, and the hydrogen atom may be substituted with a fluorine atom.

Moreover, in the repeating unit represented by the said Formula (V), VI, VII, VIII, the repeating unit represented by the following Formula (IX), Formula (X), Formula (XI), Formula (XII), Formula (XIII), or Formula (XIV) is preferable.

In the formula, R ₁₄ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, Substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group, n is 0-4 In the case of plural R ₁₄ 's, these may be the same or different.

In formula, R <_15> and R <_16> is respectively independently alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalki A silyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group, and o And p each independently represent an integer of 0 to 3, and when a plurality of R ₁₅ and R ₁₆ are each present, they may be the same or different.

In the formula, each of R ₁₇ and R ₂₀ is independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, or an arylalki A silyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, or a cyano group, and q And r each independently represent an integer of 0 to 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, and R ₁₇ and R _{When a} plurality of ₂₀ are present, they may be the same or different.

In the formula, R ₂₁ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, Substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group, s represents 0 to 2 Represents an integer of, 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, and X ₄ represents O, S, SO, SO ₂ , Se, or Te, and when there are a plurality of R _{21 s} , they may be the same or different.

In the formula, R ₂₂ and R ₂₅ are each independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, or an arylalki A silyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, or a cyano group, and t And u each independently represent an integer of 0 to 4, X ₅ represents O, S, SO ₂ , Se, Te, NR ₂₄ , or SiR ₂₅ R ₂₆ , X ₆ and X ₇ are each independently 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 arylalkyl group or a monovalent heterocyclic group, and a plurality of R ₂₂ , R ₂₃ and R ₂₇ are present. If so, they may be the same or different.

Examples of the 5-membered ring in the center of the repeating unit represented by the formula (XI) include thiadiazole, oxadiazole, triazole, thiophene, furan, and sirol.

In the formula, R ₂₈ and R ₃₃ each independently represent an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, or an arylalki A silyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, or a cyano group, and v And w each independently represent an integer of 0 to 4, and 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 And Ar ₅ represents an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure, and when a plurality of R ₂₈ and R ₃₃ are present, these may be the same or different.

In addition, it is preferable also from the viewpoint of changing the light emission wavelength, the viewpoint of improving luminous efficiency, and the heat resistance among the repeating units represented by the above formula (VI).

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 monovalent heterocyclic group, Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ and Ar ₁₀ may have a substituent, and x and y each independently represent 0 or 1, and 0 ≦ x + y ≦ 1.

Specific examples of the repeating unit represented by the general formula (XV) include those represented by the following general formulas (133) to (140).

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

In order to improve the solubility in an organic solvent, it is preferable to have one or more things other than a hydrogen atom, and it is preferable that the symmetry of the shape of the repeating unit containing a substituent is small.

In the above formula, in the substituent in which R contains alkyl, in order to improve the solubility of the high molecular compound in the solvent, it is preferable that one or more alkyl which has a cyclic or branched thing is contained.

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

In the repeating unit represented by the above formula (XV), Ar ₆ , Ar ₇ , Ar _8, and Ar ₉ are each independently an arylene group from the viewpoint of adjusting the emission wavelength, device characteristics, and the like, and Ar ₁₀ , Ar _11, and It is preferable that Ar ₁₂ each independently represent an aryl group.

Ar ₆ , Ar ₇ and Ar ₈ are each preferably an unsubstituted phenylene group, an unsubstituted biphenyl group, an unsubstituted naphthylene group, or an unsubstituted anthracenediyl group.

Ar _10, As Ar _l1 and Ar _12, the solubility, the luminous efficiency, a phenyl group, an aryl group from the point of view of stability that has three or more substituents each independently is preferable, and the Ar _10, Ar ₁₁ and Ar ₁₂ has a substituent at least three It is more preferable that it is a naphthyl group which has 3 or more substituents, or an anthranyl group which has 3 or more substituents, and it is still more preferable that Ar <_10> , Ar <_11> and Ar <_12> are phenyl groups which have 3 or more substituents.

Especially, it is preferable that Ar <_10> , Ar <_11> and Ar <_12> are respectively independently the following general formula XVa.

In formula, Re, Rf, and Rg are respectively independently alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalky And a silyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a silyloxy group, a substituted silyloxy group, a monovalent heterocyclic group or a halogen atom.

In the repeating unit represented by Chemical Formula XV, Ar ₇ is preferably the following Chemical Formula XVb or XVc.

Herein, the benzene rings included in the structures represented by the formulas XVb and XVc may each independently have one or more than four substituents, and these substituents may be the same or different from each other, and a plurality of substituents may be linked to A ring may be formed and another aromatic hydrocarbon ring or heterocyclic ring may be adjacent to the benzene ring.

As a repeating unit represented by the said Formula (XV), what is shown by following formula (141)-142 is mentioned as an especially preferable specific example.

In the formula, Re to Rg are as described above.

In the above formula, Re to Rg is the same as that of the formula (1) to (132). In order to improve the solubility to a solvent, it is preferable to have one or more things other than a hydrogen atom, and it is preferable that there is little symmetry of the shape of the repeating unit which contained the substituent.

In the above formula, in the substituent in which R contains an alkyl chain, in order to increase the solubility of the high molecular compound in the solvent, it is preferable that at least one alkyl chain having a cyclic or branched chain is included.

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

In addition, the polymer compound of the present invention may include repeating units other than the repeating units represented by the above formulas (Ia), (Ib), (Ic) and (V) to (XV) within a range that does not impair the luminescence properties or the charge transport properties. . In addition, these repeating units or other repeating units may be linked to non-conjugated units, and these non-conjugated portions may be included in the repeating units. As a coupling structure, what combined two or more of what is shown below, and what is shown below is illustrated. Here, R is group selected from the same substituent as the above, Ar represents a C6-C60 hydrocarbon group.

Among the polymer compounds of the present invention, those containing only the repeating unit represented by the formula (Ia), and / or containing only the repeating unit represented by the formula (Ib), and / or containing only the repeating unit represented by the formula (Ic). It is preferable to include at least one of the repeating units represented by the above formulas (Ia) and / or (Ib) and / or (Ic) and the above formulas (V) to (XV).

Further, 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 block copolymer random copolymer. From the viewpoint of obtaining a polymer light emitting body having a high quantum yield of fluorescence or phosphorescence, a block copolymer or a block copolymer or a graft copolymer having a block property is preferable to a completely random copolymer. Branches have a branched structure in the main chain, and include a dendrimer or a case having three or more terminal portions.

In addition, the terminal group of the polymer compound of the present invention may be protected by a stable group since the luminescence properties and lifespan of the device may be reduced if the polymerization active group remains as it is. It is preferable to have a conjugated bond continuous with the conjugated structure of the main chain, and for example, a structure bonded to an aryl group or a heterocyclic group via a carbon-carbon bond is illustrated. Specifically, the substituent etc. which are described in the formula (10) of Unexamined-Japanese-Patent No. 9-45478 are illustrated.

In the polymer compound of the present invention, it is preferable that at least one of the terminal ends of the molecular chain is an aromatic terminal group selected from a monovalent heterocyclic group, a monovalent aromatic amine group, a monovalent group derived from a heterocyclic coordination metal complex, and an aryl group. . 1 type may be sufficient as this aromatic terminal group, and 2 types may be sufficient as it. It is preferable that terminal groups other than an aromatic terminal group do not exist substantially from a viewpoint of a fluorescent characteristic or an element characteristic. Here, the molecular chain terminal is an aromatic terminal group present at the terminal of the high molecular compound by the production method of the present invention, the leaving group of the monomer used for polymerization, the leaving group present at the terminal of the high molecular compound without leaving at the time of polymerization, The hydrogen atom which the aromatic terminal group of the leaving group derived from the monomer which exists in the terminal of a high molecular compound fell, did not couple | bond, but couple | bonded instead. Among these molecular chain ends, the polymer compound of the present invention is used by using a leaving group which is a leaving group of the monomer used for polymerization and which does not leave at the time of polymerization but is present at the terminal of the high molecular compound, for example, a monomer having a halogen atom as a raw material. In the case of manufacture, since fluorescent property etc. tend to fall when halogen remains in the terminal of a high molecular compound, it is preferable that the leaving group of a monomer does not remain in the terminal substantially.

In the high molecular compound, at least one of the molecular chain ends is sealed with an aromatic end group selected from a monovalent heterocyclic group, a monovalent aromatic amine group, a monovalent group derived from a heterocyclic coordination metal complex, or an aryl group having a formula weight of 90 or more. It is expected to add various characteristics to a high molecular compound by this. Specifically, the effect of increasing the time required for lowering the brightness of the device, the effect of increasing the charge injection property, the charge transporting property, the light emission characteristics, and the like, the effect of increasing the compatibility or interaction between the copolymers, the anchoring effect, and the like.

As a monovalent aromatic amine group, the structure which sealed one of two bonds which have two in the structure of the said general formula (XV) with R is illustrated.

As a monovalent group guide | induced from a heterocyclic coordination metal complex, the structure which sealed one of two bonding hands which has two in the bivalent group which has the metal complex structure mentioned above with R is illustrated.

Among the aromatic end groups possessed by the polymer compound of the present invention, the aryl group having a formula weight of 90 or more usually has 6 to 60 carbon atoms. Here, the formula weight of an aryl group means the sum of the product of the number of atoms of each element multiplied by the atomic weight of each element in the formula when the aryl group is represented by the formula.

As an aryl group, the group which has a phenyl group, a naphthyl group, anthracenyl group, a fluorene structure, a condensed cyclic compound group, etc. are mentioned.

As a phenyl group sealing the terminal, for example

Can be mentioned.

As a naphthyl group which seals a terminal, for example

Can be mentioned.

As an anthracenyl group, for example

Can be mentioned.

As a group containing a fluorene structure, for example

Can be mentioned.

As a condensed cyclic compound group, for example

Can be mentioned.

As a terminal group which improves charge injection property and charge transport property, a monovalent heterocyclic group, a monovalent aromatic amine group, and a condensed cyclic compound group are preferable, and a monovalent heterocyclic group and a condensed cyclic compound group are more preferable.

As a terminal group which improves luminescence property, the monovalent group derived from a naphthyl group, anthracenyl group, a condensed cyclic compound group, and a heterocyclic coordination metal complex is preferable.

As a terminal group which has the effect of lengthening time required for the brightness fall of an element, the aryl group which has a substituent is preferable, and the phenyl group which has 1-3 alkyl groups is preferable.

