DE112006001016T5 - Polymer compound and polymeric light-emitting device using them - Google Patents

Abstract

Formel 1 (wobei Ring A, Ring B und Ring C jeweils unabhängig einen aromatischen Ring oder nicht aromatischen Ring darstellen, die gegebenenfalls einen Substituenten aufweisen, Z₁, Z₂, Z₃, Z₄ und Z₅ jeweils unabhängig C-(Q)_z oder ein Stickstoffatom darstellen, Q einen Substituenten oder ein Wasserstoffatom darstellt, z 0 oder 1 darstellt, der Ring A und der Ring B sich neben Z₅ ein Atom teilen können, das jeden Ring bildet, und ein oder mehrere oder zwei oder weniger der Ringe A, B und C nicht aromatische Ringe sind).Polymer compound comprising at least one of the radicals of compounds of the following formula (1):

Formula 1 (wherein Ring A, Ring B and Ring C each independently represent an aromatic ring or non-aromatic ring optionally having a substituent, Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z _{5 are} each independently C- (Q) _{z represents} a nitrogen atom, Q represents a substituent or a hydrogen atom, z represents 0 or 1, the ring A and the ring B may share, besides Z _5, one atom forming each ring, and one or more or two or less of Rings A, B and C are not aromatic rings).

Description

Technical field

The The present invention relates to a polymer compound and a polymeric one light emitting device using them.

State of the art

light emitting Materials and high molecular weight charge transporting materials in a solvent soluble and for forming an organic layer in a light-emitting Device capable by an application method and are widely studied. Polyfluorenes are known as polymer compounds known as light-emitting Materials or charge-transporting materials in electron devices, such as polymeric light-emitting devices (polymer LED) and Like. Can be used (International publication No. 99/54385).

The Performance of the device of the devices using the polymer compound described above as a light-emitting However, material or charge transporting material and the like is not necessarily already on a practically satisfactory Level.

To the Example show polymer LEDs using the above described Polymer compound is not a practically satisfactory level in their performance in devices, such as light emission efficiency, Hue of the emitted light and the like.

Disclosure of the invention

The The object of the present invention is to provide a polymer compound the capable is to give an electron device, the excellent performance the device, when used as the material of the electron device is used.

Formel 1 (wobei Ring A, Ring B und Ring C jeweils unabhängig einen aromatischen Ring oder nicht aromatischen Ring darstellen, die gegebenenfalls einen Substituenten aufweisen, Z₁, Z₂, Z₃, Z₄ und Z₅ jeweils unabhängig C-(Q)_z oder ein Stickstoffatom darstellen, Q einen Substituenten oder ein Wasserstoffatom darstellt, z 0 oder 1 darstellt, sich der Ring A und der Ring B ein Atom neben Z₅ teilen können, das jeden Ring bildet, und ein oder mehrere oder zwei oder weniger der Ringe A, B und C nicht aromatische Ringe sind).That is, the present invention provides a polymer compound comprising at least one of the groups of the compounds of the following formula (1):

Formula 1 (wherein Ring A, Ring B and Ring C each independently represent an aromatic ring or non-aromatic ring optionally having a substituent, Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z _{5 are} each independently C- (Q) _{z represents} a nitrogen atom, Q represents a substituent or a hydrogen atom, z represents 0 or 1, the ring A and the ring B may share an atom adjacent to Z ₅ forming each ring, and one or more or two or less of Rings A, B and C are not aromatic rings).

Best mode of implementation of the invention

In of the formula (1), the ring A, ring B and ring C each independently aromatic ring or non-aromatic ring, optionally have a substituent.

When aromatic ring are listed those, the (4n + 2) π electrons contained in the ring structure. In particular, aromatic hydrocarbon rings, such as a benzene ring, cyclodecane pentaene ring and the like; and aromatic Hetero rings, such as a furan ring, thiophene ring, pyrrole ring, pyridine ring, Pyrimidine ring, pyridazine ring and the like. Listed.

Of the not aromatic ring closes alicyclic rings, such as a cyclopentane ring, cyclopentene ring, cyclopentadiene ring, Cyclohexane ring, cyclohexene ring, cyclohexadiene ring, cycloheptane ring, Cycloheptene ring, cycloheptadiene ring, cycloheptatriene ring, cyclooctane ring, Cyclooctene ring, cyclooctadiene ring, cyclooctatriene ring, cyclooctatetraene ring, Cyclononane ring, cyclonone ring, cyclononadiene ring, cyclononatriene ring, Cyclodecane ring, cyclodecene ring, cyclodecane ring, cyclodecantriene ring, Cyclodecane tetraene ring, cyclododecane pentaene ring, cycloundecane ring, Cycloundecene ring, cycloundecanedione ring, cycloundecanetrene ring, cycloundecanetetraine ring, Cycloundeanpentaene ring, cycloundecane hexaene ring and the like; and not aromatic hetero rings, such as a pyran ring, thiopyran ring and Like., A.

If the aromatic ring or non-aromatic ring has a substituent has closed the substituent is an alkyl radical, alkoxy radical, alkylthio radical, aryl radical, Aryloxy, arylthio, arylalkyl, arylalkoxy, arylalkylthio, Arylalkenyl radical, arylalkynyl radical, a substituted amino group, substituted silyl group, a fluorine atom, an acyl group, acyloxy group, Amide group, acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group and a nitro group a, and more preferred are an alkyl radical, alkoxy radical, aryl radical, Aryloxy, arylalkyl, arylalkoxy and arylalkylthio.

Here The alkyl radical may be any of linear, branched or cyclic and has a number of carbon atoms of usually about 1 to 20, preferably 3 to 20, and as specific examples thereof a methyl group, ethyl group, propyl group, i-propyl group, 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 preferred are a pentyl group, isoamyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group and 3,7-dimethyloctyl group.

Of the Alkoxy may be any linear, branched or cyclic and has a number of carbon atoms of usually about 1 to 20, preferably 3 to 20, and as specific examples thereof will be one 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 and the like. Listed, and preferred are a pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group and 3,7-dimethyloctyloxy group.

Of the Alkylthio may be any linear, branched or cyclic and has a number of carbon atoms of usually about 1 to 20, preferably 3 to 20, and as specific examples thereof will be one Methylthio group, ethylthio group, propylthio group, i-propylthio group, Butylthio group, i-butylthio group, t-butylthio group, pentylthio group, Hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, Laurylthio group, trifluoromethylthio group and the like, and preferred are a pentylthio group, hexylthio group, octylthio group, 2-ethylhexylthio group, decylthio group and 3,7-dimethyloctylthio group.

The aryl group is an atomic group obtained by cleaving a hydrogen atom from an aromatic hydrocarbon, and also includes those having a condensed ring and those formed by bonding two or more independent benzene rings or condensed rings directly or through a vinylene group and the like can be obtained. The aryl group has a number of carbon atoms of usually about 6 to 60, preferably 7 to 48, and as specific examples thereof, a phenyl group, C ₁ -C ₁₂ alkoxyphenyl groups (C ₁ to C _{12 represents} a number of carbon atoms of 1 to 12. Also applicable in the later descriptions.), C ₁ -C ₁₂ alkylphenyl groups, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, pentafluorophenyl group and the like, and preferred C ₁ -C ₁₂ -alkoxyphenyl radicals and C ₁ -C ₁₂ -alkylphenyl radicals. Specifically exemplified as C ₁ -C ₁₂ alkoxy are methoxy, ethoxy, propoxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3 , 7-dimethyloctyloxy, lauryloxy and the like.

Particularly exemplified as the C ₁ -C ₁₂ alkylphenyl group are a methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, i-propylphenyl group, butylphenyl group, i-butylphenyl group, t-butylphenyl group, pentylphenyl group, isoamyl phenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group and the like.

The aryloxy group has a number of carbon atoms of usually about 6 to 60, preferably 7 to 48, and specific examples thereof include a phenoxy group, C ₁ -C ₁₂ alkoxyphenoxy radicals, C ₁ -C ₁₂ alkylphenoxy radicals, a 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group and the like, and preferred are C ₁ -C ₁₂ alkoxyphenoxy and C ₁ -C ₁₂ alkylphenoxy.

Specifically exemplified as C ₁ -C ₁₂ alkoxy are methoxy, ethoxy, propoxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3 , 7-dimethyloctyloxy, lauryloxy and the like.

Specifically exemplified as C ₁ -C ₁₂ alkylphenoxy group are a methylphenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-trimethylphenoxy group, methylethylphenoxy group, i-propylphenoxy group, butylphenoxy group, i-butylphenoxy group, t-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, Heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group, dodecylphenoxy group and the like.

The arylthio group has a number of carbon atoms of usually about 3 to 60 carbon atoms, and specific examples thereof include a phenylthio group, C ₁ -C ₁₂ alkoxyphenylthio, C ₁ -C ₁₂ alkylphenylthio, 1-naphthylthio, 2-naphthylthio, pentafluorophenylthio and the like, and preferred are C ₁ -C ₁₂ alkoxyphenylthio radicals and C ₁ -C ₁₇ alkylphenylthio radicals.

The arylalkyl radical has a number of carbon atoms of usually about 7 to 60, preferably 7 to 48, and specific examples thereof include phenyl-C ₁ -C ₁₂ -alkyl radicals, C ₁ -C ₁₂ -alkoxyphenyl-C ₁ -C ₁₂ - alkyl radicals, C ₁ -C ₁₂ alkylphenyl C ₁ -C ₁₂ alkyl radicals, 1-naphthyl C ₁ -C ₁₂ alkyl radicals, 2-naphthyl C ₁ -C ₁₂ alkyl radicals and the like, and C is preferred C ₁ -C ₁₂ -alkoxyphenyl-C ₁ -C ₁₂ -alkyl radicals and C ₁ -C ₁₂ -alkylphenyl-C ₁ -C ₁₂ -alkyl radicals.

The arylalkoxy group has a number of carbon atoms of usually about 7 to 60, preferably 7 to 48, and specific examples thereof include phenyl-C ₁ -C ₁₂ alkoxy groups such as a phenylmethoxy group, phenylethoxy group, phenylbutoxy group, phenylpentyloxy group, phenylhexyloxy group, phenylheptyloxy group, Phenyloctyloxy group and the like, C ₁ -C ₁₂ -alkoxyphenyl-C ₁ -C ₁₂ -alkoxy radicals, C ₁ -C ₁₂ -alkylphenyl-C ₁ -C ₁₂ -alkoxy radicals, 1-naphthyl-C ₁ -C ₁₂ -alkoxy radicals, 2-Naphthyl-C ₁ -C ₁₂ alkoxy radicals and the like, and preferred are C ₁ -C ₁₂ alkoxyphenyl C ₁ -C ₁₂ alkoxy radicals and C ₁ -C ₁₂ alkylphenyl C ₁ -C ₁₂ alkoxy radicals ,

The arylalkylthio radical has a number of carbon atoms of usually about 7 to 60, preferably 7 to 48, and specific examples thereof include phenyl-C ₁ -C ₁₂ -alkylthio radicals, C ₁ -C ₁₂ -alkoxyphenyl-C ₁ -C ₁₂ - alkylthio radicals, C ₁ -C ₁₂ alkylphenyl C ₁ -C ₁₂ alkylthio radicals, 1-naphthyl C ₁ -C ₁₂ alkylthio radicals, 2-naphthyl C ₁ -C ₁₂ alkylthio radicals and the like, and preferably C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkylthio and C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkylthio groups.

The arylalkene radical has a number of carbon atoms of usually about 8 to 60, and specific examples thereof include phenyl-C ₂ -C ₁₂ -alkenyl radicals, C ₁ -C ₁₂ -alkoxyphenyl-C ₂ -C ₁₂ -alkenyl radicals, C ₁ -C ₁₂ -alkylphenyl-C ₂ -C ₁₂ -alkenyl radicals, 1-naphthyl-C ₂ -C ₁₂ -alkenyl radicals, 2-naphthyl-C ₂ -C ₁₂ -alkenyl radicals and the like, and preferred are C ₁ -C ₁₂ -alkoxyphenyl -C ₂ -C ₁₂ -alkenyl and C ₂ -C ₁₂ -alkylphenyl-C ₁ -C ₁₂ -akenylreste.

The arylalkynyl radical has a number of carbon atoms of usually about 8 to 60 carbon atoms, and specific examples thereof include phenyl-C ₂ -C ₁₂ -alkynyl radicals, C ₁ -C ₁₂ -alkoxyphenyl-C ₂ -C ₁₂ -alkynyl radicals, C ₁ - C ₁₂ alkylphenyl C ₂ -C ₁₂ alkynyl radicals, 1-naphthyl C ₂ -C ₁₂ alkynyl radicals, 2-naphthyl C ₂ -C ₁₂ alkynyl radicals and the like, and preferably C ₁ -C ₁₂ - Alkoxyphenyl-C ₂ -C ₁₂ -alkynyl radicals and C ₁ -C ₁₂ -alkylphenyl-C ₂ -C ₁₂ -alkynyl radicals.

The substituted amino group includes amino groups, which with one or two radicals are selected, selected from alkyl radicals, aryl radicals, Arylalkyl radicals or monovalent heterocyclic radicals, and the Alkyl, aryl, arylalkyl or monohydric heterocyclic Rest may have a substituent. The number of carbon atoms the substituted amino group is usually about 1 to 60, except the number of carbon atoms of the substituent, preferably 2 to 48.