As a terminal group which has the effect of raising the compatibility and interaction between high molecular compounds, the aryl group which has a substituent is preferable. Moreover, an anchoring effect can be exhibited by using the phenyl group which the C6 or more alkyl group substituted. An anchor effect means the effect which an end group plays an anchor role with respect to the aggregate of a polymer, and raises interaction.

As group which improves an element characteristic, the following structure is preferable.

In the formula, R is exemplified above.

The number average molecular weight of polystyrene conversion of the high molecular compound of this invention is about 10 <^3> -10 <^8> , Preferably it is 10 <^4> -10 <^6> . Further, the weight average molecular weight in terms of polystyrene is from 10 ³ to 10 ^8, preferably from 10 ⁴ to 5 × 10 ^6.

Examples of the good solvent for the polymer compound of the present invention include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, n-butylbenzene and the like. Although dependent also on the structure and molecular weight of a high molecular compound, it can usually melt | dissolve in these solvent 0.1weight% or more.

The polymer compound of the present invention can emit light with a short wavelength compared with the corresponding polyfluorene derivative.

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

Among the high molecular compounds of the present invention, for example, those having a repeating unit represented by the formulas (Ia), (Ib) and (Ic) can be produced by polymerizing using at least compounds represented by the following formulas (XVIa, XVIb and XVIc) as raw materials.

In the formula, A ring, B ring, C ring, 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.

Among the compounds represented by the formula (XVIa), the compounds represented by the following formula (XVIIa) are preferable.

In formula, R <_1> , R <_2> , a, b, D ring, Q, z, Y <_1> and Y <_2> represent the same meaning as the above.

Among the compounds represented by the formula (XVIIa), structures represented by the following formulas (XVIIIa, XVIIIb, XVIIIc and XVIIId) are more preferable.

Moreover, among the compounds represented by general formula (XVIb), the compound represented by the following general formula (XVIIb) is preferable.

In the formula, ring B, ring C, Z ₂ , Z ₃ , Z ₄ , Y ₃ and Y ₄ represent the same meaning as described above, and Z ₆ , Z ₇ and Z ₈ are each independently 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 described above, R ₄ represents a substituent, and e represents an integer of 0 to 2, When there are a plurality of R ₄ , they may be the same or different, and R ₄ may be bonded to each other to form a ring.

Moreover, among the compounds represented by general formula (XVIc), the compound represented by the following general formula (XVIIc) is preferable.

In the formula, A ring, B ring, Z ₁ , Z ₄ , Z ₅ , Y ₅ and Y ₆ have the same meaning as above, and Z ₁₀ , Z ₁₁ , Z ₁₂ and Z ₁₃ are each independently 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 to 2, When there are a plurality of R _{5 s} , they may be the same or different, and R ₅ may be bonded to each other to form a ring.

In the production method of the present invention, the substituents involved in the polymerization include a halogen atom, an alkylsulfonate group, an arylsulfonate group, an arylalkylsulfonate group, a boric acid ester group, a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, A monohalogenated methyl group, -B (OH) ₂ , a formyl group, a cyano group, a vinyl group, etc. are mentioned.

Here, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. From the viewpoint of improving the degree of polymerization, bromine atoms and iodine atoms are preferred.

Examples of the alkylsulfonate group include a methanesulfonate group, an ethanesulfonate group, a trifluoromethanesulfonate group and the like, and an arylsulfonate group include a benzenesulfonate group and a p-toluenesulfonate group. Benzyl sulfonate group etc. are illustrated as a nate group.

As a boric acid ester group, group represented by a following formula is illustrated.

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

As a sulfonium methyl group, group represented by a following formula is illustrated.

_{^{-CH 2 S + Me 2 X -}} , -CH 2 S + Ph 2 X -

In the formula, X represents a halogen atom, and Ph represents a phenyl group.

As a phosphonium methyl group, group represented by a following formula is illustrated.

-CH ₂ P ⁺ Ph ₃ X ^-

In the formula, X represents a halogen atom.

As a phosphonate methyl group, group represented by a following formula is illustrated.

-CH ₂ PO (OR ') ₂

In the formula, X represents a halogen atom, and R 'represents an alkyl group, an aryl group, or an arylalkyl group.

Examples of the monohalogenated methyl group include methyl fluoride group, methyl chloride group, methyl bromide group, and methyl iodide group.

Preferred substituents for the substituents involved in the polymerization are different depending on the type of polymerization reaction. For example, when a zero-valent nickel complex such as a Yamamoto coupling reaction is used, a halogen atom, an alkylsulfonate group, an arylsulfonate group or an aryl Alkyl sulfonate group is mentioned. Moreover, when using a nickel catalyst or a palladium catalyst, such as a Suzuki coupling reaction, an alkylsulfonate group, a halogen atom, a boric acid ester group, -B (OH) _2, etc. are mentioned.

In particular, the polymer compound having a repeating unit of formula IVa may be hydrogenated by a catalyst in which a high molecular compound having repeating units of formulas IVb to IVd is supported on palladium, platinum, rhodium, ruthenium, or a mixed precious metal on activated carbon. You can get it.

On the contrary, the high molecular compound having repeating units of formulas IVb to IVd may be a 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) or a base as the high molecular compound having a repeating unit of formula IVa. It can also be obtained by oxidation using tetrabutylammonium bromide under the conditions.

In addition, when the polymer compound of the present invention has a repeating unit other than the formula (Ia) or the formula (Ib) or the formula (Ic), the compound having a substituent involved in two polymerizations, which is a repeating unit other than the formula (Ia) or the formula (Ib) or the formula (Ic) It is preferable to coexist and superpose | polymerize.

In addition to the compounds represented by the above formulas XVIa, XVIb or XVIc, the compounds represented by any one of the following formulas XIX to XXII can be used as raw materials.

In the formula, 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 substituent that can be polymerized.

In addition to the units represented by the above formulas (Ia), (Ib) or (Ic), a polymer compound having one or more units of the formula (V), (VI), (VII) or (VIII) may be prepared in order.

Moreover, as a compound which has a substituent which participates in two superposition | polymerization corresponding to the said Formula (XV) used as repeating units other than the repeating unit represented by the said Formula (Ia), (Ib) or (Ic), the compound represented by following formula (XVg) is mentioned. .

In the formula, Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ , Ar ₁₀ , Ar ₁₁ , Ar ₁₂ , x and y are the same as above, and Y ₁₅ and Y ₁₆ each independently represent a substituent involved in polymerization.

More preferably, it is a compound represented by following formula (XVh) or formula (XVi).

In the formula, Re to Rg are as described above, and Y ₁₇ , Y ₁₈ , Y ₁₉ , and Y ₂₀ each independently represent a substituent involved in polymerization.

In the production method of the present invention, a compound having a plurality of substituents involved in a polymerization reaction, specifically, a monomer, is dissolved in an organic solvent, if necessary, for example, by using an alkali or a suitable catalyst or more, It can carry out below boiling point. See, for example, Organic Reactions, Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965, Organic Syntheses, Collective Vol. 6, pp. 407-411, John Wiley & Sons, Inc., 1988, Chem. Rev., Vol. 95, p. 2457 (1995)], J. 0rganomet. Chem., 576, p. 147 (1999), Makromol. Chem., Macromol. Symp., Vol. 12, p. 229 (1987) and the like can be used.

In the manufacturing method of the high molecular compound of this invention, as a method of superposing | polymerizing, it can manufacture by using a well-known polymerization reaction according to the substituent which participates in superposition | polymerization of the compound represented by the said general formula (XVIa-XVIc) and XXII-XXV.

In the superposition | polymerization of the high molecular compound of this invention, when producing a double bond, the method of Unexamined-Japanese-Patent No. 5-202355 is mentioned, for example. That is, polymerization 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 by Wittig reaction, a compound having a vinyl group and a compound having a halogen atom ( Heck) polymerization, polymerization by dehalogenation of compounds having two or more monohalogenated methyl groups, polymerization by sulfonium salt decomposition of compounds having two or two sulfoniummethyl groups, formyl groups Examples thereof include a method such as polymerization by a Knoevenagel reaction of a compound having a compound with a cyano group, and a polymerization by a McMurry reaction of a compound having two or two formyl groups. do.

When the high molecular compound of this invention produces | generates triple bond in a principal chain by superposition | polymerization, hex reaction and Sonogashira reaction can be used, for example.

In addition, when a double bond or a triple bond is not produced, the method of superposition | polymerization by the Suzuki coupling reaction from the corresponding monomer, the method of superposition | polymerization by a Grignard reaction, the method of superposition | polymerization by a Ni (0) complex, for example. , A method of polymerization with an oxidizing agent such as FeCl ₃ , a method of electrochemically oxidizing polymerization, a method by decomposition of an intermediate polymer having a suitable leaving group, and the like.

Among them, the polymerization by the Wittig reaction, the polymerization by the Heck reaction, the polymerization by the Kneubenagel reaction, and the polymerization by the Suzuki coupling reaction, the polymerization by the Grignard reaction, the polymerization by the nickel zero complex. The method is preferable because the structure control is easy.

In the production method of the present invention, when polymerizing a compound represented by the formula (XVIa), XVIb or XVIc alone or at least one selected from the compounds represented by the formulas (XIX to XXII), 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 , Y ₂₀ Each of these is independently a halogen atom, an alkylsulfonate group, an arylsulfonate group or an arylalkylsulfonate group, and a production method of condensation polymerization in the presence of a nickel zero complex is preferable.

Examples of the starting compound include a dihalogenated compound, a bis (alkylsulfonate) compound, a bis (arylsulfonate) compound, a bis (arylalkylsulfonate) compound or a halogen-alkylsulfonate compound, a halogen-arylsulfonate compound, a halogen-arylalkyl Sulfonate compounds, alkylsulfonate-arylsulfonate compounds, alkylsulfonate-arylalkylsulfonate compounds, and arylsulfonate-arylalkylsulfonate compounds.

In the production method of the present invention, when the compound represented by the formula (XVIa), (XVIb) or (XVIc) is polymerized alone or with one or more selected from the compounds represented by the formulas (XIX to XXII), 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 , Each Y ₂₀ is independently a halogen atom, an alkylsulfonate group, an arylsulfonate group, an arylalkylsulfonate group, -B (OH) ₂ , or a boric acid ester group, and a halogen atom, an alkylsulfonate group, or an arylsulfonate group And the ratio of the total number of moles of the arylalkylsulfonate group to the total number of moles of the -B (OH) ₂ and boric acid ester groups is substantially 1 (usually K / J is in the range of 0.7 to 1.2), and a nickel or palladium catalyst is used. The manufacturing method which uses condensation polymerization is preferable.