In particular, a methylamino group, dimethylamino group, ethylamino are exemplified n-butylamino group, t-butylamino group, pentylamino group Cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ -alkoxyphenylamino radicals, di (C ₁ -C ₁₂ -alkoxyphenyl) amino radicals, di (C ₁ -C ₁₂ -alkylphenyl) amino radicals, a 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, pyrazylamino group, triazylamino group, phenyl-C ₁ -C ₁₂ -alkylamino radicals, C ₁ -C ₁₂ -alkoxyphenyl-C ₁ -C ₁₂ -alkylamino radicals, C ₁ - C ₁₂ alkylphenyl-C ₁ -C ₁₂ -a Alkylamino radicals, di (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ -alkyl) amino radicals, di (C ₁ -C ₁₂ -alkylphenyl-C ₁ -C ₁₂ -alkyl) amino radicals, 1-naphthyl-C ₁ -C _12- alkylamino radicals, 2-naphthyl-C ₁ -C ₁₂ -alkylamino radicals and the like.

The substituted silyl group includes silyl groups substituted with one, two or three radicals selected from alkyl radicals, aryl radicals, Arylalkyl radicals and monovalent heterocyclic radicals. The substituted silyl group has a number of carbon atoms of usually about 1 to 60, preferably 3 to 48, on. The alkyl radical, aryl radical, Arylalkyl or monovalent heterocyclic radical may have a substituent.

In particular, illustrates a trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-i-propylsilyl, dimethyl-i-propylsilyl, diethyl-i-propylsilyl, t-Butylsilyldimethylsilylgruppe, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-Ethylhexyldimethylsilylgruppe, nonyldimethylsilyl group, decyldimethylsilyl group, 3, 7-dimethyloctyldimethylsilyl group, lauryldimethylsilyl group, phenyl-C ₁ -C ₁₂ -alkylsilyl radicals, C ₁ -C ₁₂ -alkoxyphenyl-C ₁ -C ₁₂ -alkylsilyl radicals, C ₁ -C ₁₂ -alkylphenyl-C ₁ -C ₁₂ -alkylsilyl radicals, Naphthyl-C ₁ -C ₁₂ -alkylsilyl, 2-naphthyl-C ₁ -C ₁₂ -alkylsilyl, phenyl-C ₁ -C ₁₂ -alkyldimethylsilyl, triphenylsilyl, tri-p-xylylsilyl, tribenzylsilyl, diphenylmethylsilyl, t-butyldiphenylsilyl, dimethylphenylsilyl and the like.

Of the Acyl radical has a number of Köhlstoffatomen from usually about 2 to 20, preferably 2 to 18, and specific examples close to it an acetyl group, propionyl group, butyryl group, isobutyryl group, Pivaloyl group, benzoyl group, trifluoroacetyl group, pentafluorobenzoyl group and the like.

Of the Acyloxy group has a number of carbon atoms of usually about 2 to 20, preferably 2 to 18, and specific examples close to it an acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, Pivaloyloxy group, benzoyloxy group, trifluoroacetyloxy group, pentafluorobenzoyloxy group and the like.

The Amide group has a number of carbon atoms of usually about 2 to 20, preferably 2 to 18, and specific examples close to it a formamide group, acetamide group, propioamide group, butylamide group, Benzamide group, trifluoroacetamide group, pentafluorobenzamide group, Diformamide group, diacetamide group, dipropioamide group, dibutylamide group, Dibenzamide group, ditrifluoroacetamide group, dipentafluorobenzamide group and the like.

The acid imide includes Residues, obtained by splitting off a hydrogen atom, the attached to a nitrogen atom of an acid imide has a number Carbon atoms of about 4 to 20, and specific examples close to it the following radicals and the like.

Of the monovalent heterocyclic radical means an atomic grouping after cleavage of a hydrogen atom from a heterocyclic Compound remains, and has a number of carbon atoms of usually about 4 to 60, preferably 4 to 20 on. The number of carbon atoms of the heterocyclic residue does not close the number of carbon atoms of the substituent. Here concludes the heterocyclic compound organic compounds having a cyclic structure in which the ring forming elements not only a carbon atom, but also heteroatoms, such as oxygen, sulfur, nitrogen, phosphorus, Include boron and the like which are contained in the ring. In particular, the following will be Structures listed.

In each of the formulas described above, the R's independently Hydrogen atom, an alkyl radical, alkoxy radical, alkylthio radical, aryl radical, Aryloxy, arylthio, arylalkyl, arylalkoxy, arylalkylthio, Arylalkenyl radical, arylalkynyl radical, an amino group, substituted Amino group, silyl group, substituted silyl group, a halogen atom, an acyl radical, acyloxy radical, imine radical, an amide group, acid imide group, a monovalent heterocyclic group, a carboxyl group, substituted ones Carboxyl group or cyano group.

Among them, preferred are a thienyl group, C ₁ -C ₁₂ alkylthienyl, pyrrolyl, furyl, pyridyl, C ₁ -C ₁₂ alkylpyridyl, piperidyl, quinolyl, isoquinolyl and the like, and more preferred are thienyl, C ₁ -C _12- Alkylthienylreste, a pyridyl group, C ₁ -C ₁₂ -Alkylpyridylreste.

The substituted carboxyl group means a carboxyl group with an alkyl group, aryl group, arylalkyl group or monohydric heterocyclic group Rest substituted, and has a number of carbon atoms from usually about 2 to 60, preferably 2 to 48, on. Specific examples of it shut down a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, i-propoxycarbonyl group, butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, Cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3.7 Dimethyloctyloxycarbonylgruppe, Dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, Perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxycarbonyl group, Phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group and the like. The alkyl radical, aryl radical, arylalkyl radical or monovalent heterocyclic radical may have a substituent. The number the carbon atoms of the substituted carboxyl group does not close the number of carbon atoms of the substituent.

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

Of the Substituent Q closes an alkyl radical, alkoxy radical, alkylthio radical, aryl radical, aryloxy radical, Arylthio, arylalkyl, arylalkoxy, arylalkylthio, Arylalkenyl radical, arylalkynyl radical, a substituted amino group, substituted Silyl group, a fluorine atom, an acyl radical, acyloxy radical, an amide group, acid imide, a monovalent heterocyclic group, a carboxyl group, substituted ones Carboxyl group, cyano group, nitro group and the like, and definitions and specific examples thereof are the same as described above.

The ring A and the ring B may share, in addition to Z _5, a ring atom forming each ring, and one or more and two or less of the rings A, B and C are not aromatic rings.

Preferably, the ring A and the ring B in addition to Z ₅ share a ring atom. Further, it is preferable that a non-aromatic ring is present.

(wobei der Ring A, Ring B und Ring C jeweils unabhängig einen aromatischen Ring oder nicht aromatischen Ring darstellen, die gegebenenfalls einen Substituenten aufweisen, Z₁, Z₂, Z₃, Z₄ und Z₅ jeweils unabhängig C-(Q)_z oder ein Stickstoffatom darstellen, Q einen Substituenten oder ein Wasserstoffatom darstellt, z 0 oder 1 darstellt, der Ring A und der Ring B neben Z₅ ein Ringatom teilen können, die Substituenten an den Ringen miteinander verbunden sein können, wobei weiter ein Ring gebildet wird, und ein oder mehrere Ringe, die keine verbindende Bindung zwischen den Ringen A, B und C aufweisen, nicht aromatische Ringe sind).Preferably, the polymer compound of the present invention contains a repeating unit of the following formula (1-1), (1-2) or (1-3):

(wherein Ring A, Ring B and Ring C each independently represent an aromatic ring or non-aromatic ring optionally having a substituent; Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z _{5 are} each independently C- (Q) _z or represents a nitrogen atom, Q represents a substituent or a hydrogen atom, z represents 0 or 1, the ring A and the ring B in addition to Z ₅ can share a ring atom, the substituents on the rings may be connected to each other, wherein a ring is further formed and one or more rings having no linking bond between rings A, B and C are not aromatic rings).

und dgl. und jene, die einen Substituenten an diesen Einheiten aufweisen.Specific examples of the repeating unit of the formula (1-1) include:

and the like, and those having a substituent on these units.

und dgl. und jene, die einen Substituenten an diesen Einheiten aufweisen. Bestimmte Beispiele der Wiederholungseinheit der Formel (1-3) schließen ein:

und dgl. und jene, die einen Substituenten an diesen Einheiten aufweisen.Specific examples of the repeating unit of the formula (1-2) include:

and the like, and those having a substituent on these units. Specific examples of the repeating unit of the formula (1-3) include:

and the like, and those having a substituent on these units.

In the repeating units of the formulas described above (1-1) to (1-3) Atoms forming rings A, B and C ("atom forming a ring") an atom that is the skeleton of the ring), atoms such as nitrogen, oxygen, sulfur, silicon, Selenium and the like, in addition to a carbon atom, and in terms of adjustment the charge transportability It is preferred that atoms forming the rings A, B and C all Are carbon atoms.

in the In view of the increase the solubility a polymer compound, with a view to adjusting the wavelength of Light emission and with regard to the adjustment of the charge transportability it is preferred that at least one of the rings A, B and C is a Substituent has.

Further are repeating units in terms of charge transportability preferably, having a structure of the formula described above (1-1) or (1-2), and are in view of easy synthesis Structures of the above-described formula (1-1) are more preferred.

Formel (2-1) (wobei R₁ und R₂ jeweils unabhängig einen Substituenten darstellen, der Ring D einen nicht aromatischen Ring darstellt, der gegebenenfalls einen Substituenten aufweist, a eine ganze Zahl von 0 bis 2 darstellt, b eine ganze Zahl von 0 bis 3 darstellt und, wenn zwei oder mehrere R₁ bzw. zwei oder mehrere R₂ vorhanden sind, sie gleich oder verschieden sein können und R₁ und R₂ miteinander verbunden sein können, wobei ein Ring gebildet wird. R₁ und/oder R₂ können mit Ring D verbunden sein, wobei ein Ring gebildet wird, und Q und z weisen die gleichen Bedeutungen wie vorstehend beschrieben auf).Further, it is more preferable that the above-described formula (1-1) has the following formula (2-1) is:

Formula (2-1) (wherein R ₁ and R ₂ each independently represent a substituent, ring D represents a non-aromatic ring optionally having a substituent, a represents an integer of 0 to 2, b represents an integer of 0 to 3 and, when two or more R ₁ or two or more R ₂ are present, they may be the same or different and R ₁ and R _{2 may} be linked together to form a ring. R ₁ and / or R ₂ may be connected to ring D, forming a ring, and Q and z have the same meanings as described above).

Formel (3-1) (wobei R₁, R₂, Ring D, Q, z, a und b die gleichen Bedeutungen wie vorstehend beschrieben aufweisen).Preferably, the repeating unit containing the above-described formula (2-1) is a repeating unit of the following formula (3-1):

Formula (3-1) (wherein R ₁ , R ₂ , ring D, Q, z, a and b have the same meanings as described above).

(wobei R_1a, R_1b, R_2a bis R_2c und R_3a bis R_3g einen Substituenten darstellen. In den Formeln (4-1) bis (4-3) können R_2c und R_3g miteinander verbunden sein, wobei ein Ring gebildet wird.Among the repeating units of the formula (3-1), those of the following formulas (4-1), (4-2), (4-3) and (4-4) are more preferable from the viewpoint of adjusting the charge transportability.

(wherein R _1a , R _1b , R _2a to R _2c and R _3a to R _{3g represent} a substituent) In the formulas (4-1) to (4-3), R _2c and R _{3g may} be bonded to each other with one ring is formed.

In the formula (4-4), R _2c and R _{3e may be} bonded together to form a ring).

When Ring formed by joining together becomes aromatic Rings and non-aromatic rings and the like listed, and Specific examples thereof are the same as described above.

The Units of the formulas (4-1) to (4-3) are in the case of the formula (3-1) in which z = 1 and the unit of formula (4-4) in the case of formula (3-1), where z = 0.

Specific examples of the repeating unit of the above-described formula (4-1) include:

Specific examples of the repeating unit of the above-described formula (4-2) include one:

Specific examples of the repeating unit of the above-described formula (4-3) include:

Specific examples of the repeating unit of the above-described formula (4-4) include:

In In the formulas Me represents a methyl group or Et represents one Ethyl group.

The Sum of repeating units, the structures of the above described formulas (1-1), (1-2), (1-3), (2-1), (3-1), (4-1), (4-2), (4-3) and (4-4) is usually 1 mol% or more and 100 mol% of the less, preferably 5 mol% or more and 100 mol% or less, based on the sum of all Wiederolungseinheiten in the polymer compound of the present invention.

The Polymer compound of the present invention is preferably one Copolymer, in addition to the repeat units of the formulas described above (1-1), (1-2), (1-3), (2-1), (3-1), (4-1), (4-2), (4-3) and (4 -4) at least one of the other repeating units with regard to the variation of the wavelength the light emission, in terms of increasing the efficiency of the Light emission, with a view to improving the heat resistance and the like. Contains.

As the other repeating units besides the repeating units of the above-described formulas (1-1), (1-2), (1-3), (2-1), (3-1), (4-1), (4 -2), (4-3) and (4-4), repeating units of the following formula (5), (6), (7) or (8) are preferable. -Ar ₁ - (5) - (Ar ₂ - X ₁ ) _ff -Ar ₃ - (6) -Ar ₄ -X ₂ - (7) -X ₃ - (8) (wherein Ar _{1 ,} Ar ₂ , Ar ₃ and Ar ₄ each independently represent an arylene radical, divalent heterocyclic radical or divalent radical 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, aryl group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, aryl group, monovalent heterocyclic group, arylalkyl group or substituted amino group. Ff represents 1 or 2. m represents an integer of 1 to 12 two or more R ₉ , two or more R ₁₀ , two or more R ₁₁ , two or more R _12, or two or more R ₁₃ are present, they may be the same or different).

Here the arylene radical is an atomic group obtained by cleavage of two hydrogen atoms of one aromatic hydrocarbon, and close those with a condensed ring and those obtained by tying of two or more independent Benzene rings or condensed rings directly or via a Vinylene group and the like. The arylene group may have a substituent exhibit.

Of the Substituent closes Alkyl radicals, alkoxy radicals, alkylthio radicals, aryl radicals, aryloxy radicals, Arylthio radicals, arylalkyl radicals, arylalkoxy radicals, arylalkylthio radicals, Arylalkenyl radicals, arylalkynyl radicals, an amino group, substituted Amino groups, a silyl group, substituted silyl groups, halogen atoms, an acyl group, acyloxy group, an imine residue, an amide group, acid imide, monovalent heterocyclic radicals, a carboxyl group, substituted Carboxyl groups and a cyano group.

The Number of carbon atoms of a part of an aryl group excluding the Substituents, is usually about 6 to 60, and preferably 6 to 20. The total number of carbon atoms, including the Substituents of an arylene group is usually about 6 to 100.

Examples close the arylene radical Phenylene groups (e.g., the following formulas 1 to 3), naphthalenediyl groups (the following formulas 4 to 13), anthracenediyl groups (the following Formulas 14 to 19), biphenyldiyl groups (the following formulas 20 to 25), fluorenediyl groups (the following formulas 36 to 38), terphenyldiyl groups (the following formulas 26 to 28), residues of a condensed ring compound (the following formulas 29 to 35), stilbenediyl groups (the following Formulas A to D), distilbendiyl groups (the following formulas E and F) and the like. Among them are phenylene groups, biphenylene groups, Fluoro-diyl groups and stilbenediyl groups are preferred.

The divalent heterocyclic radical Ar ₁ , Ar ₂ , Ar ₃ or Ar ₄ means a remaining atomic group obtained by cleaving two hydrogen atoms from a heterocyclic compound, and may have a substituent. Here, the heterocyclic compound includes organic compounds having a cyclic structure in which elements forming the ring not only a carbon atom but also Heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, arsenic and the like contained in the ring. Of divalent heterocyclic radicals, aromatic heterocyclic radicals are preferred.

Of the Substituent closes Alkyl radicals, alkoxy radicals, alkylthio radicals, aryl radicals, aryloxy radicals, Arylthio radicals, arylalkyl radicals, arylalkoxy radicals, arylalkylthio radicals, Arylalkenyl radicals, arylalkynyl radicals, an amino group, substituted Amino groups, a silyl group, substituted silyl groups, halogen atoms, an acyl group, acyloxy group, an imine residue, an amide group, acid imide, monovalent heterocyclic radicals, a carboxyl group, substituted Carboxyl groups and a cyano group.

The Number of carbon atoms of a part of a divalent heterocyclic Rest, except the substituent is usually about 3 to 60. The total number of carbon atoms, including the Substituents of a divalent heterocyclic group is usually about 3 to 100.

Examples of the divalent heterocyclic group include the following groups.

a divalent heterocyclic radical containing nitrogen as a heteroatom includes; Pyridinediyl groups (the following formulas 39 to 44), diazaphenylene groups (the following formulas 45 to 48), quinolinediyl groups (the following Formulas (49 to 63), quinoxalinediyl groups (the following formulas 64 to 68), acridinediyl groups (the following formulas 69 to 72), Bipyridyldiyl groups (the following formulas 73 to 75), phenanthrolinediyl groups (the following formulas 76 to 78) and the like.

residues which contain silicon, nitrogen, selenium and the like as a hetero atom and a fluorene structure (the following formulas 79 to 93).

heterocyclic 5-membered ring radicals containing silicon, nitrogen, sulfur, Selenium and the like as a hetero atom (the following formulas 94 to 98).

heterocyclic Residues with fused 5-membered radicals containing silicon, nitrogen, Selenium and the like as a hetero atom (the following formulas 99 to 110, 102 to 110).

heterocyclic 5-membered ring radicals containing silicon, nitrogen, sulfur, Selenium and the like as a heteroatom and a bond in Have a position of its heteroatom, wherein a dimer or oligomer is formed (the following formulas 111 to 112).

heterocyclic 5-membered ring radicals containing silicon, nitrogen, sulfur, Selenium and the like as a heteroatom and a bond in a position of their heteroatom to a phenyl group (the following formulas 113 to 119).

heterocyclic Residues with fused 5-membered radicals containing oxygen, nitrogen, Sulfur and the like as a heteroatom and having a phenyl group, Furyl group or thienyl group are substituted (the following Formulas 120 to 125).

The bivalent radical having a metal complex structure represented by Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ means a bivalent radical remaining after cleaving two hydrogen atoms from an organic ligand of a metal complex with an organic ligand.

The Number of carbon atoms of the organic ligand is usually about 4 to 60, and examples thereof include 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenylpyridine and derivatives thereof, 2-phenylbenzothiazole and derivatives thereof, 2-phenylbenzoxazole and derivatives thereof, porphyrin and derivatives thereof and the like.

Listed as central metal of the complex are, for example, aluminum, zinc, Beryllium, iridium, platinum, gold, europium, terbium and the like.

When Metal complex with an organic ligand become metal complexes, Triplet light-emitting complexes and the like listed, the as fluorescent materials or phosphorescent materials are known with lower molecular weight.

As the bivalent radical having a metal complex structure, the following radicals (126 to 132) are particularly exemplified.

In the above-described formulas 1 to 132, R each independently represents a hydrogen atom, an alkyl group, alkoxy group, allylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, Arylalkylthio, arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halogen, acyl, acyloxy, imino, amide, acidimide, monovalent heterocyclic, carboxyl, substituted or cyano. The carbon atoms in The radicals 1 to 132 may be replaced by a nitrogen atom, oxygen atom or sulfur atom, and hydrogen atoms in these radicals may be replaced by a fluorine atom.

(wobei R₁₄ einen Alkylrest, Alkoxyrest, Alkylthiorest, Arylrest, Aryloxyrest, Arylthiorest, Arylalkylrest, Arylalkoxyrest, Arylalkylthiorest, Arylalkenylrest, Arylalkinylrest, eine Aminogruppe, substituierte Aminogruppe, Silylgruppe, substituierte Silylgruppe, ein Halogenatom, eine Acylgruppe, Acyloxygruppe, einen Iminrest, eine Amidgruppe, Säureimidgruppe, einen einwertigen heterocyclischen Rest, eine Carboxylgruppe, substituierte Carboxylgruppe oder Cyanogruppe darstellt. n stellt eine ganze Zahl von 0 bis 4 dar. Wenn zwei oder mehr R₁₄ vorhanden sind, können sie gleich oder verschieden sein).

(wobei R₁₅ und R₁₆ jeweils unabhängig einen Alkylrest, Alkoxyrest, Alkylthiorest, Arylrest, Aryloxyrest, Arylthiorest, Arylalkylrest, Arylalkoxyrest, Arylalkylthiorest, Arylalkenylrest, Arylalkinylrest, eine Aminogruppe, substituierte Aminogruppe, Silylgruppe, substituierte Silylgruppe, ein Halogenatom, einen Acylrest, Acyloxyrest, Iminrest, eine Amidgruppe, Säureimidgruppe, einen einwertigen heterocyclischen Rest, eine Carboxylgruppe, substituierte Carboxylgruppe oder Cyanogruppe darstellen. o und p stellen jeweils unabhängig eine ganze Zahl von 0 bis 3 dar. Wenn zwei oder mehr R₁₅ und zwei oder mehr R₁₆ vorhanden sind, können sie gleich oder verschieden sein).

(wobei R₁₇ und R₂₀ jeweils unabhängig einen Alkylrest, Alkoxyrest, Alkylthiorest, Arylrest, Aryloxyrest, Arylthiorest, Arylalkylrest, Arylalkoxyrest, Arylalkylthiorest, Arylalkenylrest, Arylalkinylrest, eine Aminogruppe, substituierte Aminogruppe, Silylgruppe, substituierte Silylgruppe, ein Halogenatom, eine Acylgruppe, Acyloxygruppe, einen Iminrest, eine Amidgruppe, Säureimidgruppe, einen einwertigen heterocyclischen Rest, eine Carboxylgruppe, substituierte Carboxylgruppe oder Cyanogruppe darstellen. q und r stellen jeweils unabhängig eine ganze Zahl von 0 bis 4 dar. R₁₈ und R₁₉ stellen jeweils unabhängig ein Wasserstoffatom, einen Alkylrest, Arylrest, einwertigen heterocyclischen Rest, eine Carboxylgruppe, substituierte Carboxylgruppe oder Cyanogruppe dar. Wenn zwei oder mehr R₁₇ und zwei oder mehr R₂₀ vorhanden sind, können sie gleich oder verschieden sein).

(wobei R₂₁ einen Alkylrest, Alkoxyrest, Alkylthiorest, Arylrest, Aryloxyrest, Arylthiorest, Arylalkylrest, Arylalkoxyrest, Arylalkylthiorest, Arylalkenylrest, Arylalkinylrest, eine Aminogruppe, substituierte Aminogruppe, Silylgruppe, substituierte Silylgruppe, ein Halogenatom, eine Acylgruppe, Acyloxygruppe, einen Iminrest, eine Amidgruppe, Säureimidgruppe, einen einwertigen heterocyclischen Rest, eine Carboxylgruppe, substituierte Carboxylgruppe oder Cyanogruppe darstellt. s stellt eine ganze Zahl von 0 bis 2 dar. Ar₁₃ und Ar₁₄ stellen jeweils unabhängig einen Arylenrest, zweiwertigen heterocyclischen Rest oder zweiwertigen Rest mit Metallkomplexstruktur dar. ss und tt stellen jeweils unabhängig 0 oder 1 dar. X₄ stellt O, S, SO, SO₂, Se oder Te dar. Wenn zwei oder mehr R₂₁ vorhanden sind, können sie gleich oder verschieden sein).

(wobei R₂₂ und R₂₃ jeweils unabhängig einen Alkylrest, Alkoxyrest, Alkylthiorest, Arylrest, Aryloxyrest, Arylthiorest, Arylalkylrest, Arylalkoxyrest, Arylalkylthiorest, Arylalkenylrest, Arylalkinylrest, eine Aminogruppe, substituierte Aminogruppe, Silylgruppe, substituierte Silylgruppe, ein Halogenatom, eine Acylgruppe, Acyloxygruppe, einen Iminrest, eine Amidgruppe, Säureimidgruppe, einen einwertigen heterocyclischen Rest, eine Carboxylgruppe, substituierte Carboxylgruppe oder Cyanogruppe darstellen. t und u stellen jeweils unabhängig eine ganze Zahl von 0 bis 4 dar. X₅ stellt O, S, SO₂, Se, Te, N-R₂₄ oder SiR₂₅R₂₆ dar. X₆ und X₇ stellen jeweils unabhängig N oder C-R₂₇ dar. R₂₄, R₂₅, R₂₆ und R₂₇ stellen jeweils unabhängig ein Wasserstoffatom, einen Alkylrest, Arylrest, Arylalkylrest oder einwertigen heterocyclischen Rest dar. Wenn zwei oder mehr R₂₂, zwei oder mehr R₂₃ und zwei oder mehr R₂₇ vorhanden sind, können sie gleich oder verschieden sein).Further, among the repeating units of the above-described formulas (5), (6), (7) and (8), repeating units of the following formula (9), (10), (11), (12), (13) or (14) preferred.

(wherein R _{14 is} an alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkoxy, arylalkylthio, arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halogen, acyl, acyloxy, imino, an imine, Represents amide group, acidimide group, a monovalent heterocyclic group, a carboxyl group, substituted carboxyl group or cyano group, n represents an integer of 0 to 4. When two or more R ₁₄ are present, they may be the same or different).

(wherein R ₁₅ and R _{16 are} each independently alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkoxy, arylalkylthio, arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halogen, acyl, acyloxy And imine, an amide group, an acidimide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group, o and p each independently represent an integer of 0 to 3. When two or more R ₁₅ and two or more R ₁₆ are present are, they may be the same or different).

(wherein R ₁₇ and R _{20 are} each independently alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkoxy, arylalkylthio, arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halogen, acyl, acyloxy , an imine group, an amide group, an acidimide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or cyano group, q and r each independently represent an integer of 0 to 4. R ₁₈ and R ₁₉ each independently represent a hydrogen atom, a Alkyl group, aryl group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group. When two or more R ₁₇ and two or more R ₂₀ are present, they may be the same or different).

(wherein R _{21 is} alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkoxy, arylalkylthio, arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halogen, acyl, acyloxy, imine, a S represents an integer of 0 to 2. Ar ₁₃ and Ar ₁₄ each independently represent an arylene group, divalent heterocyclic group or divalent metal complex group. ss and tt each independently represent 0 or 1. X ₄ represents O, S, SO, SO _2, Se, or Te. When two or more R ₂₁ are present, they may be the same or different).

(wherein R ₂₂ and R _{23 are} each independently alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkoxy, arylalkylthio, arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halogen, acyl, acyloxy represent 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, 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 each independently represent N or CR _27. R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ each independently represent a hydrogen atom, an alkyl group, aryl group, arylalkyl group or monovalent one heterocyclic group. When two or more R ₂₂ , two or more R ₂₃ and two or more R ₂₇ are present, they may be the same or different).