As a specific raw material combination, a combination of a dihalogenated compound, a bis (alkylsulfonate) compound, a bis (arylsulfonate) compound or a bis (arylalkylsulfonate) compound with a diboric acid compound or a diboric acid ester compound is mentioned. .

Further, halogen-boric acid compound, halogen-boric acid ester compound, alkylsulfonate-boric acid compound, alkylsulfonate-boric acid ester compound, arylsulfonate-boric acid compound, arylsulfonate-boric acid ester compound, arylalkylsulfonate-boric acid compound , Arylalkyl sulfonate-boric acid compound, and arylalkylsulfonate-boric acid ester compound.

Although it changes also with the compound and reaction to be used as an organic solvent, In general, in order to suppress a side reaction, it is preferable that the solvent to be used fully deoxygenates and advances reaction in inert atmosphere. Moreover, it is preferable to perform dehydration process similarly. However, in the case of reaction in the two-phase system with water, such as a Suzuki coupling reaction, it is not limited to that.

Examples of the solvent include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, chloropentane and bromopentane. Halogenated saturated hydrocarbons such as chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene, methanol, ethanol, propanol, isopropanol, butanol and t-butyl Alcohols such as alcohols, carboxylic acids such as formic acid, acetic acid and propionic acid, ethers such as dimethyl ether, diethyl ether, methyl-t-butyl ether, tetrahydrofuran, tetrahydropyran and dioxane, trimethylamine and tri Amines such as ethylamine, N, N, N ', N'-tetramethylethylenediamine, pyridine, N, N-dimethylformamide, N, N-dimethyla Bit amide, N, N- diethylacetamide, N- methylmorpholine, and the like exemplified amides such as oxide, may be used a single solvent, mixed solvents of the foregoing. Among these, ethers are preferable, and tetrahydrofuran and diethyl ether are more preferable.

Alkali or a suitable catalyst is added suitably for reaction. These may be selected according to the reaction to be used. It is preferable that the said alkali or a catalyst is melt | dissolved in the solvent used for reaction fully. As a method of mixing an alkali or a catalyst, the method of adding an alkali or a catalyst solution slowly, stirring a reaction liquid in inert atmosphere, such as argon or nitrogen, or the method of slowly adding a reaction liquid to an alkali or a catalyst solution is illustrated.

When the polymer compound of the present invention is used in a polymer LED or the like, since its purity affects device performance such as light emission characteristics, it is preferable to polymerize the monomer before polymerization after purification by a method such as distillation, sublimation purification or recrystallization. . Moreover, it is preferable to perform the purification process, such as reprecipitation purification and chromatography fractionation, after superposition | polymerization.

Formulas XVIa to XVIc, XVIIa to XVIIc and XVIIIa to XVIIId which are useful as raw materials for the polymer compound of the present invention can be obtained by brominating a compound having a structure in which Y ₁ to Y ₆ in the above formula are substituted with hydrogen atoms.

In particular, the compound having the structure of the formula (XVIIIa) can be obtained by hydrogenation of a compound having the structure of the formulas (XVIIIb) to (XVIIId) with palladium, platinum, rhodium, ruthenium, or a catalyst having a precious metal mixed thereon supported on activated carbon.

Conversely, a compound having a structure of formulas XVIIIb to XVIIId is a compound having a structure of formula XVIIIa as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), but tetrabromide under basic conditions. It can also be obtained by oxidation using butylammonium.

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

The polymer LED of the present invention has an organic layer between electrodes including an anode and a cathode, and the organic layer comprises the polymer compound of the present invention.

The organic layer may be any one of a light emitting layer, a hole transporting layer and an electron transporting layer, but is preferably a light emitting layer.

Here, the light emitting layer refers to a layer having a function of emitting light, the hole transporting layer refers to a layer having a function of transporting holes, and the electron transporting layer refers to a layer having a function of transporting electrons. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. The light emitting layer, the hole transporting layer, and the electron transporting layer may each independently use two or more layers.

When the organic layer is a light emitting layer, the light emitting layer as the organic layer may further include a hole transport material, an electron transport material, or a light emitting material. Here, a luminescent material means the material which shows fluorescence and / or phosphorescence.

When mixing the high molecular compound of this invention and a hole transport material, the mixing ratio of a hole transport material with respect to the whole mixture is 1 weight%-80 weight%, Preferably it is 5 weight%-60 weight%. When mixing the high molecular compound of this invention and an electron carrying material, the mixing ratio of an electron carrying material with respect to the whole mixture is 1 weight%-80 weight%, Preferably it is 5 weight%-60 weight%. In addition, when mixing the high molecular compound of this invention and a luminescent material, the mixing ratio of a luminescent material with respect to the whole mixture is 1 weight%-80 weight%, Preferably it is 5 weight%-60 weight%. In the case where the polymer compound of the present invention and the light emitting material, the hole transporting material and / or the electron transporting material are mixed, the mixing ratio of the light emitting material to the whole mixture is 1% by weight to 50% by weight, preferably 5% by weight. To 40% by weight, the hole transporting material and the electron transporting material are 1% by weight to 50% by weight in total, preferably 5% by weight to 40% by weight, and the content of the polymer compound of the present invention is 99% by weight. To 20% by weight.

Although the well-known low molecular weight compound, triplet light emission complex, or a high molecular compound can be used for the positive hole transport material, the electron carrying material, and the light emitting material to mix, it is preferable to use a high molecular compound. The hole transporting material, electron transporting material and light emitting material of the high molecular compound are WO99 / 13692, 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, US573636, WO98 / 21262, US5741921, WO97 / 09394, WO96 / 29356, WO96 / 10617, EP0707020, WO95 / 07955, Japanese Patent Publication No. 2001-181618, Japanese Patent Publication No. 2001-123156, Japanese Patent Publication No. 2001-3045 , Japanese Patent Publication No. 2000-351967, Japanese Patent Publication No. 2000-303066, Japanese Patent Publication No. 2000-299189, Japanese Patent Publication No. 2000-252065, Japanese Patent Publication ) 2000-136379, Japanese Patent Publication No. 2000-104057, Japanese Patent Publication No. 2000-80167, Japanese Patent Publication No. 10-324870, Japanese Patent Publication No. 10-114891, Japanese Patent Publication No. 9-111233, Japanese Patent Publication No. 9-4 Polyfluorenes, derivatives and copolymers thereof, polyarylenes, derivatives and copolymers thereof, polyarylenevinylene, derivatives and copolymers thereof, aromatic amines and derivatives thereof, and the like, disclosed in US Pat. Is illustrated.

As the fluorescent material of the low molecular weight compound, for example, naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine based, pigments such as xanthene based, coumarin based, cyanine based, 8-hydroxyquinoline or derivatives thereof Metal complexes, aromatic amines, tetraphenylcyclopentadiene or derivatives thereof, tetraphenylbutadiene or derivatives thereof and the like can be used.

Specifically, well-known things, such as those described in Unexamined-Japanese-Patent No. 57-51781 and 59-194393, can be used, for example.

Examples of the triplet light emitting complex include Ir (ppy) _{3 having} iridium as the center metal, Btp ₂ Ir (acac), PtOEP having platinum as the center metal, Eu (TTA) ₃ phen having Europium as the center metal, and the like. Can be mentioned.

As the triplet light emitting complex, specifically, for example

And the like.

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

What is necessary is just to determine the content rate of the 1 or more types of material chosen from this hole transport material, an electron transport material, and a luminescent material, and the high molecular compound of this invention according to a use.

As another embodiment of this invention, the polymer composition containing 2 or more types of high molecular compounds of this invention is illustrated.

As the film thickness of the light emitting layer of the polymer LED of the present invention, the optimum value varies depending on the material to be used, and it is preferable to select such that the driving voltage and the luminous efficiency are appropriate values. For example, it is 1 nm-1 micrometer, Preferably it is 2 nm-500 nm, More preferably, it is 5 nm-200 nm.

As a formation method of a light emitting layer, the method by film-forming from a solution is illustrated, for example. In the production of a polymer LED, when the film is formed from a solution by using the polymer compound of the present invention, the solvent may only be removed by drying after application of the solution, and even when a charge transport material or a light emitting material is mixed. The same technique can be applied, which is very advantageous in manufacturing.

As a film formation method from a solution, spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, flexographic printing Coating methods such as a printing method, an offset printing method, and an inkjet printing method can be used. Printing methods such as a screen printing method, a flexographic printing method, an offset printing method, an inkjet printing method and the like are preferable in view of easy pattern formation and multicolor coating and dividing.

As a solution used by the printing method, the ink composition of this invention can be used.

The ink composition of this invention should just contain 1 or more types of high molecular compound and solvent of this invention, and may also contain additives, such as a hole transport material, an electron transport material, a light emitting material, a stabilizer, in addition to the high molecular compound of this invention. .

The ink composition of the present invention means that it is liquid at the time of device manufacture, and is typically liquid at normal pressure (ie, 1 atmosphere) at 25 ° C.

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

The proportion of the polymer compound of the present invention in the ink composition is usually 20% by weight to 100% by weight, preferably 40% by weight to 100% by weight based on the total weight of the ink composition excluding the solvent.

The proportion of the solvent in the ink composition is 1% by weight to 99.9% by weight, preferably 60% by weight to 99.9% by weight, and more preferably 90% by weight to 99.8% by weight based on the total weight of the ink composition. to be.

Although the viscosity of the ink composition (solution) varies depending on the printing method, when the solution such as the inkjet printing method passes through the discharge device, the viscosity is 25 ° C. in order to prevent clogging or flight bending during discharge. It is preferable that it is the range of 1-20 mPa * s.

Examples of the solvent used in the ink composition of the present invention include chlorine solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, and o-dichlorobenzene, tetrahydrofuran and dioxane. Aliphatic hydrocarbons, such as ether solvents, aromatic hydrocarbon solvents, such as toluene and xylene, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane Ketone solvents such as solvents, acetone, methyl ethyl ketone, cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, Polyhydric alcohols and derivatives thereof such as ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin and 1,2-hexanediol Alcohol solvents such as ol, ethanol, propanol, isopropanol, cyclohexanol, sulfoxide solvents such as dimethyl sulfoxide, amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide Is illustrated. In addition, these organic solvents can be used individually or in combination of several. It is preferable to have a structure containing one or more benzene rings among the said solvents, and to contain 1 or more types of organic solvent whose melting | fusing point is 0 degrees C or less and a boiling point is 100 degreeC or more.