(wobei R₂₈ und R₃₃ jeweils unabhängig einen Alkylrest, Alkoxyrest, Alkylthiorest, Arylrest, Aryloxyrest, Arylthiorest, Arylalkylrest, Arylalkoxyrest, Arylalkylthiorest, Arylalkenylrest, Arylalkinylrest, eine Aminogruppe, substituierte Aminogruppe, Silylgruppe, substituierte Silylgruppe, ein Halogenatom, eine Acylgruppe, Acyloxygruppe, einen Iminrest, eine Amidgruppe, Säureimidgruppe, einen einwertigen heterocyclischen Rest, eine Carboxylgruppe, substituierte Carboxylgruppe oder Cyanogruppe darstellen. v und w stellen jeweils unabhängig eine ganze Zahl von 0 bis 4 dar. R₂₉, R₁₀, R₃₁ und R₃₂ stellen jeweils unabhängig ein Wasserstoffatom, einen Alkylrest, Arylrest, einwertigen heterocyclischen Rest, eine Carboxylgruppe, substituierte Carboxylgruppe oder Cyanogruppe dar. Ar₅ stellt einen Arylenrest, zweiwertigen heterocyclischen Rest oder zweiwertigen Rest mit Metallkomplexstruktur dar. Wenn zwei oder mehr R₂₈ und zwei oder mehr R₃₃ vorhanden sind, können sie gleich oder verschieden sein).Examples of the 5-membered ring in the middle of the repeating unit of the formula (11) include thiadiazole, oxadiazole, triazole, thiophene, furan, silole and the like.

(wherein R ₂₈ and R _{33 are} each independently alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkoxy, arylalkylthio, arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halogen, acyl, acyloxy represents an imine residue, an amide group, an acidimide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group, v and w each independently represents an integer of 0 to 4. R ₂₉ , R ₁₀ , R ₃₁ and R ₃₂ provide each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. Ar ₅ represents an arylene group, a divalent heterocyclic group or a divalent metal complex group. When two or more R ₂₈ and two or more R ₃₃ are present, they can equal or v to be different).

(wobei Ar₆, Ar₇, Ar₈ und Arg jeweils unabhängig einen Arylenrest oder zweiwertigen heterocyclischen Rest darstellen. Ar₁₀, Ar₁₁ und Ar₁₂ stellen jeweils unabhängig einen Arylenrest oder einwertigen heterocyclischen Rest dar. Ar₆, Ar₇, Ar₈, Ar₉ und Ar₁₀ können einen Substituenten aufweisen. x und y stellen jeweils unabhängig 0 oder 1 dar und 0 ≤ x + y ≤ 1).Of the repeating units of the above-described formula (6), the repeating units of the following formula (15) are preferable in view of the variation in the wavelength of light emission, in view of increasing the light emission efficiency, and in terms of increasing the heat resistance.

(wherein Ar ₆ , Ar ₇ , Ar ₈ and Arg each independently represent an arylene group or divalent heterocyclic group. Ar ₁₀ , Ar ₁₁ and Ar ₁₂ each independently represent an arylene group or monovalent heterocyclic group. Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ and Ar ₁₀ may have a substituent, x and y each independently represents 0 or 1, and 0 ≤ x + y ≤ 1).

Specific Examples of the repeating unit of the above-described Formula (15) include those of the following formulas (133 to 140).

In In the formulas described above, the radicals R are the same as in the formulas 1 to 132 described above.

To the Increase the solubility in organic solvents it is preferred that one or more substituents other than a hydrogen atom, and it is preferable that the Symmetry of the form of a repeating unit, the substituents contains is low.

If R is an alkyl in the above formulas, it is to increase the solubility of the Polymer compound in organic solvents is preferred that one or more R contains a cyclic or branched alkyl.

Further can, when the radicals R are partially an aryl radical or heterocyclic Rest contained in the above formulas, these radicals furthermore have at least one substituent.

Of the repeating units of the above-described formula (15), preferred are those in which Ar ₆ , Ar ₇ , Ar ₈ and Ar ₉ each independently represent an arylene group and Ar ₁₀ , Ar ₁₁ and Ar ₁₂ each independently represent an aryl group in view of the adjustment of the wavelength of the light emission and with regard to the properties of the device and the like

Preferably, Ar ₆ , Ar ₇ and Ar ₈ each independently represent an unsubstituted phenylene group, unsubstituted biphenyl group, unsubstituted naphthylene group or unsubstituted anthracenediyl group.

With respect to solubility, light emission efficiency and stability, Ar ₁₀ , Ar ₁₁ and Ar ₁₂ each independently preferably represent an aryl group having three or more substituents, more preferably a phenyl group having three or more substituents, naphthyl group having three or more substituents or anthranyl group having three or more substituents, more preferably a phenyl group having three or more substituents.

(wobei Re, Rf und Rg jeweils unabhängig einen Alkylrest, Alkoxyrest, Alkylthiorest, Arylrest, Aryloxyrest, Arylthiorest, Arylalkylrest, Arylalkoxyrest, Arylalkylthiorest, Arylalkenylrest, Arylalkinylrest, eine Aminogruppe, substituierte Aminogruppe, Silylgruppe, substituierte Silylgruppe, Silyloxygruppe, substituierte Silyloxygruppe, einen einwertigen heterocyclischen Rest oder ein Halogenatom darstellen).Among others, those in which Ar ₁₀ , Ar ₁₁ and Ar ₁₂ each independently represent the following formula (15-1) are preferable.

(wherein Re, Rf and Rg are each independently alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkoxy, arylalkylthio, arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, silyloxy, substituted silyloxy, monohydric represent heterocyclic radical or a halogen atom).

(wobei die Benzolringe, die in den Strukturen von (15-2) und (15-3) enthalten sind, jeweils unabhängig 1 oder mehr und 4 oder weniger Substituenten aufweisen können. Diese Substituenten können untereinander gleich oder verschieden sein. Mehrere Substituenten können verbunden sein, wobei ein Ring gebildet wird. Ferner kann ein weiterer aromatischer Kohlenwasserstoffring oder heterocyclischer Ring benachbart zu dem Benzolring verbunden sein).In the repeating unit of the above-described formula (15), Ar ₇ preferably represents the following formula (15-2) or (15-3).

(wherein the benzene rings contained in the structures of (15-2) and (15-3) each independently may have 1 or more and 4 or less substituents.) These substituents may be the same or different from each other to form a ring, further, another aromatic hydrocarbon ring or heterocyclic ring may be connected adjacent to the benzene ring).

(wobei Re bis Rg wie vorstehend beschrieben sind).As particularly preferable specific examples of the repeating unit of the above-described formula (15), repeating units of the following (formulas 141-142) are listed.

(wherein Re to Rg are as described above).

In The above-described formulas are Re to Rg as in the above described formulas 1 to 132 described. To increase the solubility in organic solvents it is preferred that one or more substituents other than a hydrogen atom are included, and it is preferred that the symmetry the form of a repeating unit containing substituents, low is.

If the radicals R are an alkyl chain in the abovementioned formulas is to increase the solubility the polymer compound in organic solvents is preferred one or more R contains a cyclic or branched alkyl chain.

Further can, when the radicals R are partially an aryl radical or heterocyclic Rest contained in the above formulas, these radicals furthermore have at least one substituent.

The inventive polymer compound can be a repeating unit, different from the repeat units the above-described formulas (1-1), (1-2), (1-3) and (5) differs to (15), in a range containing a light-emitting Property and charge-transporting property is not affected. These repeating units and other repeating units can by a non-conjugated unit, and the repeating unit may contain its non-conjugated part. As a binding structure are shown below and combinations of two or more of this is illustrated. Here, R represents a remainder that out is selected from the same substituent as described above, and Ar represents a hydrocarbon radical having 6 to 60 carbon atoms represents.

Among the polymer compounds of the present invention, those composed of only a repeating unit of the above-described formula (1-1) and / or those composed of only a repeating unit of the above-described formula (1-2), and / or those who only have one Repeating unit of the above-described formula (1-3) are constructed, and preferred those consisting essentially of a repeating unit of the above-described formula (1-1) and / or (1-2) and / or (1-3) and a Repeating unit of the above-described formula (5) to (15) are constructed.

The inventive polymer copolymer may be a random, block or graft copolymer or a polymer with an intermediate structure of it, for example a statistical one Copolymer with block character. With regard to obtaining a polymeric light-emitting material, the high quantum efficiency of fluorescence or phosphorescence are random copolymers of block character and block or graft copolymers more preferably as fully random Copolymers. The polymer compound of the present invention also includes those with a branch in the main chain and three or more End parts and dendrimers.

The end group of the polymer compound of the present invention can be protected with a stable group because if a polymerization-active group remains intact, there is a possibility of deterioration of the light-emitting property and lifetime when the compound is molded into a device. Those having a conjugated bond following a conjugated structure of a main chain are preferred, and exemplified are structures containing a bond to an aryl group or heterocyclic group through a carbon-carbon bond. In particular, there are illustrated substituents which are disclosed in the chemical formula 10 of Japanese Patent Application Laid-open (p. JP-A) No. 9-45478 are described.

In the polymer compound of the present invention, it is preferable that at least one of its molecular chain ends is an aromatic End group, selected from monovalent heterocyclic radicals, monovalent aromatic Amine groups, monovalent radicals derived from heterocyclic coordinated Metal complexes and aryl radicals. Than this aromatic End group can be one remainder or two or more Leftovers can be used. Preferably, other end groups than aromatic end groups, with regard to the fluorescence property and properties of the Device essentially not present. Here, the molecular chain end means an aromatic end group at the end of a polymer compound present by the production process of the present invention is a leaving group of a monomer used for polymerization which was not cleaved in the polymerization and in the end a polymer compound, or a hydrogen atom, instead of binding an aromatic end group to a monomer which is present at the end of a polymer compound, although a leaving group was split off from the monomer. at Preparation of a polymer compound according to the invention using a leaving group of a monomer used for the polymerization, which was not split off in the polymerization and at the end a polymer compound is present under these molecular chain ends, for example, a monomer having a halogen atom as the starting material, when a halogen remains at the end of the polymer compound, a Tendency to deteriorate the fluorescence property and the like it is preferred that essentially no leaving groups of a Monomers remain at the end.

In The polymer compound may end at least one of its molecular chains having an aromatic end group selected from monohydric heterocyclic Radicals, monovalent aromatic amine radicals, monovalent radicals, derived from heterocyclic coordinated metal complexes and Aryl radicals having a formula weight of 90 or more, are blocked wherein it is expected that the polymer compound has various properties be lent. In particular, an effect of extension the time required to reduce the luminosity of a device, an effect of increase charge usability, charge transportability, light-emitting Property and the like, an effect of increasing the compatibility and mutual Effect between copolymers, an anchor-like effect and the like listed.

When monovalent aromatic amine group structures are listed in the one or two connecting bonds in a structure of the above described formula (15) with R are completed.

When monovalent radical derived from a heterocyclic coordinated metal complex is derived, structures are illustrated in which two or more connecting bonds in the above-mentioned bivalent Rest are completed with a metal complex structure with R are.

Of the end groups of the polymer compound of the present invention, the aryl group having a formula weight of 90 or more has a number of carbon atoms of usually about 6 to 60. Here is in With respect to the formula weight of the aryl group, when the aryl group is represented by a chemical formula, the sum of the products obtained by multiplying the atomic number by the atomic weight of the elements in the chemical formula is the formula weight.

When Aryl radical are a phenyl group, naphthyl group, anthracenyl group, a residue having a fluorene structure, remnants of a fused ring compound and the like listed.

aufgeführt.As the phenyl group for terminating the end, for example

listed.

aufgeführt.As the naphthyl group for terminating the end, for example

listed.

aufgeführt.As the anthracenyl group, for example

listed.

aufgeführt.As the remainder containing a fluorene structure, for example

listed.

aufgeführt.As the remainder of a fused ring compound, for example

listed.

When End group to increase the charge injectability and the charge transportability are monovalent heterocyclic radicals, monovalent aromatic amine groups and fused ring compound residues are more preferred are monovalent heterocyclic radicals and condensed ring compound radicals.

When End group for improving the light-emitting property a naphthyl group, anthracenyl group, remnants of a fused one Ring compound and monovalent radicals derived from heterocyclic coordinated Metal complexes preferred.

When End group with the effect of prolonging the period of time for the Decrease in the brightness of a device is required Aryl radicals with one substituent preferred and phenyl groups with 1 to 3 alkyl radicals are preferred.

When End group with the effect of increasing compatibility and mutual Effect between polymer compounds are aryl radicals having a substituent prefers. By using a phenyl group containing a substituted Alkyl group having 6 or more carbon atoms, a anchor-like Effect can be achieved. The anchor effect means an effect by the one end group an anchor-like role in a coagulated body a polymer plays, whereby a mutual effect is increased.

When Remains for improving the characteristics of the device are the following Structures preferred.

When R in the formulas exemplifies the R described above.

The polymer compound of the present invention has a polystyrene-reduced number average molecular weight of usually about 10 ³ to 10 ⁸ , preferably 10 ⁴ to 10 ⁶ . The polystyrene-based weight-average molecular weight is 10 ³ to 10 ⁸ , preferably 10 ⁴ to 5 × 10 ⁶ .