As a kind of solvent, from a viewpoint of the solubility to the organic solvent of the high molecular compound of this invention, the uniformity at the time of film-forming, a viscosity characteristic, etc., an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, an ester solvent, and a ketone solvent are preferable. , Toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, mesitylene, n-propylbenzene, i-propylbenzene, n-butylbenzene, i-butylbenzene, s-butylbenzene, anisole, ethoxybenzene, 1-methylnaphthalene, cyclohexane, cyclohexanone, cyclohexylbenzene, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, methylbenzoate, 2-propylcyclohexanone , 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2-decanone, dicyclohexylketone are preferable, and xylene, anisole, mesitylene, cyclohexylbenzene More than one of bicyclohexylmethylbenzoate It is good.

It is preferable that the kind of solvent of an ink composition is 2 or more types from a viewpoint of film formability, an element characteristic, etc., It is more preferable that it is 2-3 types, It is further more preferable that it is two types.

When two solvents are contained in an ink composition, one solvent of them may be solid at 25 degreeC. From the viewpoint of film forming properties, it is preferable that one solvent is a solvent having a boiling point of 180 ° C. or higher, the other solvent is a solvent having a boiling point of 180 ° C. or lower, and one solvent is a solvent having a boiling point of 200 ° C. or higher, and the other 1 As for the solvent of a species, it is more preferable that it is a solvent whose boiling point is 180 degrees C or less. From the viewpoint of viscosity, it is preferable to dissolve 0.2 wt% or more of the polymer compound of the present invention at 60 ° C in both solvents, and 0.2 wt% or more at 25 ° C in one solvent of the two solvents. It is preferable that the high molecular compound of melt | dissolve.

When three kinds of solvents are included in the ink composition, one or two of them may be solid at 25 ° C. From the viewpoint of film forming properties, it is preferable that at least one solvent of the three solvents is a solvent having a boiling point of 180 ° C. or more, and the at least one solvent is a solvent having a boiling point of 180 ° C. or less, and at least one solvent of the three solvents has a boiling point. It is a solvent which is 200 degreeC or more and 300 degrees C or less, and it is more preferable that 1 or more types of solvent are solvents whose boiling point is 180 degrees C or less. Further, from the viewpoint of viscosity, it is preferable that at least 60% by weight of the polymer compound of the present invention is dissolved in two solvents among the three solvents, and 0.2 at 25 ° C in one solvent of the three solvents. It is preferable that the polymer compound of the present invention by weight or more is dissolved.

When two or more solvents are included in the ink composition, from the viewpoint of viscosity and film formability, the solvent having the highest boiling point is preferably 40 to 90% by weight of the total solvent weight of the ink composition, and more preferably 50 to 90% by weight. It is preferable and it is more preferable that it is 65-85 weight%.

As ink compositions of the present invention, from the viewpoint of viscosity and film formability, a composition comprising anisole and bicyclohexyl, a composition comprising anisole and cyclohexylbenzene, a composition comprising xylene and bicyclohexyl, xylene and cyclohexylbenzene Preferred is a composition comprising a, a composition comprising mesitylene and methylbenzoate.

Among the additives that may be included in the ink composition of the present invention,

Examples of the hole transport material include polyvinylcarbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having an aromatic amine in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof. , Polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylenevinylene) or derivatives thereof, or poly (2,5-thienylenevinylene) or derivatives thereof.

Examples of the electron transporting material include oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinone or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, and fluorenone derivatives. , Diphenyl dicyanoethylene or derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxy quinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof have.

Examples of the luminescent material include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine series, xanthene series, coumarin series, cyanine series and other pigments, 8-hydroxyquinoline or a metal complex of derivatives thereof, aromatic amines and tetra Phenyl cyclopentadiene or its derivative (s), or tetraphenyl butadiene or its derivative (s) etc. are mentioned.

The ink composition (solution) of this invention may contain the additive for adjusting a viscosity and / or surface tension other than the high molecular compound of this invention. As said additive, it is preferable to use suitably combining high molecular weight high molecular compound (thickening agent), a poor solvent, a low molecular weight compound for reducing a viscosity, surfactant for reducing surface tension, etc. suitably.

The high molecular weight polymer compound may be one that is soluble in the same solvent as that for the high molecular compound of the present invention and does not inhibit light emission or charge transport. For example, a high molecular weight polystyrene, polymethyl methacrylate, or the high molecular weight among the high molecular compounds of the present invention can be used. 500,000 or more are preferable and, as for a weight average molecular weight, 1 million or more are more preferable.

A poor solvent can also be used as a thickener. That is, a viscosity can be raised by adding a small amount of the poor solvent with respect to solid content in a solution. When adding a poor solvent for this purpose, it is preferable to select the kind and addition amount of a solvent in the range in which solid content in a solution does not precipitate.

Moreover, the ink composition (solution) of this invention may contain antioxidant other than the high molecular compound of this invention in order to improve storage stability. As antioxidant, what is necessary is just to be soluble in the same solvent as the high molecular compound of this invention, and to not inhibit light emission and charge transport, A phenolic antioxidant, phosphorus antioxidant, etc. are illustrated.

From the viewpoint of the solubility of the polymer compound of the present invention in the 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 solubility parameter of a solvent and the solubility parameter of the high molecular compound of this invention can be calculated | required by the method as described in a "solvent handbook" (the high yarn publication, 1976).

As the polymer LED of the present invention, a polymer LED having an electron transporting layer between the cathode and the light emitting layer, a polymer LED having a hole transporting layer between the anode and the light emitting layer, an electron transporting layer between the cathode and the light emitting layer, and a hole between the anode and the light emitting layer The polymer LED etc. which provided the transport layer are mentioned.

For example, specifically, the structure of the following a) -d) is illustrated.

a) anode / light emitting layer / cathode

b) anode / hole transport layer / light emitting layer / cathode

c) anode / light emitting layer / electron transport layer / cathode

d) anode / hole transport layer / light emitting layer / electron transport layer / cathode

(Where / indicates that the layers are stacked adjacent to each other, and are the same below)

The polymer LED of the present invention includes those in which the polymer compound of the present invention is contained in the hole transport layer and / or the electron transport layer.

When the polymer compound of the present invention is used in the hole transport layer, it is preferable that the polymer compound of the present invention is a polymer compound containing a hole transporting group, and specific examples thereof include copolymers with aromatic amines, copolymers with stilbene, and the like. This is illustrated.

In addition, when the high molecular compound of this invention is used for an electron carrying layer, it is preferable that the high molecular compound of this invention is a high molecular compound containing an electron carrying group, As a specific example, It is a copolymer with oxadiazole and a triazole. The copolymer, the copolymer with quinoline, the copolymer with quinoxaline, the copolymer with benzothiadiazole, etc. are illustrated.

When the polymer LED of the present invention has a hole transporting layer, the hole transporting material used may include polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in the side chain or the main chain, a pyrazoline derivative, an arylamine derivative , Stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylenevinylene) or derivatives thereof, or poly (2,5-thienylenevinyl) Lene) or derivatives thereof, and the like.

Specifically, Japanese Patent Laid-Open No. 63-70257, Japanese Patent Laid-Open No. 63-175860, Japanese Patent Laid-Open No. 2-135359, Japanese Patent No. 2-135361, Japanese Patent Laid-Open No. 209988, 3-37992, 3-152184, etc. are illustrated.

Among these, as the hole transporting material used for the hole transporting layer, polyvinylcarbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having aromatic amine compound groups in the side chain or main chain, polyaniline or derivatives thereof, polythiophene or derivatives thereof, Polymer hole transport materials such as poly (p-phenylenevinylene) or derivatives thereof, or poly (2,5-thiethylenevinylene) or derivatives thereof are preferable, and more preferably polyvinylcarbazole or derivatives thereof, Polysilanes or derivatives thereof, polysiloxane derivatives having aromatic amines in the side or main chain.

Moreover, as a hole transport material of a low molecular weight compound, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, and a triphenyl diamine derivative are illustrated. In the case of a low molecular hole transport material, it is preferable to disperse | distribute to a polymeric binder and to use.

As the polymer binder to be mixed, one which does not inhibit charge transport as much as possible, and one which does not have strong absorption of visible light is preferably used. As the polymer binder, poly (N-vinylcarbazole), polyaniline or derivatives thereof, polythiophene or derivatives thereof, poly (p-phenylenevinylene) or derivatives thereof, poly (2,5-thienylenevinylene) or Derivatives thereof, polycarbonates, polyacrylates, polymethylacrylates, polymethylmethacrylates, polystyrenes, polyvinyl chlorides, polysiloxanes and the like.

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

As polysilanes or derivatives thereof, Chem. Rev., Vol. 89, p. 1359 (1989)], and compounds described in British Patent GB2300196 publication specification and the like. Although the synthesis | combination method can also use the method as described in these, Especially a kipping method is used preferably.

Since polysiloxane or derivatives thereof have little hole transporting property in the siloxane skeleton structure, those having the structure of the low molecular hole transporting material in the side chain or the main chain are preferably used. In particular, what has a hole transport aromatic amine in a side chain or a main chain is illustrated.

Although there is no restriction | limiting in the film-forming method of a hole transport layer, The method by film-forming from the mixed solution with a polymeric binder is illustrated by the low molecular-hole hole transport material. In the polymer hole transport material, a method by film formation from a solution is exemplified.

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

As a film formation method from a solution, spin coating from a solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method And coating methods such as flexographic printing, offset printing, and inkjet printing.

As the film thickness of the hole transport layer, the optimum value is different depending on the material used, and the driving voltage and the luminous efficiency may be selected to be an appropriate value.At least, a thickness at which pinholes do not occur is required. This is not preferable because it is high. Therefore, as a film thickness of the said hole transport layer, it is 1 nm-1 micrometer, for example, Preferably it is 2 nm-500 nm, More preferably, it is 5 nm-200 nm.

When the polymer LED of the present invention has an electron transporting layer, a known one can be used as the electron transporting material to be used, and may include oxadiazole derivatives, anthraquinomethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof. , Anthraquinone or derivatives thereof, tetracyanoanthraquinomdimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, poly Quinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof and the like.

Specifically, Japanese Patent Application Laid-Open No. 63-70257, Japanese Patent Application Laid-Open No. 63-175860, Japanese Patent Application Laid-Open No. 2-135359, Japanese Patent No. 2-135361, Japanese Patent Application No. 2-209988, Examples of those disclosed in 3-37992, 3-152184, and the like are exemplified.

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

Although it does not restrict | limit especially as a film-forming method of an electron carrying layer, The method by the vacuum evaporation method from powder or the film-forming from a solution or molten state in the low molecular electron transport material is the method by the film-forming from a solution or molten state in a polymer electron transport material. Each of these is illustrated. At the time of film-forming from a solution or molten state, the said polymeric binder can also be used together.

There is no restriction | limiting in particular as a solvent used for film-forming from a solution as long as it dissolves an electron carrying material and / or a polymeric binder. As the solvent, chlorine solvents such as chloroform, methylene chloride and dichloroethane, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone and methyl ethyl ketone, ethyl acetate and butyl acetate And ester solvents such as ethyl cellosolve acetate.

As a film forming method from a solution or molten state, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, an immersion coating method, a spray coating method, a screen printing method And coating methods such as flexographic printing, offset printing, and inkjet printing.

As the film thickness of the electron transporting layer, the optimum value is different depending on the material used, and the driving voltage and the luminous efficiency may be selected to be an appropriate value.At least, a thickness at which no pinholes are generated is required. It is not preferable to become high. Therefore, as a film thickness of the said electron carrying layer, it is 1 nm-1 micrometer, for example, Preferably it is 2 nm-500 nm, More preferably, it is 5 nm-200 nm.

Among the charge transport layers provided adjacent to the electrodes, those having the function of improving the charge injection efficiency from the electrodes and the effect of lowering the driving voltage of the device are particularly called charge injection layers (hole injection layer, electron injection layer). Also commonly called.

In addition, in order to improve adhesion to the electrode and to improve charge injection from the electrode, the charge injection layer or an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode, and for the purpose of improving the adhesion of the interface or preventing mixing, etc. A thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.

The order and number of layers to be laminated and the thickness of each layer can be appropriately used in consideration of light emission efficiency and device life.

The polymer compound of the present invention can be used as a polymer field effect transistor as an organic semiconductor thin film. As the structure of the polymer field effect transistor, it is usually preferable that the source electrode and the drain electrode are provided in contact with an active layer containing a polymer, and the gate electrode is provided with an insulating layer in contact with the active layer.

The polymer field effect transistor is usually formed on a support substrate. Although it does not restrict | limit especially if the material of a support substrate does not impair the characteristic as a field effect transistor, A glass substrate, a flexible film substrate, or a plastic substrate can also be used.

A field effect transistor can be manufactured by a well-known method, for example by the method of Unexamined-Japanese-Patent No. 5- 110069.

When forming the active layer, it is preferable to use an organic solvent soluble polymer because it is very advantageous in production. As a film formation method from the solution which melt | dissolved the polymer in the organic solvent, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen Coating methods, such as a printing method, a flexographic printing method, an offset printing method, and the inkjet printing method, can be used.

The sealed polymer field effect transistor formed by manufacturing and then sealing a polymer field effect transistor is preferable. Thereby, a polymer field effect transistor is interrupted | blocked from air | atmosphere, and the fall of the characteristic of a polymer field transistor can be suppressed.

As a method of sealing, the method of covering with UV curable resin, a thermosetting resin, an inorganic SiONx film, etc., the method of joining a glass plate and a film with UV curable resin, a thermosetting resin, etc. are mentioned. In order to effectively block the atmosphere, it is preferable to perform the steps from the manufacture of the polymer field effect transistor until the sealing is performed without exposing the atmosphere to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).

In the present invention, as the polymer LED provided with the charge injection layer (electron injection layer, hole injection layer), a polymer LED having the charge injection layer adjacent to the cathode and a polymer LED having the charge injection layer adjacent to the anode Can be mentioned.

For example, the structure of the following e) -p) is mentioned specifically.

e) anode / charge injection layer / light emitting layer / cathode

f) anode / light emitting layer / charge injection layer / cathode

g) anode / charge injection layer / light emitting layer / charge injection layer / cathode

h) anode / charge injection layer / hole transport layer / light emitting layer / cathode

i) Anode / hole transport layer / light emitting layer / charge injection layer / cathode

j) anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode

k) anode / charge injection layer / light emitting layer / electron transport layer / cathode

l) anode / light emitting layer / electron transport layer / charge injection layer / cathode

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

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

Specific examples of the charge injection layer include a layer containing a conductive polymer, a layer provided between the anode and the hole transport layer, and a layer including a material having a median ionization potential between the anode material and the hole transport material included in the hole transport layer, and the cathode. And a layer provided between the electron transporting layer and a material having a median electron affinity between the cathode material and the electron transporting material included in the electron transporting layer.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, and in order to reduce leakage current between light emitting pixels, 10 ⁻⁵ S It is more preferable that it is more than / cm and 10 ² S / cm, and it is more preferable that it is ^10-5 S / cm or more and 10 ¹ S / cm or less.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, and in order to reduce leakage current between light emitting pixels, 10 ⁻⁵ S It is more preferable that it is more than / cm and less than 10 ² S / cm, and it is further more preferable that it is ^10-5 S / cm or more and 10 ¹ S / cm or less.

Usually, in order to make the electrical conductivity of the said conductive polymer into ^10-5 S / cm or more and 10 ³ S / cm or less, an appropriate amount of ions are doped into the conductive polymer.

Kinds of ions to be doped are anions if the hole injection layer and cations if the electron injection layer. Examples of the anion include polystyrene sulfonic acid ions, alkylbenzene sulfonic acid ions, camphorsulfonic acid ions and the like, and examples of the cations include lithium ions, sodium ions, potassium ions, tetrabutylammonium ions and the like.

As a film thickness of a charge injection layer, it is 1 nm-100 nm, for example, and 2 nm-50 nm are preferable.

The material used for the charge injection layer can be appropriately selected from the relationship with the material of the electrode or the adjacent layer, and polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylenevinylene and its Derivatives, polythienylenevinylene and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanine (such as copper phthalocyanine), carbon and the like This is illustrated.

An insulating layer having a thickness of 2 nm or less has a function of facilitating charge injection. As a material of the said insulating layer, a metal fluoride, a metal oxide, an organic insulating material, etc. are mentioned. As a polymer LED provided with an insulating layer having a thickness of 2 nm or less, a polymer LED having an insulating layer having a thickness of 2 nm or less adjacent to a cathode and a polymer LED having an insulating layer having a thickness of 2 nm or less adjacent to an anode are provided. Can be mentioned.

Specifically, the structures of the following q) to ab) are mentioned.

q) anode / film thickness of 2 nm or less, insulating layer / light emitting layer / cathode

r) anode / light emitting layer / insulating layer / cathode having a thickness of 2 nm or less;

s) anode / film thickness of 2 nm or less, insulating layer / light emitting layer / film thickness of 2 nm or less, insulating layer / cathode

t) anode / insulation layer / hole transport layer / light emitting layer / cathode of 2 nm or less in thickness

u) anode / hole transporting layer / light emitting layer / insulating layer / cathode having a film thickness of 2 nm or less;

v) anode / film thickness of 2 nm or less, insulating layer / hole transport layer / light emitting layer / film thickness of 2 nm or less, insulating layer / cathode

w) anode / film thickness of 2 nm or less, insulating layer / light emitting layer / electron transporting layer / cathode

x) anode / light emitting layer / electron transporting layer / insulating layer / cathode having a thickness of 2 nm or less

y) anode / film thickness 2 nm or less, insulating layer / light emitting layer / electron transport layer / film thickness 2 nm or less, insulating layer / cathode

z) Insulation layer / hole transport layer / light emitting layer / electron transport layer / cathode with anode / film thickness of 2 nm or less

aa) anode / hole transporting layer / light emitting layer / electron transporting layer / insulation layer / cathode of 2 nm or less in thickness

ab) anode / film thickness 2 nm or less, insulating layer / hole transport layer / light emitting layer / electron transport layer / film thickness 2 nm or less, insulation layer / cathode

The board | substrate which forms the polymer LED of this invention should just be a thing which does not change when forming an electrode and forming an organic substance layer, For example, glass, a plastic, a polymer film, a silicon substrate, etc. are illustrated. In the case of an opaque substrate, it is preferable that the opposite electrode is transparent or translucent.

Usually, at least one of the positive electrode and the negative electrode of the polymer LED of the present invention is transparent or translucent. It is preferable that the anode side is transparent or semitransparent.

As the material of the anode, a conductive metal oxide film, a semitransparent metal thin film, or the like is used. Specifically, a film (NESA, etc.) manufactured using a conductive glass containing indium oxide, zinc oxide, tin oxide, and indium, tin, oxide (ITO), indium zinc oxide, or the like thereof, , Gold, platinum, silver, copper and the like are used, and ITO, indium zinc oxide and tin oxide are preferable. As a manufacturing method, a vacuum vapor deposition method, sputtering method, an ion plating method, a plating method, etc. are mentioned. Moreover, organic transparent conductive films, such as polyaniline or its derivative (s), polythiophene or its derivative (s), can also be used as said anode.

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

In order to facilitate charge injection, a layer containing a phthalocyanine derivative, a conductive polymer, carbon, or the like, or a layer having an average film thickness of 2 nm or less including a metal oxide, a metal fluoride, an organic insulating material, or the like is provided on the anode. It may be.

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

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

As the method for producing the cathode, a vacuum deposition method, a sputtering method, a lamination method for thermocompression bonding a metal thin film, or the like is used. In addition, a layer containing a conductive polymer or a layer having an average film thickness of 2 nm or less including a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided between the cathode and the organic material layer. A protective layer may be attached. In order to use the polymer LED for long term stability, it is preferable to mount a protective layer and / or a protective cover to protect the device from the outside.

As the protective layer, a high molecular compound, a metal oxide, a metal fluoride, a metal boride, or the like can be used. As the protective cover, a glass plate, a plastic plate having a low water permeability treatment on the surface thereof, or the like can be used, and a method of bonding the cover to the element substrate with a heat effect resin or a photocurable resin and sealing is preferably used. By using a spacer to maintain space, it is easy to prevent the device from being damaged. When an inert gas such as nitrogen or argon is enclosed in the space, oxidation of the cathode can be prevented, and a desiccant such as barium oxide can be provided in the space to prevent the moisture adsorbed in the manufacturing process from damaging the device. Becomes easy. It is preferable to take any one or more of these measures.

The polymer LED of the present invention can be used for a planar light source, a segment display device, a dot matrix display device, and a liquid crystal display device (for example, a backlight of a liquid crystal display device).