When good solvent for the inventive polymer compound chloroform, dichloromethane, dichloroethane, tetrahydrofuran, Toluene, xylene, mesitylene, tetralin, decalin, n-butylbenzene and the like. illustrated. Dependent of the structure and molecular weight of the polymer compound For example, the polymer compounds in these solvents can usually in an amount of 0.1% by weight or more.

The inventive polymer compound is compared to emitting light at a shorter wavelength with the corresponding polyfluorene derivative.

When next becomes the process for producing a polymer compound of the present invention described.

(wobei Ring A, Ring B, Ring C und Z₁ bis Z₅ die gleichen Bedeutungen wie vorstehend beschrieben aufweisen. Y₁, Y₂, Y₃, Y₄, Y₅ und Y₆ stellen jeweils unabhängig einen Substituenten dar, der mit der Polymerisation in Beziehung steht).Polymer compounds of the present invention having, for example, a repeating unit of the formula (1-1), (1-2) or (1-3) can be obtained by polymerizing at least one compound of the following formula (16-1), (16-2 ) or (16-3) are prepared as starting material:

(wherein Ring A, Ring B, Ring C, and Z ₁ to Z _{5 have} the same meanings as described above.) Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y _5, and Y ₆ each independently represent a substituent represented by the polymerization is related).

(wobei R₁, R₂, a, b, Ring D, Q, z, Y₁ und Y₂ die gleichen Bedeutungen wie vorstehendbeschrieben aufweisen).Among the compounds of formula (16-1), compounds of formula (17-1) are preferred.

(wherein R ₁ , R ₂ , a, b, ring D, Q, z, Y ₁ and Y _{2 have} the same meanings as described above).

Under the compounds of the formula (17-1) are compounds of the formulas (18-1), (18-2), (18-3) and (18-4) are preferable.

(wobei Ring B, Ring C, Z₂, Z₃, Z₄, Y₃ und Y₄ die gleichen Bedeutungen wie vorstehend beschrieben aufweisen. Z₆, Z₇ und Z₈ stellen jeweils unabhängig C-(Q)_z oder ein Stickstoffatom dar. Z_ia, Z_5a und Z₉ stellen jeweils unabhängig ein Kohlenstoffatom dar. Q und z weisen die gleichen Bedeutungen wie vorstehend beschrieben auf. R₄ stellt einen Substituenten dar. e stellt eine ganze Zahl von 0 bis 2 dar. Wenn zwei oder mehr R₄ vorhanden sind, können sie gleich oder verschieden sein. Die Reste R₄ können miteinander verbunden sein, wobei ein Ring gebildet wird).Among the compounds of the formula (16-2), compounds of the formula (17-2) are preferred.

(wherein Ring B, Ring C, Z ₂ , Z ₃ , Z ₄ , Y ₃ and Y _{4 have} the same meanings as described above.) Z ₆ , Z ₇ and Z ₈ each independently represent C- (Q) _z or a nitrogen atom Z _ia , Z _5a and Z ₉ each independently represent a carbon atom Q and z have the same meanings as described above R ₄ represents a substituent. e represents an integer of 0 to 2 more R ₄ exist, they may be the same or different. The R ₄ may be joined together to form a ring is formed).

(wobei Ring A, Ring B, Z₁, Z₄, Z₅, Y₅ und Y- die gleichen Bedeutungen wie vorstehend beschrieben aufweisen. Z₁₀, Z₁₁, Z₁₂ und Z₁₃ stellen jeweils unabhängig C-(Q)_z oder ein Stickstoffatom dar. Z_2a und Z_3a stellen jeweils unabhängig ein Kohlenstoffatom dar. Q und z weisen die gleichen Bedeutungen wie vorstehend beschrieben auf. R₅ stellt einen Substituenten dar. f stellt eine ganze Zahl von 0 bis 2 dar. Wenn zwei oder mehr R₅ vorhanden sind, können sie gleich oder verschieden sein. Die Reste R₅ können miteinander verbunden sein, wobei ein Ring gebildet wird).Among the compounds of the formula (16-3), compounds of the formula (17-3) are preferred.

(wherein Ring A, Ring B, Z ₁ , Z ₄ , Z ₅ , Y ₅ and Y- have the same meanings as described above.) Z ₁₀ , Z ₁₁ , Z ₁₂ and Z ₁₃ each independently represent C- (Q) _z Z _2a and Z _3a each independently represent a carbon atom Q and z have the same meanings as described above R ₅ represents a substituent f represents an integer of 0 to 2 When two or two more R ₅ are present, they may be the same or different. The R ₅ may be joined together to form a ring is formed).

In the production process of the present invention, the substituent related to the polymerization includes halogen atoms, alkylsulfonate radicals, arylsulfonate radicals, arylalkylsulfonate radicals, borate groups, a sulfoniummethyl group, phosphoniummethyl group, phosphonate methyl group, methylmonohalide groups, -B (OH) ₂ , a formyl group, cyano group, vinyl group and the like.

Here includes the halogen atom is a fluorine atom, chlorine atom, bromine atom and iodine atom. With a view to improving the degree of polymerization a bromine atom and iodine atom are preferred.

Examples of the alkylsulfonate residue a methanesulfonate group, ethanesulfonate group, trifluoromethanesulfonate group and the like, examples of the arylsulfonate test include one Benzenesulfonate group, p-toluenesulfonate group and the like, and examples of the arylsulfonate residue a benzylsulfonate group and the like.

When Borate group are illustrated residues of the following formulas.

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

As the sulfonium methyl group, groups of the following formulas are exemplified -CH ₂ S ⁺ Me ₂ X ^- , -CH ₂ S ⁺ Ph ₂ X (wherein X represents a halogen atom and Ph represents a phenyl group).

As phosphoniummethyl group, radicals of the following formula are illustrated -CH ₂ P ⁺ Ph ₃ X ^- (wherein X represents a halogen atom).

As Phosphonatmethylgruppe radicals of the following formula are illustrated -CH ₂ PO (OR ') ₂ (wherein X represents a halogen atom and R 'represents an alkyl group, aryl group or arylalkyl group).

Examples the methylmonohalide group include a methyl fluoride group, Methyl chloride group, methyl bromide group and methyl iodide group.

Preferred substituent substituents related to the polymerization vary depending on the kind of the polymerization reaction and when, for example, a zerovalent nickel complex is used as in the Yamato coupling reaction and the like, halogen atoms, alkylsulfonate radicals, arylsulfo natreste and Arylalkylsulfonatreste listed. When a nickel catalyst or palladium catalyst is used, as in the Suzuki coupling reaction and the like, alkyl sulfonate groups, halogen atoms, borate groups, -B (OH) ₂ and the like are listed.

Especially may be a polymer compound having a repeating unit of the formula (4-1) also by hydrogenation of a polymer compound having a repeating unit of formulas (4-2) to (4-4) with a catalyst obtained by Application of palladium, platinum, rhodium, ruthenium or a Precious metal, prepared by mixing, can be obtained on activated carbon.

in the In contrast, a polymer compound having a repeating unit of the formulas (4-2) to (4-4) also by oxidizing a polymer compound with a repeating unit of the formula (4-1) using of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) or using tetrabutylammonium bromide under basic Conditions are obtained.

If the polymer compound of the present invention has other repeating units as that of the formula (1-1), (1-2) or (1-3), it may be advantageous be that the polymerization under simultaneous presence a compound having two substituents is reacted with the polymerization which are other repeating units than that of the formula (1-1), (1-2) or (1-3).

In addition to the compounds of the above-described formula (16-1), (16-2) or (16-3), compounds having any one of the following formulas (19) to (22) may be used as the starting material. Y ₇ -Ar ₁ -Y ₈ (19) Y ₉ - (Ar ₂ -X ₁ ) _ff -Ar ₃ -Y ₁₀ (20) Y ₁₁ -Ar ₄ -X ₂ -Y ₁₂ (21) Y ₁₃ -X ₃ -Y ₁₄ (22) (wherein Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , ff, X ₁ , X ₂ and X ₃ are as defined above. Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Y ₁₃ and Y ₁₄ each independently represent a polymerizable substituent).

polymer compounds with at least one unit of (5), (6), (7) or (8) in succession in addition to the unit of the above-described formula (1-1), (1-2) or (1-3) can getting produced.

(wobei Ar₆, Ar₇, Ar₈, Ar₉, Ar₁₀, Ar₁₁, X₁₂, x und y die vorstehend angegebene Bedeutung haben. Y₁₅ und Y₁₆ stellen jeweils unabhängig einen Substituenten dar, der mit der Polymerisation in Beziehung steht).As the compound having two substituents related to the polymerization corresponding to the above-described formula (15) which are repeating units other than the repeating units of the above-described formula (1-1), (1-2) or ( 1-3) compounds of the following formula (15-7) are listed.

(wherein Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ , Ar ₁₀ , Ar ₁₁ , X ₁₂ , x and y are as defined above.) Y ₁₅ and Y ₁₆ each independently represent a substituent related to the polymerization stands).

(wobei Re bis Rg die vorstehend angegebenen Bedeutung haben. Y₁₇, Y₁₈, Y₁₉ und Y₂₀ stellen jeweils unabhängig einen Substituenten dar, der mit der Polymerisation in Beziehung steht).Further preferred are compounds of the formula (15-8) or the formula (15-9).

(wherein Re to Rg are as defined above. Y ₁₇ , Y ₁₈ , Y ₁₉ and Y ₂₀ each independently represent a substituent related to the polymerization).

Specifically, the production method of the present invention can be obtained by dissolving a compound having plural substituents related to the condensation polymerization as a monomer, if necessary in an organic solvent, and using, for example, an alkali and a suitable catalyst at temperatures of the melting point or higher and the boiling point or lower of the organic solvent. Known methods, for example, in Organic Reactions, Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965 . Organic Syntheses, Collective Volume VI, pp. 407-411, John Wiley & Sons, Inc., 1988 . Chem. Rev., Vol. 95, p. 2457 (1995), J. Organmet. Chem., Vol. 576, p. 147 (1999) . Makromol. Chem., Macromol. Symp., Vol. 12, p. 229 (1987) and the like can be used.

at the process for producing a polymer compound of the present invention Invention may be a known polymerization reaction according to a Substituents are used, which with the polymerization of a Compound of the above-described formulas (16-1) to (16-3) and (22) to (25).

When the polymer compound of the present invention gives a double bond in the polymerization, for example, in JP-A No. 5-202355 described method listed. More specifically, methods of polymerizing a compound having a formyl group and a compound having a phosphoniummethyl group or polymerizing a compound having a formyl group and a phosphoniummethyl group by the Wittig reaction, polymerizing a compound having a vinyl group and a compound having a halogen atom by the Heck reaction, Polymerization of a compound having two or more methylmonohalide groups by a dehalogenation hydrogen method, polymerization of a compound having two or more sulfonium methyl groups by a sulfonium salt decomposition method, polymerization of a compound having a formyl group and a cyano group by the Knoevenagel reaction, and the like A method of polymerizing a compound having two or more formyl groups by the McMurry reaction and the like.

If the polymer compound of the invention has a triple bond in a main chain can, for Example using the Heck reaction or the Sonogashira reaction become.

When no double bond or triple bond is produced, a method of polymerization from the corresponding monomer by the Suzuki coupling reaction, a method of polymerization by the Grignard reaction, a method of polymerization with a nickel (0) complex, a method of polymerization with an oxidizing agent such as FeCl ₃ and the like, a method of electrochemical oxidation polymerization, a method by decomposing a polymer intermediate having a suitable leaving group and the like.

From They are the polymerization by the Wittig reaction, polymerization by the Heck reaction, polymerization by the Knoevenagel reaction, the method of polymerization by the Suzuki coupling reaction, Method of polymerization by the Grignard reaction and method the polymerization with a zerovalent nickel complex because of lightweight structure control preferred.

Among the production processes of the present invention, a production process is preferred in which, when polymerizing a compound of formula (16-1), (16-2) or (16-3) individually or together with at least one compound selected from formulas (19) to (22), Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ , Y ₁₈ , Y ₁₉ and Y ₂₀ each independently represent a halogen atom, an alkylsulfonate residue, arylsulfonate residue or arylalkylsulfonate residue, and the condensation polymerization is carried out in the presence of a zero-valent nickel complex.

When The starting substance is dihalide compounds, bis (alkylsulfonate) compounds, Bis (arylsulfonate) compounds, bis (arylalkylsulfonate) compounds or haloalkylsulfonate compounds, Halo-arylsulfonate compounds, halo-arylalkylsulfonate compounds, alkylsulfonate-arylsulfonate compounds, Alkylsulfonate Arylalkylsulfonatverbindungen and arylsulfonate arylalkyl sulfonate compounds.

Among the production processes of the present invention, a preparation process is preferred in which, when polymerizing a compound of the formula (16-1), (16-2) or (16-3) individually or together with at least one compound selected from the formulas (19) bis (22), Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ , Y ₁₈ , Y ₁₉ and Y ₂₀ each independently represent a halogen atom, an alkylsulfonate residue, arylsulfonate residue, arylalkylsulfonate residue, -B (OH) ₂ or a borate group, the ratio of the sum of the moles of halogen atoms, alkylsulfonate residues, arylsulfonate residues and Arylalkylsulfonatreste to the sum of the number of moles of -B (OH) ₂ and borate groups is substantially 1 (usually K / J is in the range of 0.7 to 1.2) and the condensation polymerization is carried out using a nickel or palladium catalyst.