In order to obtain planar light emission using the polymer LED of the present invention, it is preferable to arrange the planar anode and the cathode so as to overlap. In addition, in order to obtain pattern light emission, a method of providing a mask having a patterned window on the surface of the planar light emitting element, a method of forming an organic layer of the non-light emitting part as thick as possible and making it substantially non-emission, among the anode or the cathode There is a method of forming either or both electrodes in a pattern form. By forming a pattern by any of these methods and arranging several electrodes so that they can be turned ON / OFF independently, a segment type display element capable of displaying numbers, letters, simple symbols, and the like is obtained. In addition, in order to make a dot matrix element, it is preferable to arrange | position both an anode and a cathode in stripe form, and orthogonally cross. Partial color display and multi-color display can be performed by the method of separately applying a polymer fluorescent substance having a plurality of light emission colors or by using a color filter or a fluorescence conversion filter. The dot matrix element can also be passively driven and can be actively driven in combination with a TFT or the like. These display elements can be used as display devices such as computers, televisions, portable terminals, portable telephones, car navigation systems, and view finders of video cameras.

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

Hereinafter, although an Example is shown in order to demonstrate this invention further in detail, this invention is not limited to these.

(Number average molecular weight and weight average molecular weight)

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

(Fluorescence spectrum)

The fluorescence spectrum was measured by the following method. A thin film of polymer was prepared by spin coating a 0.8 wt% solution of the polymer onto quartz. This thin film was excited at a wavelength of 350 nm, and the fluorescence spectrum was measured using a fluorescence spectrophotometer (Furulog, manufactured by HORIBA Corporation). In order to obtain the relative fluorescence intensity in the thin film, the fluorescence spectrum obtained by wavenumber plotting the Raman line intensity of water as a standard was integrated into the spectrum measurement range, and the absorbance at the excitation wavelength measured using a spectrophotometer (Cary5E, manufactured by Verian). The divided value was obtained.

(HPLC measurement)

Measuring instrument: Agilent 1100LC

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

Liquid A: Acetonitrile, Liquid B: THF

Gradient

B amount:

0% (60 minutes) → 10% increment / minute → 100% (10 minutes),

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

Injection volume: 1 μL

Detection wavelength: 350 nm

Synthesis Example 1

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

In an inert atmosphere, 225 g of acetic acid was added to a 500 ml three-necked flask, and 24.3 g of 5-t-butyl-m-xylene was added. Subsequently, after adding 31.2 g of bromine, it reacted at 15-20 degreeC for 3 hours.

The reaction solution was added to 500 ml of water, and the precipitated precipitate was filtered out. Washed twice with 250 ml water to afford 34.2 g of a white solid.

<Synthesis of N, N'-diphenyl-N, N'-bis (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine>

In an inert atmosphere, 36 ml of dehydrated toluene degassed was put into a 100 ml three-necked flask, and 0.63 g of tri (t-butyl) phosphine was added. Next, 0.41 g of tris (dibenzylideneacetone) dipalladium, 9.6 g of 1-bromo-4-t-butyl-2,6-dimethylbenzene, 5.2 g of t-butoxy sodium, N, N'-diphenyl- After adding 4.7 g of 1,4-phenylenediamine, the mixture was reacted at 100 ° C for 3 hours.

The reaction solution was added to 300 ml of saturated brine, and extracted with 300 ml of chloroform warmed to about 50 deg. After distilling off the solvent, 100 ml of toluene was added, the mixture was heated and cooled until the solid was dissolved, and then the precipitate was filtered to give 9.9 g of a white solid.

<Synthesis of N, N'-bis (4-bromophenyl) -N, N'-bis (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine>

In an inert atmosphere, 350 ml of dehydrated N, N-dimethylformamide was placed in a 1000 ml three-necked flask, and N'-diphenyl-N, N'-bis (4-t-butyl-2,6-dimethylphenyl) -1 After dissolving 5.2 g of, 4-phenylenediamine, 3.5 g / N, N-dimethylformamide solution of N-bromosuccinimide was added dropwise under an ice bath to react overnight.

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

Synthesis Example 2

<Synthesis of N, N'-diphenyl-N, N'-bis (4-t-butyl-2,6-dimethylphenyl) -benzidine

In an inert atmosphere, 1660 ml of dehydrated toluene degassed was put into a 300 ml three-neck flask, and 275.0 g of N, N'-diphenylbenzidine and 449.0 g of 4-t-butyl-2,6-dimethylbromobenzene were added thereto. Subsequently, 7.48 g of tris (dibenzylideneacetone) dipalladium and 196.4 g of sodium t-butoxy were added, followed by 5.0 g of tri (t-butyl) phosphine. Then, it reacted at 105 degreeC for 7 hours.

2000 ml of toluene was added to the reaction mixture, and the mixture was filtered through Celite. The filtrate was washed three times with 1000 ml of water, and then concentrated to 700 ml. 1600 ml of a toluene / methanol (1: 1) solution was added thereto, and the precipitated crystal | crystallization was filtered and wash | cleaned with methanol. 479.4 g of a white solid were obtained.

<Synthesis of N, N'-bis (4-bromophenyl) -N, N'-bis (4-t-butyl-2,6-dimethylphenyl) -benzidine

472.8 g of the above-mentioned N, N'-diphenyl-N, N'-bis (4-t-butyl-2,6-dimethylphenyl) -benzidine was dissolved in 4730 g of chloroform under an inert atmosphere, followed by N under shading and an ice bath. -281.8 g of bromosuccinimide were added in 12 portions over 1 hour and allowed to react for 3 hours.

1439 mL of chloroform was added to the reaction solution, and the mixture was filtered. The chloroform solution of the filtrate was washed with 2159 mL of 5% sodium thiosulfate, and toluene was distilled off from the solvent to obtain white crystals. The obtained white crystals were recrystallized from toluene / ethanol to give 678.7 g of white crystals.

MS (APCI (+)): (M + H) ⁺ 815.2

Example 1 Synthesis of Compound B

(Synthesis of 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 dissolve completely. The inside of the system was substituted with argon, and 30 ml of toluene and 5.0 g (24 mmol) of 1,2,3,10b-tetrahydrofluoranthene were added and stirred to dissolve. Subsequently, 2.3 g (7.3 mmol) of tetrabutylammonium bromide and 9.4 g (48 mmol) of octyl bromide were added and reacted at 40 ° C. for 3 hours. The mixture was separated with toluene and water to extract an organic layer, and then dried over sodium sulfate. After distilling off the solvent, hexane was purified by a silica gel column having a developing solvent, to thereby obtain 6.45 g of pale yellow crystals.

(Synthesis of 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 an argon-substituted reaction vessel, and the mixture was stirred at room temperature to dissolve. Subsequently, 14 g (36 mmol) of benzyl trimethylammonium tribromide were added and zinc chloride was added with stirring until the benzyl trimethylammonium tribromide was completely dissolved. Benzyltrimethylammonium tribromide and zinc chloride were added as appropriate while tracking the reaction with HPLC. After completion of the reaction, the mixture was separated with chloroform and water, the organic layer was extracted, washed twice, and neutralized with an aqueous potassium carbonate solution. After drying over sodium sulfate, the solvent was distilled off and the residue was purified by a silica gel column 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.

<Example 2>

(Synthesis of Polymer Compound 1)

Compound B (0.1 g) and 2,2'-bipyridyl (0.089 g) were dissolved in 19 mL of dehydrated tetrahydrofuran, and then bis (1,5-cyclooctadiene) nickel (0) was added to the solution under nitrogen atmosphere. ) {Ni (COD) ₂ } (0.156 g) was added, and it heated up to 60 degreeC, and made it react for 3 hours. The reaction solution was cooled to room temperature, added dropwise into 25% ammonia water 1 mL / methanol 19 mL / ion exchange water 19 mL mixed solution, stirred for 1 hour, and the precipitated 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 number average molecular weight of polystyrene conversion 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 (0.557 g), N, N'-bis (4-bromophenyl) -N, N'-bis (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine ( 0.096 g) and 2,2'-bipyridyl (0.548 g) were dissolved in 140 mL of dehydrated tetrahydrofuran, followed by bubbling with argon to nitrogen-substitute the system. After the temperature was raised to 60 ° C, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.965 g) was added to the solution under nitrogen atmosphere, followed by stirring for 3 hours. The reaction solution was cooled to room temperature, added dropwise into a 25% mixed solution of 5 ml of ammonia / 140 ml of methanol / 140 ml of ion-exchanged water and stirred for 1 hour, and then the precipitated precipitate was filtered out and dried under reduced pressure, and dissolved in 40 ml of toluene. I was. After dissolution, 1.6 g of radiolite was added and stirred for 30 minutes, and the insoluble matter was filtered off. The filtrate obtained was purified through an alumina column. Subsequently, 80 ml of 5.2% hydrochloric acid was added, followed by stirring for 3 hours, and then the aqueous layer was removed. Subsequently, 80 ml of 4% ammonia water was added, and after stirring for 2 hours, the aqueous layer was removed. Further, after adding about 80 ml of ion-exchanged water to the organic layer and stirring for 1 hour, the aqueous layer was removed. Thereafter, the organic layer was added to 160 ml of methanol, stirred for 1 hour, and the precipitated 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 number average molecular weight and weight average molecular weight of polystyrene conversion were Mn = 1.6x10 <^4> , Mw = 8.7 * 10 <^4> , respectively.

<Example 4>

<Synthesis of Polymer Compound 3>

Compound B (0.433 g), N, N'-bis (4-bromophenyl) -N, N'-bis (4-t-butyl-2,6-dimethylphenyl) -benzidine (0.318 g), 2, 2'-bipyridyl (0.548 g) was dissolved in 140 mL of dehydrated tetrahydrofuran, followed by bubbling with argon to nitrogen-substitute the system. After heating up to 60 degreeC, bis (1, 5- cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.965g) was added to the said solution, and it stirred for 3 hours in nitrogen atmosphere. The reaction solution was cooled to room temperature, added dropwise into a 25% mixed solution of 5 ml of ammonia / 140 ml of methanol / 140 ml of ion-exchanged water and stirred for 1 hour, and then the precipitated precipitate was filtered out and dried under reduced pressure, and dissolved in 40 ml of toluene. I was. After dissolution, 1.6 g of radiolite was added and stirred for 30 minutes, and the insoluble matter was filtered off. The filtrate obtained was purified through an alumina column. Subsequently, 80 ml of 5.2% hydrochloric acid was added, followed by stirring for 3 hours, and then the aqueous layer was removed. Subsequently, 80 ml of 4% ammonia water was added, and after stirring for 2 hours, the aqueous layer was removed. Further, after adding about 80 ml of ion-exchanged water to the organic layer and stirring for 1 hour, the aqueous layer was removed. Thereafter, the organic layer was added to 160 ml of methanol, stirred for 1 hour, and the precipitated 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 number average molecular weight and weight average molecular weight of polystyrene conversion were Mn = 1.0 * 10 <^4> , Mw = 6.1 * 10 <^4> , respectively.