When certain combinations of starting compounds become combinations of dihalide compounds, bis (alkylsulfonate) compounds, bis (arylsulfonate) compounds or bis (arylalkylsulfonate) compounds with diboronic acid compounds or diborate compounds.

Further become halogen boric acid compounds, Halogenated borate compounds, alkylsulfonate-boric acid compounds, Alkyl sulfonate borate compounds, aryl sulfonate boric acid compounds, Aryl sulfonate borate compounds, aryl alkyl sulfonate boric acid compounds, Aryl alkyl sulfonate-boric acid compounds, Aryl alkyl sulfonate-borate compounds listed

The organic solvents varies depending from the compound to be used and the implementation, and it is preferred that the solvent to be used sufficient one Deoxidation treatment is subjected, and the reaction under an inert atmosphere to expire in the General side reactions to suppress. Similarly, a dehydration treatment preferably performed. Here is the case of a conversion in a two-phase system with Water, such as the Suzuki coupling reaction, not included.

Demonstrates as a solvent become saturated Hydrocarbons, such as pentane, hexane, heptane, octane, cyclohexane and the like, unsaturated Hydrocarbons, such as benzene, toluene, ethylbenzene, xylene and the like., Halogenated saturated Hydrocarbons, such as carbon tetrachloride, chloroform, dichloromethane, Chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, Chlorocyclohexane, bromocyclohexane and the like, halogenated unsaturated hydrocarbons, such as chlorobenzene, dichlorobenzene, trichlorobenzene and the like, alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, t-butyl alcohol and Like., Carboxylic acids, like formic acid, Acetic acid, propionic and the like, ethers, such as dimethyl ether, diethyl ether, methyl t-butyl ether, tetrahydrofuran, Tetrahydropyran, dioxane and the like, amines, such as trimethylamine, triethylamine, N, N, N ', N'-tetramethylethylenediamine, pyridine and Like., And amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methylmorpholine and the like, and these may be used singly or in admixture be used. Of these, ethers are preferred and tetrahydrofuran and diethyl ether are more preferred.

For the implementation For example, alkalis or suitable catalysts are conveniently added. these can advantageously dependent be chosen by the implementation to be used. As alkalis or catalysts those are preferred that are sufficiently in one in the implementation used solvents to solve. As a method for mixing an alkali or the catalyst illustrates a method wherein a solution of an alkali or a Catalyst slowly while stirring the reaction liquid under an inert atmosphere, such as argon or nitrogen and the like, is added or vice versa the reaction liquid slowly to a solution of alkali or catalyst.

If the polymer compound of the present invention in a polymer LED and the like is used, the purity thereof has an influence on the Properties of a device, such as light-emitting property and Like., It is therefore preferred that the monomers before the polymerization by a process such as distillation, sublimation purification, recrystallization and the like, before performing be purified the polymerization. It is preferable after the Polymerization a refining treatment, such as reprecipitation cleaning, Fractionation by chromatography and the like., Perform.

(16-1) to (16-3), (17-1) to (17-3) and (18-1) to (18-4) which are suitable as the starting materials of the polymer compound of the present invention are brominated obtained from compounds that by substituting Y ₁ to Y ₆ in the above-described formulas with hydrogen atoms.

Especially For example, a compound having a structure of the formula (18-1) may also be exemplified by Hydrogenation of a compound having a structure of the formulas (18-2) to (18-4) with a catalyst obtained by supporting palladium, Platinum, rhodium, ruthenium or a precious metal made by Mixing on charcoal, to be obtained.

in the In contrast, a compound may have a structure of formulas (18-2) to (18-4) also by oxidation of a compound with a Structure of the formula (18-1) using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) or use of tetrabutylammonium bromide under basic Conditions are obtained.

When next the polymer LED of the present invention is illustrated.

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

The organic layer may be a hole-transporting one of a light-emitting layer Layer, electron transporting layer or the like, and Preferably, the organic layer is a light-emitting layer.

Here The light-emitting layer means a layer having a function the light emission, the hole transporting layer means one Layer with a function of transporting holes and the electron-transporting Layer means a layer with the function of transporting Electrons. The electron transporting layer and the hole transporting Layer, in summary, is a charge-transporting layer called. Two or more light-emitting layers, two or more hole-transporting layers or two or more electron-transporting layers Layers can each independently be used.

If the organic layer is a light-emitting layer can the light-emitting layer as an organic layer further a hole transporting material, electron transporting Material or light emitting material included. Here means the light-emitting material is a material that has fluorescence and / or fluorescence Phosphorescence shows.

If a polymer compound of the present invention and a hole transporting agent Material to be mixed is the mixing ratio of the hole-transporting material 1 wt.% to 80 wt.%, preferably 5 wt .-% to 60 wt .-%, based on the total mixture. When a Polymer compound of the present invention and an electron transporting Material to be mixed is the mixing ratio of the electron-transporting material 1 wt .-% to 80 wt .-%, preferably from 5% by weight to 60% by weight, based on the total mixture. Furthermore, when a polymer compound of the present invention and a light-emitting Material to be mixed, the mixing ratio of the light-emitting Material 1 wt.% To 80 wt.%, Preferably 5 wt.% To 60 wt. based on the total mixture. When a polymer compound of the present invention and a light-emitting material, hole-transporting Material and / or electron-transporting material mixed be, is the mixing ratio of the light-emitting material 1 wt% to 50 wt%, preferably 5 wt .-% to 40 wt .-%, the sum of the hole-transporting material and the electron-transporting material is 1 wt .-% to 50 wt .-%, preferably 5 wt .-% to 40 wt .-%, and the content of Polymer compound of the present invention is 99 wt% to 20 wt .-%, based on the total mixture.

As the hole-transporting material, electron-transporting material and light-emitting material to be mixed, known lower molecular weight compounds, triplet light-emitting complexes or polymer compounds can be used, and polymer compounds are preferably used. Examples of the hole-transporting material, electron-transporting material, and light-emitting material as a polymer compound include polyfluorenes, derivatives and copolymers thereof, polyarylenes, derivatives and copolymers thereof, polyarylenevinylenes, derivatives and copolymers thereof, and (co) polymers of aromatic amines and derivatives thereof disclosed in US Pat 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 / 34772 . WO99 / 24526 . WO00 / 22027 . WO00 / 22026 . WO98 / 27136 . US573636 . WO98 / 21262 . US5741921 . WO97 / 09394 . WO96 / 29356 . WO96 / 10617 . EP0707020 . WO95 / 07955 , Japanese Laid-Open Patent Applications ( JP-A) No. 2001-181618 . 2001-123156 . 2001-3045 . 2000-351967 . 2000-303066 . 2000-299189 . 2000-252065 . 2000-136379 . 2000-104057 . 2000-80167 . 10-324870 . 10-114891 . 9-111233 . 9-45478 and the like, a.

When fluorescent material as a lower molecular weight compound can for example naphthalene derivatives, anthracene or derivatives thereof, Perylene or derivatives thereof; coloring Substances such as polymethine, xanthene, coumarin, cyanine and the like; metal complexes of 8-hydroxyquinoline or derivatives thereof; aromatic amines, tetraphenylcyclopentadiene or derivatives thereof, or tetraphenylbutadiene or derivatives thereof and the like can be used.

In particular, known compounds, such as those in JP-A No. 57-51781 and 59-194393 and the like described.

Examples of the triplet light-emitting complex include Ir (ppy) ₃ containing iridium as a central metal, Btp ₂ Ir (acac), PtOEP containing platinum as a central metal, Eu (TAA) ₃ phen containing europium as a central metal, and the like.

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

The Composition of the present invention contains at least one material selected from hole transporting materials, electron transporting Materials and light-emitting materials, and a polymer compound of the present invention and may be used as a light-emitting material or charge transporting material.

The relationship the content of the at least one material selected from hole-transporting materials, electron-transporting materials and light-emitting materials, to a polymer compound of The present invention may be advantageously dependent on the application.

When other embodiment the present invention illustrates a polymer composition the two or more polymer compounds of the present invention contains.

The Thickness of a light-emitting layer in a polymer LED of present invention has an optimum value depending on a material to be used varies, and may advantageously so chosen be that suitable operating voltage and light emission efficiency and is for example 1 nm to 1 μm, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm.

When A method of forming a light-emitting layer becomes, for example illustrates a method of film formation from solution. If the film formation from a solution using a polymer compound of the present invention When making a polymer LED can be a simple Removing a solvent be possible by drying after application of this solution, and also during mixing a charge transporting material and a light emitting Materials can be analogous Means are used extremely advantageously for the production.

When Methods for film formation from a solution can be applied such as spin coating method, casting method, microgravure coating method, Gravure coating process, knife coating process, roll coating process, Wire bar coating method, dip coating method, spray coating method, Screen printing, flexographic printing, offset printing, inkjet printing and the like can be used. In terms of simplicity of patterning and multicolor splitting paint are printing processes such as screen printing, Flexographic printing, offset printing, inkjet printing and the like, preferred.

The Inventive ink composition can as a solution used in printing processes.

In the ink composition of the invention may be at least one polymer compound of the present invention and a solvent be included, and additives, like hole transporting materials, electron transporting Materials, light-emitting materials, stabilizers and the like, can also additionally to the polymer compound of the present invention.

The Ink composition of the present invention means a composition which is liquid in the manufacture of a device, and typically, which is liquid at normal pressure (i.e., 1 atm.) and 25 ° C.

It is not necessarily required that the ink composition dyed the present invention is.

Of the Proportion of the polymer compound of the present invention in the ink composition is usually From 20% by weight to 100% by weight, preferably from 40% by weight to 100% by weight, based on the total weight of the ink composition except one Solvent.

Of the Proportion of a solvent in the ink composition is 1 wt% to 99.9 wt%, preferably From 60% by weight to 99.9% by weight, more preferably from 90% by weight to 99.8% by weight, based on the total weight of the ink composition.

The viscosity of the ink composition varies depending on the printing method, and when the In ink composition, as in an ink-jet printing method and the like, at 25 ° C, the viscosity is preferably in the range of 2 to 20 mPa · s in order to prevent clogging and a flying curve upon removal.

Demonstrates as a solvent, that in the ink composition of the invention It is used as a solvent chlorine-based, such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2-trichloroethane, Chlorobenzene, o-dichlorobenzene and the like, ethereal solvents, such as tetrahydrofuran, Dioxane and the like, aromatic hydrocarbon solvents such as toluene, xylene and the like, aliphatic hydrocarbon solvents such as cyclohexane, Methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and Like., Ketone solvent, such as acetone, methyl ethyl ketone, cyclohexanone and the like, ester solvents, such as ethyl acetate, butylacatate, ethylcellosolve acetate and the like, polyvalent ones Alcohols, such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, Ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, Triethylene glycol monoethyl ether, glycerol, 1,2-hexanediol and the like, and derivatives thereof, alcohol solvents, such as methanol, ethanol, propanol, isopropanol, cyclohexanol and the like., sulfoxide such as dimethyl sulfoxide and the like, and amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide and the like. These organic solvents can used singly or in combination of two or more. Of the solvents described above, at least an organic solvent having a structure containing at least one benzene ring and one Melting point of 0 ° C or lower and has a boiling point of 100 ° C or higher, preferably contain.

In Terms of the type of solvent are aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, Esterlösungsmittel and ketone solvent in terms of solubility the polymer compound of the invention in an organic solvent, uniformity in film formation, viscosity property and the like, and toluene, xylene, ethylbenzene, diethylbenzene, Trimethylbenzene, mesitylene, n-propylbenzene, i-propylbenzene, n-butylbenzene, i-butylbenzene, s-butylbenzene, anisole, ethoxybenzene, 1-methylnaphthalene, Cyclohexanone, cyclohexylbenzene, dicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, methylbenzoate, 2-propylcyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2-decanone and dicyclohexyl ketone are preferred and at least one of xylene, anisole, mesitylene, Cyclohexylbenzene, bicyclohexyl and methyl benzoate are more preferably included.

The Number of types of solvents in the ink composition is preferably 2 or more, stronger preferably 2 to 3, more preferably 2 in view of the film formability and in view of the characteristics of the device and the like.

If two solvents in the ink composition, a solvent may be used of which in solid state at 25 ° C be. With regard to the film formability is preferred that a Solvent one Boiling point of 180 ° C or higher and another solvent a boiling point of 180 ° C or lower, and it is more preferable that a solvent a boiling point of 200 ° C or higher and another solvent a boiling point of 180 ° C or lower. In terms of viscosity is preferred that both of the two solvents a polymer compound of the present invention in an amount of 0.2% by weight or more at 60 ° C solve and it is preferred that one of the two solvents be a polymer compound of the present invention in an amount of 0.2% by weight or more at 25 ° C solves.

If three solvents in the ink composition, one to two solvents may be used of which at 25 ° C be in the solid state. In terms of film-making is preferably that at least one of the three solvents has a boiling point from 180 ° C or higher and at least one solvent a boiling point of 180 ° C or lower, and is more preferable that at least one of the three solvents a boiling point of 200 ° C or higher and 300 ° C or lower and at least one solvent has a boiling point from 180 ° C or lower. In terms of viscosity is preferred that two of the three solvents a polymer compound of the present invention in an amount of 0.2% by weight or more at 60 ° C solve and it is preferred that one of the three solvents is a polymer compound of the present invention in an amount of 0.2% by weight or more at 25 ° C solves.

If two or more solvents in the ink composition, the proportion of a solvent with the highest Boiling point preferably 40 to 90% by weight, more preferably 50 to 90% by weight, more preferably 65 to 85% by weight, based on the weight of all solvent in the ink composition in terms of viscosity and film formability.

When Ink compositions of the present invention are in view on viscosity and Filmbildbarkeit a composition consisting of anisole and Bicyclohexyl, a composition consisting of anisole and cyclohexylbenzene, a composition consisting of xylene and bicyclohexyl, a Composition consisting of xylene and cyclohexylbenzene, and a Composition consisting of mesitylene and methyl benzoate, preferred.

From the additives, those contained in the ink composition of the present invention could be, are used as a hole-transporting layer of polyvinylcarbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having a aromatic amine in a 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 and poly (2,5-thienylenevinylene) or derivatives thereof.

Listed as electron-transporting material are oxadiazole derivatives, anthraquinodimethane or Derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or Derivatives thereof, anthraquinone or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or Derivatives thereof, diphenoquinone derivatives; Metal complexes of 8-hydroxyquinoline or derivatives thereof; Polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof.

Listed as light-emitting material are naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof; coloring substances, such as polymethine, xanthene, coumarin, cyanine and the like; metal complexes of 8-hydroxyquinoline or derivatives thereof; aromatic amines, tetraphenylcyclopentadiene or derivatives thereof, tetraphenylbutadiene or derivatives thereof and like.

The Ink composition (solution) The present invention may contain additives for adjusting the viscosity and / or surface tension additionally to the polymer compound of the present invention. When additions can Polymer compounds with higher Molecular weight (thickener) to increase viscosity, poor Solvent, Lower molecular weight compounds for reducing the Viscosity, surfactants Means for reducing the surface tension and the like. Suitably combined and used.

When above-described polymer compound of higher molecular weight those in the same solvent as for the polymer compound of the present invention are soluble and do not disturb the light emission and the charge transport, advantageous. For example, you can Polystyrene and polymethyl methacrylate of higher molecular weight or Higher molecular weight polymer compounds of the present invention and the like can be used. The weight average molecular weight is preferably 500,000 or more and more preferably 1,000,000 or more.

One bad solvent can also be used as a thickener. That is, the viscosity can be through Add a small amount of bad solvent for solid Ingredients in a solution elevated become. If a bad solvent For this Purpose is added the type and amount of added solvent advantageously chosen so be that they have no deposition of solid components in one solution cause.

The Ink composition (solution) The present invention can provide an antioxidant for improvement the preservation stability additionally to the polymer compound of the present invention. When Antioxidants are those that are in the same solvent as for the polymer compound of the present invention are soluble and do not disturb the light emission and the charge transport, and illustrate phenol-based antioxidants, Phosphorus antioxidant and the like

in the With regard to solubility the polymer compound of the present invention in a solvent is the difference between the solubility parameter of the solvent and solubility parameters the polymer compound is preferably 10 or less, more preferably 7 or less.

The solubility parameter of the solvent and the solubility parameter of the polymer compound of the present invention can be measured by a method described in U.S. Pat. Solvent Handbook (Kodansha Ltd. Publishers, 1976) "is described.

Listed as Polymer LED of the present invention will be a polymer LED with an electron transporting layer between a cathode and a light-emitting layer, a polymer LED with a hole-transporting layer between an anode and a light-emitting layer, a polymer LED with an electron transporting layer between one Cathode and a light-emitting layer is provided, and with a hole transporting layer between one Anode and a light-emitting layer is provided, and like.

• a) Anode/lichtemittierende Schicht/Kathode
• b) Anode/lochtransportierende Schicht/lichtemittierende Schicht/Kathode
• c) Anode/lichtemittierende Schicht/elektronentransportierende Schicht/Kathode
• d) Anode/lochtransportierende Schicht/lichtemittierende Schicht/elektronentransportierende Schicht/Kathode

(wobei/eine benachbarte Laminierung von Schichten bezeichnet, auch in den folgenden Beschreibungen anwendbar).For example, the following structures a) to d) are particularly illustrated.

• a) anode / light emitting layer / cathode
• b) anode / hole transporting layer / light emitting layer / cathode
• c) anode / light emitting layer / electron transporting layer / cathode
• d) anode / hole transporting layer / light emitting layer / electron transporting layer / cathode

(where / denotes adjacent lamination of layers, also applicable in the following descriptions).

The Polymer LED of the present invention also includes those in which a polymer compound of the present invention in a hole transporting Layer and / or an electron-transporting layer included is.

If the polymer compound of the present invention in a hole transporting Layer is used, it is preferred that the polymer compound the present invention is a polymer compound having a contains hole transporting remainder, and certain examples thereof include a copolymer having a aromatic amine, a copolymer with stilbene and the like.

If the polymer compound of the present invention in an electron transporting layer is used, it is preferred that the polymer compound of the present Invention is a polymer compound having an electron transporting Contains rest, and certain examples thereof include a copolymer with oxadiazole, a copolymer with triazole, a copolymer with quinoline, a copolymer with quinoxaline, a copolymer with benzothiaziazole and the like.

If the polymer LED according to the invention has a hole transporting layer are to be used as hole-transporting material polyvinylcarbazole or its derivatives, Polysilane or its derivatives, polysiloxane derivatives with an aromatic Amine in a side chain or main chain, pyrazoline derivatives, arylamine derivatives, Stilbene derivatives, triphenyldiamine derivatives, polyaniline or its Derivatives, polythiophene or its derivatives, polypyrrole or its Derivatives, poly (p-phenylenevinylene) or its derivatives, poly (2,5-thienylenevinylene) or its derivatives and the like listed.

In particular, as the hole-transporting material, those used in JP-A No. 63-70257 and 63-175860 . JP-A No. 2-135359 . 2-135361 . 2-209988 . 3-37992 and 3-152184 are described, and the like. Listed.

Under They are preferred as a hole transporting material that is in a hole transporting layer is used, hole transporting High molecular weight materials such as polyvinylcarbazole or its derivatives, polysilane or its derivatives, polysiloxane derivatives with a residue of an aromatic amine compound in a side chain or main chain, polyaniline or its derivatives, polythiophene or its derivatives, poly (p-phenylenevinylene) or its derivatives, poly (2,5-thienylenevinylene) or its derivatives and the like, and more preferred are polyvinylcarbazole or its Derivatives, polysilane or its derivatives and polysiloxane derivatives with an aromatic amine in a side chain or main chain.

When hole transporting material of a low molecular weight compound be pyrazoline derivatives, arylamine derivatives, stilbene derivatives and Triphenyldiamine derivatives illustrated. In the case of a hole transporting It is preferably in low molecular weight material in a polymer binder dispersed in use.

As the polymer binder to be mixed, those which do not extremely disturb the charge transport are preferable, and those which do not show strong absorption of visible rays are suitably used. As polymer binders are poly (N-vinylcarbazole), polyaniline or its derivatives, polythiophene or its derivatives, poly (p-phenylenevinylene) or its derivatives, poly (2,5-thienylenevinylene) or its Deri vate, polycarbonate, polyacrylate, polymethylacrylate, polymethylmethacrylate, polystyrene, polyvinylchloride, polysiloxane and the like.

polyvinylcarbazole or its derivatives are, for example, vinyl monomers cationic polymerization or radical polymerization.

As polysilane or its derivatives, compounds described in Chem. Rev., Vol. 89, p. 1359 (1989), GB Patent No. 2300196 and the like, illustrated. Also, as the synthesis method, methods described in these publications can be used, and in particular, the kipping method is suitably used.

When Polysiloxane or its derivatives are those having a structure of aforementioned hole transporting material with low Suitable molecular weight in its side chain or main chain, because the siloxane skeleton structure low hole transport characteristic shows. In particular, those will with a hole-transporting aromatic amine in a side chain or main chain illustrated.

Even though the method of forming a hole transporting layer is not is particularly limited is a method of film formation from a mixed solution with a polymer binder in the case of a hole transporting material illustrated with low molecular weight. A method of Film formation from a solution becomes in the case of a high molecular weight hole transporting material illustrated.

When Solvent, that for film formation from a solution are used, those are a hole transporting material can not solve especially limited. Illustrated as a solvent become solvents chlorine-based, such as chloroform, dichloromethane, 1,2-dichloroethane and Like., Ether solvents, such as Tetrahydrofuran and the like, aromatic hydrocarbon solvents, such as toluene, xylene and the like, ketone solvents such as acetone, methyl ethyl ketone and the like, ester solvents, such as ethyl acetate, butyl acetate, ethyl cellosolve acetate and the like.

When Methods of film formation from a solution can be applied such as a spin coating method, casting method, microgravure coating method, Gravure coating process, knife coating process, roll coating process, Wire bar coating method, dip coating method, spray coating method, Screen printing, flexographic printing, offset printing, inkjet printing and the like., From a solution be used.

Of the optimum value of the thickness of a hole-transporting layer varies dependent of a material to be used, and the thickness can be advantageously so chosen be that suitable operating voltage and appropriate efficiency the light emission, and at least one thickness, the no generation of pinholes is required, and if it is too thick, the operating voltage of a device decreases undesirable to. So is the thickness of the hole-transporting layer, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm.

If the polymer LED of the present invention is an electron transporting agent Layer may have known materials as an electron transporting agent to be used Material are used, and exemplified are oxadiazole derivatives, Anthraquinodimethane or its derivatives, benzoquinone or its Derivatives, naphthoquinone or its derivatives, anthraquinone or its Derivatives, tetracyanoanthraquinodimethane or its derivatives, fluorenone derivatives, Diphenyldicyanoethylene or its derivatives, diphenoquinone derivatives or metal complexes of 8-hydroxyquinoline or its derivatives, polyquinoline or its derivatives, polyquinoxaline or its derivatives, polyfluorene or its derivatives and the like.

In particular, those illustrated in FIG JP-A No. 63-70257 and 63-175860 . JP-A No. 2-135359 . 2-135361 . 2-209988 . 3-37992 and 3-152184 and the like are described.

From they are oxadiazole derivatives, benzoquinone or its derivatives, anthraquinone or its derivatives or metal complexes of 8-hydroxyquinoline or its derivatives, polyquinoline or its derivatives, polyquinoxaline or its derivatives, polyfluorene or its derivatives, and 2- (4-biphenylyl) - (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, Anthraquinone, tris (8-quinolinol) aluminum and polyquinoline are more preferred.

The method for forming an electron transporting layer is not particularly limited and in a low molecular weight electron transporting material, a vacuum evaporation method from a powder or a film forming method from a solution or a molten state is exemplified, or in a high molecular weight electron transporting material, a film forming method from a solution or molten state is exemplified. Upon film formation from a solution or molten state, the above polymer binder may be used together.

When Solvent, that for film formation from a solution are used, those which are electron transporting are suitable Material and / or polymer binder can solve. Illustrated as a solvent become solvents chlorine-based, such as chloroform, dichloromethane, dichloroethane and Like., Ether solvents, such as tetrahydrofuran and the like, aromatic hydrocarbon solvents, such as toluene, xylene and the like, ketone solvents such as acetone, methyl ethyl ketone and the like, ester solvents, such as ethyl acetate, butyl acetate, ethyl cellosolve acetate and the like.

When Methods of film formation from a solution can be applied such as a spin coating method, casting method, microgravure coating method, Gravure coating process, knife coating process, roll coating process, Wire bar coating method, dip coating method, spray coating method, Screen printing, flexographic printing, offset printing, inkjet printing and the like., From a solution be used.

Of the optimum value of the thickness of an electron-transporting layer varies depending of a material to be used, and the thickness can be advantageously so chosen be that suitable operating voltage and appropriate efficiency of the light emission, and at least one thickness, none Creation of pinholes is required, and when If it is too thick, the operating voltage of a device undesirably increases. So is the thickness of the electron-transporting layer, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm.

From the charge transporting layers adjacent to one Be provided electrode, those who have a function the improvement of the efficiency of the charge injection from a Have electrode and an effect of reducing the operating voltage a device, in particular in particular charge injection layer (Hole injection layer, electron injection layer) in some make called.

Further can improve the close adhesion with an electrode and the Improve the charge injection from an electrode the above called charge injection layer or an insulation layer with a thickness of 2 nm or less, adjacent to an electrode, be provided, and to improve the close adhesion of a interface and for preventing mixing and the like. Can be a thin buffer layer at an interface a charge transporting layer or a light emitting layer Layer inserted become.

The Order and number of layers to be laminated and the thicknesses of the respective layers can in terms of light emission efficiency and lifetime the device chosen suitable become.

The inventive polymer compound can also be used as a polymeric electric field effect transistor as a organic thinner Semiconductor film can be used. In terms of the structure of the polymeric electric field effect transistor, it is usually advantageous that a source electrode and a drain electrode in close proximity to one another are provided active layer composed of a polymer is, and gate electrodes are provided, which is an insulating layer in close proximity surrounded to an active layer.

Of the Polymeric electric field effect transistor is usually mounted on a carrier substrate educated. The material of the carrier substrate is not particularly limited with the measure, that it does not have a property as an electric field effect transistor disturbs, and a glass substrate, flexible film substrate and plastic substrate can also be used.

The electric field effect transistor can be produced by known methods, for example, a in JP-A No. 5-110069 described method.

It is very advantageous and preferred for the preparation to use a polymer which is soluble in an organic solvent when forming the active layer. As a method of film formation from a Lö A solution prepared by dissolving a polymer in an organic solvent can employ deposition methods such as spin coating method, casting method, microgravure coating method, gravure coating method, knife coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, offset printing method, ink jet printing method and the like.