Example 5

<Synthesis of Polymer Compound 4>

Compound B (0.588 g), N, N'-bis (4-bromophenyl) -N, N'-bis (4-t-butyl-2,6-dimethylphenyl) -benzidine (0.053 g), 2, 2'-bipyridyl (0.548 g) was dissolved in 140 mL of dehydrated tetrahydrofuran, followed by bubbling with argon to nitrogen-substitute the system. After heating up to 60 degreeC, bis (1, 5- cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.965g) was added to the said solution, and it stirred for 3 hours in nitrogen atmosphere. The reaction solution was cooled to room temperature, added dropwise into a 25% mixed solution of 5 ml of ammonia / 140 ml of methanol / 140 ml of ion-exchanged water and stirred for 1 hour, and then the precipitated precipitate was filtered out and dried under reduced pressure, and then to 40 ml of toluene. Dissolved. After dissolution, 1.6 g of radiolite was added and stirred for 30 minutes, and the insoluble matter was filtered off. The filtrate obtained was purified through an alumina column. Subsequently, 80 ml of 5.2% hydrochloric acid was added, followed by stirring for 3 hours, and then the aqueous layer was removed. Subsequently, 80 ml of 4% ammonia water was added, and after stirring for 2 hours, the aqueous layer was removed. Further, after adding about 80 ml of ion-exchanged water to the organic layer and stirring for 1 hour, the aqueous layer was removed. Thereafter, the organic layer was added to 160 ml of methanol, stirred for 1 hour, and the precipitated 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 number average molecular weight and weight average molecular weight of polystyrene conversion were Mn = 2.5 * 10 <^4> , Mw = 1.2 * 10 <^5> , respectively.

Example 6 Fabrication and Performance of EL Device

(Adjustment of solution)

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

(Manufacture of EL element)

A suspension of poly (3,4) ethylenedioxythiophene / polystyrenesulfonic acid (Baytron P AI4083, manufactured by Bayer) was filtered through a 0.2 μm membrane filter on a glass substrate having an ITO film attached to a thickness of 150 nm by sputtering. A thin film was formed to a thickness of 70 nm by spin coating using a liquid and dried at 200 ° C. for 10 minutes on a hot plate. Subsequently, the film was formed at a rotational speed of 3400 rpm by spin coating using the toluene solution obtained above. The film thickness after film formation was about 95 nm. After drying this at 80 ° C. under reduced pressure for 1 hour, lithium fluoride was deposited at about 4 nm, and calcium was deposited at about 5 nm, followed by aluminum at about 80 nm, to prepare an EL device. In addition, metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.

(EL device performance)

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

Example 7 Fabrication and Performance of EL Device

(Adjustment of solution)

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

(Manufacture of EL element)

EL elements were manufactured in exactly the same manner as in Example 6, except that the toluene solution obtained above was used. In addition, the rotation speed in the spin coating of the polymer solution was 3300 rpm, and the film thickness after film formation of the polymer film was 95 nm.

(EL device performance)

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

Example 8 Fabrication and Performance of EL Device

(Adjustment of solution)

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

(Manufacture of EL element)

EL elements were manufactured in exactly the same manner as in Example 6, except that the toluene solution obtained above was used. In addition, the rotation speed in the spin coating of the polymer solution was 2500 rpm, and the film thickness after film formation of the polymer film was 90 nm.

(EL device performance)

By applying a voltage to the obtained device, EL light emission showing a peak at 425 nm was obtained from this device. When the EL emission color was expressed by the CIE color coordinate value, x was 0.55 and y was 0.074, which showed very good blue color. The intensity of EL light emission was almost proportional to the current density. In addition, the device showed light emission start from 5.8V. The luminous efficiency monotonously increased in the measured voltage range (0 V to 12 V), but the value at 12 V was relatively high at 0.57 cd / m ² .

Example 9 Synthesis of Compound D

(Synthesis of Compound C)

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 dissolve completely. The inside of the system was substituted with argon, and 30 ml of toluene and 5.0 g (24 mmol) of 1,2,3,10b-tetrahydrofluoranthene were added and stirred to dissolve. Subsequently, 2.3 g (7.3 mmol) of tetrabutylammonium bromide and 9.4 g (48 mmol) of 2-ethylhexyl bromide were added and reacted at 40 ° C. for 3 hours. The mixture was separated with toluene and water to extract an organic layer, and then dried over sodium sulfate. After distilling off the solvent, 6.88 g of a yellow oil was obtained by purification with a silica gel column using hexane as a developing solvent.

(Synthesis of 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 placed in an argon-substituted reaction vessel, followed by stirring at room temperature. Subsequently, 18 g (47 mmol) of benzyltrimethylammonium tribromide was dissolved in 150 ml of dichloromethane and added dropwise thereto. After completion of the dropwise addition, the mixture was allowed to react at room temperature for 2 hours, followed by 30 minutes each at 40 ° C and 50 ° C, and then the reaction was stopped by adding chloroform and 5% aqueous sodium hydrogen sulfite solution. The organic layer was separated by extraction with chloroform and water, washed twice, and neutralized with an aqueous potassium carbonate solution. After drying over sodium sulfate, the solvent was distilled off and the residue was purified three times with a silica gel column using hexane as a developing solvent, thereby obtaining 1.73 g of Compound D as a yellow oil (white crystallization when left at room temperature).

Example 10 Synthesis of Polymer Compound 5

Compound D (0.476 g) and 2,2'-bipyridyl (0.422 g) were dissolved in 72 mL of dehydrated tetrahydrofuran under a nitrogen atmosphere, followed by stirring to dissolve. Bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.743 g) was added to this solution, followed by stirring at 60 ° C for 3 hours. The reaction solution was cooled to room temperature, added dropwise into 25% aqueous ammonia solution 4 ml / methanol 72 ml / ion exchange water 72 ml and stirred for 1 hour, and then the precipitated precipitate was filtered out and dried under reduced pressure and dissolved in 20 ml of toluene. I was. After dissolution, 1.6 g of radiolite was added and stirred for 30 minutes, and the insoluble matter was filtered off. The filtrate obtained was purified through an alumina column. Subsequently, 40 ml of 5.2% hydrochloric acid was added and the mixture was stirred for 3 hours, after which the aqueous layer was removed. Subsequently, 40 ml of 4% aqueous ammonia was added and stirred for 2 hours, and then the aqueous layer was removed. Further, about 40 ml of ion-exchanged water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. Thereafter, the organic layer was added to 80 ml of methanol, stirred for 1 hour, and the precipitated 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 number average molecular weight and weight average molecular weight of polystyrene conversion were Mn = 1.1 * 10 <^5> , Mw = 3.2 * 10 <^5> , respectively.

Comparative Example 1

<Synthesis of Polymer Compound 6>

0.22 g (0.40 mmol) of 2,7-dibromo-9,9-dioctylfluorene and N, N'-bis (4-bromophenyl) -N, N'-bis (4-t-butyl- 0.20 g (0.27 mmol) of 2,6-dimethylphenyl) -1,4-phenylenediamine and 0.24 g (1.5 mmol) of 2,2'-bipyridyl were placed in a reaction vessel, and the reaction system was replaced with nitrogen gas. It was. To this was added 20 ml of tetrahydrofuran (dehydrated solvent) degassed by bubbling with argon gas in advance. Next, 0.42 g (1.5 mmol) of bis (1,5-cyclooctadiene) nickel (0) was added to the mixed solution, and the mixture was reacted at 60 ° C for 3 hours. In addition, reaction was performed in nitrogen gas atmosphere. After the reaction, the solution was cooled, then introduced into a mixed solution of 10% 25ml ammonia water / 120ml methanol / 50ml ion-exchanged water and stirred for about 1 hour. The resulting precipitate was then recovered by filtration. This precipitate was washed with ethanol and dried under reduced pressure for 2 hours. Subsequently, the precipitate was dissolved in 50 ml of toluene, 50 ml of 1 N hydrochloric acid was added and stirred for 1 hour, the aqueous layer was removed, 50 ml of 4% aqueous ammonia was added to the organic layer, and the aqueous layer was removed after stirring for 1 hour. The organic layer was added dropwise to 120 ml of methanol, and stirred for 1 hour. The precipitated precipitate was filtered off, dried under reduced pressure for 2 hours, and dissolved in 40 ml of toluene. Thereafter, purification was performed through an alumina column (alumina amount 20 g), and the recovered toluene solution was added dropwise to 120 ml of methanol, stirred for 1 hour, and the precipitated 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 reduced number average molecular weight of the high molecular compound 6 was 2.0 × 10 ⁴ , and the polystyrene reduced weight average molecular weight was 1.1 × 10 ⁵ .

Comparative Example 2 Fabrication and Performance of EL Device

(Adjustment of solution)

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

(Manufacture of EL element)

On a glass substrate with an ITO film attached to a thickness of 150 nm by the sputtering method, a film was formed into a thickness of 50 nm by spin coating using a poly (ethylenedioxythiophene) / polystyrenesulfonic acid solution (Baytron P), Dry at 200 ° C. for 10 minutes on a hot plate. Subsequently, the film was formed at a rotational speed of 2500 rpm by spin coating using the chloroform solution prepared above. The film thickness was about 100 nm. After drying for 1 hour at 80 DEG C under reduced pressure, an EL device was fabricated by depositing about 4 nm of LiF as a cathode buffer layer, about 5 nm of calcium as a cathode, and then about 80 nm of aluminum. In addition, after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.

(EL device performance)

EL light emission with a peak at 448 nm was obtained by applying a voltage to the obtained device. EL emission color was changed to C.I.E. Color coordinate values showed x = 0.155 and y = 0.133. The device exhibited a maximum luminous efficiency at about 10 V and its value was 0.14 cd / A.

When used as a material of an electronic device, the high molecular compound of this invention provides the electronic device excellent in the device performance.

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

Moreover, the said high molecular compound has the outstanding charge transport ability, and can be used suitably as a material for polymer LED and a charge transport material. The polymer LED using the polymer light emitter is a high performance polymer LED capable of driving at low voltage and high efficiency. Therefore, the said polymer LED can be used suitably for apparatuses, such as a curved or flat light source, a segment type display element, and a dot matrix flat panel display for backlight or illumination of a liquid crystal display.

The polymer compound of the present invention can also be used as a conductive thin film material such as a dye for a laser, a material for an organic solar cell, an organic semiconductor for an organic transistor, a conductive thin film, or an organic semiconductor thin film.

It can also be used as a luminescent thin film material that emits fluorescence or phosphorescence.

Claims (34)

A polymer compound, characterized in that it comprises at least one of the residues of the compound represented by the formula (I). <Formula I>

In the formula, the A ring, the B ring and the C ring each independently represent an aromatic ring or a non-aromatic ring which may have a substituent, and 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, z represents 0 or 1, and A and B rings other than Z ₅ constituting each ring each other The atoms of may be shared, and at least one of the A ring, the B ring and the C ring is a non-aromatic ring. A high molecular compound comprising a repeating unit represented by the following formula (Ia), (Ib) or (Ic). <Formula Ia>

<Formula Ib>

<Formula Ic>

In the formula, the A ring, the B ring and the C ring each independently represent an aromatic ring or a non-aromatic ring which may have a substituent, and 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, z represents 0 or 1, and the A and B rings may share atoms of a ring other than Z ₅ ; In addition, the substituents of each ring may be bonded to each other to further form a ring, and at least one of the rings having no bonding hand among the A ring, the B ring, and the C ring is a non-aromatic ring. The polymer compound according to claim 1 or 2, wherein all of the atoms constituting the rings of the A ring, the B ring, and the C ring are carbon atoms. The polymer compound according to claim 2 or 3, wherein the repeating unit represented by the formula (Ia) is a repeating unit represented by the following formula (IIa). <Formula IIa>

In the formula, R ₁ And R ₂ each independently represent a substituent, the D ring represents a non-aromatic ring which may have a substituent, a represents an integer of 0 to 2, b represents an integer of 0 to 3, and R ₁ And when a plurality of R _{2 's} are each present, they may be the same or different, R ₁ and R ₂ may be bonded to each other to form a ring, and R ₁ And / or R ₂ may be bonded to a D ring to form a ring, and Q and z represent the same meaning as described above. The polymer compound according to claim 2 or 3, wherein the repeating unit represented by the general formula (IIa) is a repeating unit represented by the following general formula (IIIa). <Formula IIIa>

In formula, R <_1> , R <_2> , D ring, Q, z, a, and b show the same meaning as the above. The polymer compound according to claim 5, wherein the repeating unit represented by the formula (IIIa) is a repeating unit represented by the following formula (IVa), (IVb), (IVc) or (IVd). <Formula IVa>

<Formula IVb>

<Formula IVc>

<Formula IVd>

Wherein R _1a , R _1b , R _2a to R _2c , and R _3a to R _3g each independently represent a hydrogen atom or a substituent, and in Formulas IVa to IVc, R _2c and R _3g are bonded to each other to form a ring; In the general formula (IVd), R _2c and R _3e may combine with each other to form a ring. The polymer compound according to any one of claims 1 to 6, further comprising a repeating unit represented by the following formula (V), (VI), (VII) or (VIII). <Formula V>

<Formula VI>

<Formula VII>

<Formula VIII>

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 represent a -CR. ₉ = CR _10- , -C≡C-, -N (R ₁₁ )-or-(SiR ₁₂ R ₁₃ ) _m- , and R ₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group, an aryl group, 1 Is a 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 arylalkyl group or a substituted amino group, and ff is 1 Or 2, m represents an integer of 1 to 12, and in the case where a plurality of R ₉ , R ₁₀ , R ₁₁ , R _12, and R ₁₃ are each present, they may be the same or different. The polymer compound according to any one of claims 1 to 6, further comprising a repeating unit represented by the following formula (IX, X, XI, XII, XIII or XIV). <Formula IX>

In the formula, R ₁₄ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, or a substituted amino group. , Silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group or nitro group, n is 0 to 4 In the case of plural R ₁₄ 's, these may be the same or different. <Formula X>

In formula, R <_15> and R <_16> is respectively independently alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalki It represents a silyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group. , o and p each independently represent an integer of 0 to 3, and when a plurality of R ₁₅ and R ₁₆ are each present, they may be the same or different. <Formula XI>

In the formula, each of R ₁₇ and R ₂₀ is independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, or an arylalki It represents a silyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group. , q and r each independently represent an integer of 0 to 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, and R ₁₇ And when there are a plurality of R _{20 's} , they may be the same or different. <Formula XII>

In the formula, R ₂₁ represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group. , Silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group or nitro group, s represents 0 to 2 Represents an integer of, 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, and X ₄ represents O, S, SO, SO ₂ , Se, or Te, and when there are a plurality of R _{21 s} , they may be the same or different. <Formula XIII>

In the formula, each of R ₂₂ and R ₂₃ is independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, or an arylalki It represents a silyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group. , t and u each independently represent an integer of 0 to 4, X ₅ represents O, S, SO ₂ , Se, Te, NR ₂₄ or SiR ₂₅ R ₂₆ , and X ₆ and X ₇ are each independently 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 arylalkyl group or a monovalent heterocyclic group, and a plurality of R ₂₅ , R ₂₆ and R ₂₇ are present. If so, they may be the same or different. <Formula XIV>

In the formula, R ₂₈ and R ₃₃ each independently represent an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, or an arylalki It represents a silyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group. , v and w each independently represent an integer of 0 to 4, and R ₂₉ , R ₃₀ , R ₃₁ and R ₃₂ 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 cya A no group, Ar ₅ represents an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure, and when a plurality of R ₂₈ and R ₃₃ are present, they may be the same or different. The polymer compound according to any one of claims 1 to 6, further comprising a repeating unit represented by the following general formula (XV). <Formula XV>

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 monovalent heterocyclic group, Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ and Ar ₁₀ may have a substituent, and x and y each independently represent 0 or 1, and 0 ≦ x + y ≦ 1. A method for producing the polymer compound according to any one of claims 1 to 9, wherein the polymer is polymerized using at least a compound represented by the following formula (XVIa), (XVIb) or (XVIc) as a raw material. <Formula XVIa>

<Formula XVIb>

<Formula XVIc>

In the formula, A ring, B ring, C ring, Z ₁ to Z ₅ represent the same meaning 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 production method according to claim 10, wherein the compound represented by the general formula (XVIa) is a compound represented by the following general formula (XVIIa). <Formula XVIIa>

In formula, R <_1> , R <_2> , a, b, D ring, Q, z, Y <_1> and Y <_2> represent the same meaning as the above. The method according to claim 11, wherein the compound represented by the formula (XVIIa) is a compound represented by the following formula (XVIIIa, XVIIIb, XVIIIc or XVIIId). <Formula XVIIIa>

<Formula XVIIIb>

<Formula XVIIIc>

<Formula XVIIId>

In the formula, R _1a , R _1b , R _2a to R _2c , R _3a to R _3g , Y ₁ and Y ₂ represent the same meaning as described above. The production method according to claim 10, wherein the compound represented by the formula (XVIb) is a compound represented by the following formula (XVIIb). <Formula XVIIb>

In the formula, ring B, ring C, Z ₂ , Z ₃ , Z ₄ , Y ₃ and Y ₄ represent the same meaning as described above, and Z ₆ , Z ₇ and Z ₈ are each independently 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 described above, R ₄ represents a substituent, and e represents an integer of 0 to 2, When there are a plurality of R ₄ , they may be the same or different, and R ₄ may be bonded to each other to form a ring. The production method according to claim 10, wherein the compound represented by the formula (XVIc) is a compound represented by the following formula (XVIIc). <Formula XVIIc>

In the formula, A ring, B ring, Z ₁ , Z ₄ , Z ₅ , Y ₅ and Y ₆ have the same meaning as above, and Z ₁₀ , Z ₁₁ , Z ₁₂ and Z ₁₃ are each independently 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 to 2, When there are a plurality of R _{5 s} , they may be the same or different, and R ₅ may be bonded to each other to form a ring. The compound according to any one of claims 10 to 14, wherein in addition to the compound represented by the formula (XVIa), (XVIb) or (XVIc), the compound represented by any one of the formulas (XIX) to (XXII) as a raw material is polymerized. Manufacturing method. <Formula XIX>

<Formula XX>

<Formula XXI>

<Formula XXII>

In formula, Ar <_1> , Ar <_2> , Ar <_3> , Ar <_4> , ff, X <_1> , X <_2> and X <_3> represent the same meaning as the above, 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. The compound according to any one of claims 10 to 15, wherein when the compound represented by the formula (XVIa), (XVIb) or (XVIc) is polymerized with one or more selected from compounds represented by the formulas (XIX to XXII), Y_One, Y₂, Y₃, Y₄, Y₅, Y₆, Y₇, Y₈, Y₉, Y₁₀, Y₁₁, Y₁₂, Y₁₃ And Y₁₄Are each independently a halogen atom, an alkylsulfonate group, an arylsulfonate group or an arylalkylsulfonate group, and the condensation polymerization is carried out in the presence of a nickel valent complex. The compound according to any one of claims 10 to 15, wherein when polymerized with one or more selected from formulas XVIa, XVIb or XVIc, alone or with one or more selected from formulas XIX to XXII, 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 is each independently a halogen atom, an alkylsulfonate group, an arylsulfonate group, an arylalkylsulfonate group, -B (OH) ₂ or a boric acid ester group, and a halogen atom, an alkylsulfonate group, an arylsulfonate group And the ratio of the total number of moles of the arylalkylsulfonate group to the total number of moles of the -B (OH) ₂ and the boric acid ester groups is substantially 1, and the condensation polymerization is carried out using a nickel or a palladium catalyst. A compound represented by the formula (XVIIa). A compound represented by the formula XVIIIa, XVIIIb, XVIIIc or XVIIId. A compound represented by the above formula (XVIb) or XVIc. A compound represented by the formula XVIIb or XVIIc. A composition comprising at least one material selected from a hole transporting material, an electron transporting material and a light emitting material and the polymer compound according to any one of claims 1 to 9. An ink composition comprising the polymer compound according to any one of claims 1 to 9 and a solvent. The ink composition according to claim 23, wherein the viscosity is 1 to 20 mPa · s at 25 ° C. The light emitting thin film containing the high molecular compound in any one of Claims 1-9. The conductive thin film containing the high molecular compound in any one of Claims 1-9. An organic semiconductor thin film containing the polymer compound according to any one of claims 1 to 9. A polymer light emitting device comprising an organic layer between electrodes comprising an anode and a cathode, wherein the organic layer comprises the polymer compound according to any one of claims 1 to 9. The polymer light emitting device according to claim 28, wherein the organic layer is a light emitting layer. 30. The polymer light emitting device of claim 29, wherein the light emitting layer further comprises a hole transport material, an electron transport material, or a light emitting material. A planar light source comprising the polymer light emitting device according to any one of claims 28 to 30. A segment display device comprising the polymer light emitting device according to any one of claims 28 to 30. A dot matrix display device comprising the polymer light emitting device according to any one of claims 28 to 30. A liquid crystal display device comprising the polymer light emitting device according to any one of claims 28 to 30.