One sealed polymeric electric field effect transistor obtained under performing a sealing after the production of a polymeric electrical Field effect transistor is preferred. This becomes a polymeric one electric field effect transistor protected from atmospheric air, and a deterioration of a property of a polymeric electrical Field effect transistor can be suppressed.

When Sealing methods become a method for covering with a UV curing Resin, thermosetting Resin, inorganic SiONx film and the like, a method of sticking with glass plates or foils together with a UV curing Resin, thermosetting Resin and the like, and other methods listed. To be effective against atmospheric To protect air For example, it is preferred that a method of preparing a polymeric electric field effect transistor to the isolation thereof without Exposure to atmospheric air (For example, in a dried nitrogen atmosphere, in a vacuum and the like.) Is performed.

In of the present invention are provided as a polymer LED with one Charge injection layer (electron injection layer, hole injection layer) a polymer LED with a charge injection layer adjacent to a cathode, and a polymer LED having a charge injection layer lists provided adjacent to an anode.

• e) Anode/Locheinspeisungsschicht/lichtemittierende Schicht/Kathode
• f) Anode/lichtemittierende Schicht/Ladungseinspeisungsschicht/Kathode
• g) Anode/Ladungseinspeisungsschicht/lichtemittierende Schicht/Ladungseinspeisungsschicht/Kathode
• h) Anode/Ladungseinspeisungsschicht/lochtransportierende Schicht/lichtemittierende Schicht/Kathode
• i) Anode/lochtransportierende Schicht/lichtemittierende Schicht/Ladungseinspeisungsschicht/Kathode
• j) Anode/Ladungseinspeisungsschicht/lochtransportierende Schicht/lichtemittierende Schicht/Ladungseinspeisungsschicht/Kathode
• k) Anode/Ladungseinspeisungsschicht/lichtemittierende Schicht/elektronentransportierende Schicht/Kathode
• l) Anode/lichtemittierende Schicht/elektronentransportierende Schicht/Ladungseinspeisungsschicht/Kathode
• m) Anode/Ladungseinspeisungsschicht/lichtemittierende Schicht/elektronentransportierende Schicht/Ladungseinspeisungsschicht/Kathode
• n) Anode/Ladungseinspeisungsschicht/lochtransportierende Schicht/lichtemittierende Schicht/elektronentransportierende Schicht/Kathode
• o) Anode/lochtransportierende Schicht/lichtemittierende Schicht/elektronentransportierende Schicht/Ladungseinspeisungsschicht/Kathode
• p) Anode/Ladungseinspeisungsschicht/lochtransportierende Schicht/lichtemittierende Schicht/elektronentransportierende Schicht/Ladungseinspeisungsschicht/Kathode

For example, the following structures e) to p) are specifically listed.

• e) anode / hole feed 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 transporting layer / light emitting layer / cathode
• i) anode / hole transporting layer / light emitting layer / charge injection layer / cathode
• j) anode / charge injection layer / hole transporting layer / light emitting layer / charge injection layer / cathode
• k) anode / charge injection layer / light emitting layer / electron transporting layer / cathode
• l) anode / light emitting layer / electron transporting layer / charge injection layer / cathode
• m) anode / charge injection layer / light emitting layer / electron transporting layer / charge injection layer / cathode
• n) anode / charge injection layer / hole transporting layer / light emitting layer / electron transporting layer / cathode
• o) anode / hole transporting layer / light emitting layer / electron transporting layer / charge injection layer / cathode
• p) anode / charge injection layer / hole transporting layer / light emitting layer / electron transporting layer / charge injection layer / cathode

When certain examples of the charge injection layer become a layer, which contains an electrically conductive polymer, a layer between an anode and a hole transporting layer is and a material with an ionization potential with an intermediate value between that of an anode material and that of a hole transporting Material contained in the hole-transporting layer, contains a layer between a cathode and an electron transporting Layer is provided and a material with electron affinity with a Intermediate value between that of a cathode material and that of a electron-transporting material contained in the electron-transporting layer is provided, is included and the like listed.

When the above-mentioned charge injection layer contains an electroconductive polymer, the electrical conductivity of the electroconductive polymer is preferably 10 ^-5 S / cm or more and 10 ³ or less, and more preferably 10 ^-5 S / cm for reducing the leakage current between light-emitting pixels or more and 10 ² or less, more preferably 10 ^-5 S / cm or more and 10 ¹ or less.

When the above-mentioned charge injection layer contains an electroconductive polymer, For example, the electrical conductivity of the electroconductive polymer is preferably 10 ^-5 S / cm or more and 10 ³ or less, and more preferably 10 ^-5 S / cm or more and 10 ² or less, more preferably 10 to reduce the leakage current between light-emitting picture elements ^-5 S / cm or more and 10 ¹ or less.

Usually, to adjust the electroconductivity of the electroconductive polymer to 10 ^-5 S / cm or more and 10 ³ or less, the electroconductive polymer is doped with an appropriate amount of ions.

In Referring to the kind of ion to be doped, an anion becomes one Locheinspeisungsschicht used, and a cation is in one Electron feed layer used. Examples of the anion include Polystyrene sulfonation, alkylbenzene sulfonation, camphorsulfonation and the like, and examples of the cation include lithium ion, sodium ion, Potassium ion, tetrabutylammonium ion and the like.

The Thickness of a charge injection layer is, for example, 1 nm to 100 nm, preferably 2 nm to 50 nm.

The Material used in a charge injection layer may advantageously geeigent with respect to a material of an electrode or adjacent Layer selected and illustrate polyaniline and its derivatives, Polythiophene and its derivatives, pyrrole and its derivatives, polyphenylenevinylene and its derivatives, polythienylenevinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, electrically conductive polymers, such as a polymer that has an aromatic amine structure in a main chain or side chain, metal phthalocyanine (copper phthalocyanine and the like), carbon and the like.

The Insulating layer with a thickness of 2 nm or less has the Function to make the charge injection easy. As a material the above-mentioned insulating layer are metal fluorides, metal oxides, organic insulating materials and the like. listed. As a polymer LED, with an insulating layer having a thickness of 2 nm or less is a polymer LED with an insulating layer with a Thickness of 2 nm or less provided adjacent to a cathode, and a polymer LED with an insulating layer having a thickness of 2 nm or less, provided adjacent to an anode.

• q) Anode/Isolationsschicht mit einer Dicke von 2 nm oder weniger/lichtemittierende Schicht/Kathode
• r) Anode/lichtemittierende Schicht/Isolationsschicht mit einer Dicke von 2 nm oder weniger/Kathode
• s) Anode/Isolationsschicht mit einer Dicke von 2 nm oder weniger/lichtemittierende Schicht/Isolationsschicht mit einer Dicke von 2 nm oder weniger/Kathode
• t) Anode/Isolationsschicht mit einer Dicke von 2 nm oder weniger/lochtransportierende Schicht/lichtemittierende Schicht/Kathode
• u) Anode/lochtransportierende Schicht/lichtemittierende Schicht/Isolationsschicht mit einer Dicke von 2 nm oder weniger/Kathode
• v) Anode/Isolationsschicht mit einer Dicke von 2 nm oder weniger/lochtransportierende Schicht/lichtemittierende Schicht/Isolationsschicht mit einer Dicke von 2 nm oder weniger/Kathode
• w) Anode/Isolationsschicht mit einer Dicke von 2 nm oder weniger/lichtemittierende Schicht/elektronentransportierende Schicht/Kathode
• x) Anode/lichtemittierende Schicht/elektronentransportierende Schicht/Isolationsschicht mit einer Dicke von 2 nm oder weniger/Kathode
• y) Anode/Isolationsschicht mit einer Dicke von 2 nm oder weniger/lichtemittierende Schicht/elektronentransportierende Schicht/Isolationsschicht mit einer Dicke von 2 nm oder weniger/Kathode
• z) Anode/Isolationsschicht mit einer Dicke von 2 nm oder weniger/lochtransportierende Schicht/lichtemittierende Schicht/elektronentransportierende Schicht/Kathode
• aa) Anode/lochtransportierende Schicht/lichtemittierende Schicht/elektronentransportierende Schicht/Isolationsschicht mit einer Dicke von 2 nm oder weniger/Kathode
• ab) Anode/Isolationsschicht mit einer Dicke von 2 nm oder weniger/lochtransportierende Schicht/lichtemittierende Schicht/elektronentransportierende Schicht/Isolationsschicht mit einer Dicke von 2 nm oder weniger/Kathode

In particular, the following structures q) to ab) are listed, for example.

• q) anode / insulation layer with a thickness of 2 nm or less / light-emitting layer / cathode
• r) anode / light-emitting layer / insulation layer having a thickness of 2 nm or less / cathode
• s) anode / insulation layer having a thickness of 2 nm or less / light-emitting layer / insulation layer having a thickness of 2 nm or less / cathode
• t) anode / insulating layer having a thickness of 2 nm or less / hole transporting layer / light emitting layer / cathode
• u) anode / hole transporting layer / light emitting layer / insulating layer having a thickness of 2 nm or less / cathode
• v) An anode / insulating layer having a thickness of 2 nm or less / hole transporting layer / light emitting layer / insulating layer having a thickness of 2 nm or less / cathode
• w) anode / insulation layer having a thickness of 2 nm or less / light-emitting layer / electron-transporting layer / cathode
• x) anode / light emitting layer / electron transporting layer / insulating layer having a thickness of 2 nm or less / cathode
• y) anode / insulating layer having a thickness of 2 nm or less / light emitting layer / electron transporting layer / insulating layer having a thickness of 2 nm or less / cathode
• z) anode / insulation layer having a thickness of 2 nm or less / hole transporting layer / light emitting layer / electron transporting layer / cathode
• aa) Anode / hole transporting layer / light emitting layer / electron transporting layer / insulating layer having a thickness of 2 nm or less / cathode
• ab) anode / insulation layer having a thickness of 2 nm or less / hole transporting layer / light emitting layer / electron transporting layer / insulating layer having a thickness of 2 nm or less / cathode

The base plate for forming a polymer LED of the present invention may advantageously be those which do not change in forming an electrode and forming a layer of an organic material and examples thereof include glass, plastic, polymeric films, silicon base plates, and the like. In an opaque baseplate, it is preferred that the opposing electrode be transparent or semi-transparent.

Usually At least one of anode and cathode in a polymer LED according to the invention is transparent or semitransparent. Preferably, the anode side is transparent or semitransparent.

When Material of the anode become electrically conductive metal oxide membranes, semi-transparent metal films and the like used. In particular, be Membranes (NESA and the like) formed using an electric conductive glass composed of indium oxide, zinc oxide, tin oxide and their compounds indium · tin · oxide (ITO), Indium · Zinc · Oxide and Like., And gold, platinum, silver, copper and the like. Used, and preferred are ITO, indium · zinc · oxide and Tin oxide. As a manufacturing method, a vacuum evaporation method, Sputtering process, ion plating process, electroplating process and the like listed. When Anode can organic transparent conductive membranes of polyaniline or its Derivatives, polythiophene or its derivatives and the like. Used become.

The Thickness of an anode may be suitable in terms of light transmission and electrical conductivity are chosen, and is for example 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm.

Around To make the charge injection easy, a layer can be built up of a phthalocyanine derivative, electrically conductive polymer, carbon and the like, or a layer having an average thickness of 2 nm or less, composed of a metal oxide, metal fluoride, organic Insulating material or the like., Are provided on an anode.

When Material of a cathode that is present in a polymer LED Are used, are materials with a small work function prefers. For example, metals such as lithium, sodium, potassium, rubidium, cesium, Beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, Vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, Ytterbium and the like, alloys composed of at least two or more several of them, alloys, composed of at least one of them and at least one of gold, silver, platinum, copper, manganese, titanium, Cobalt, nickel, tungsten and tin, and graphite or graphite intercalation compounds and the like are used. As examples of the alloy, a Magnesium-silver alloy, magnesium indium alloy, magnesium-aluminum alloy, Indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, Lithium-indium alloy, calcium-aluminum alloy and the like. The Cathode may have a lamination structure consisting of two or more Layers exists.

The Thickness of the cathode may be in terms of electrical conductivity and durability suitably chosen be, and is for example 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm.

When Methods of making a cathode are a vacuum deposition method, Sputtering method, lamination method of thermal press bonding a metal film and the like. Used. Between a cathode and a layer of an organic substance, a layer can be constructed of an electrically conductive polymer or a layer with a average thickness of 2 nm or less, composed of a metal oxide, Metal fluoride, organic insulating material or the like become. After making a cathode, a protective layer for Protect the polymer LED are attached. For stable use of the polymer LED for one long period is preferred, a protective layer and / or protective cover to protect to install the device against environmental influences.

As the protective layer, there may be used polymer compounds, metal oxides, metal fluorides, metal borides and the like. As a protective cover, a glass plate, a plastic plate having a surface subjected to a water-permeation-reducing treatment and the like, and a method of sealing by adhering the cover to a base plate of the thermosetting resin or photo-curing resin device may be used suitably used. When a distance is maintained by using a spacer, it is easy to prevent scratching of a device. When the space is filled with an inert gas such as nitrogen and argon, oxidation of a cathode can be prevented. Further, by introducing a drying agent such as barium oxide and the like into the gap, damage to a device by moisture absorbed in the production process is easily suppressed. Among them, one or more of the methods is preferably ver applies.

The Polymer LED of the present invention can be used for area light sources, segment displays, Dot Matrix Displays, Liquid Crystal Displays (for example, backlight of a liquid crystal display) become.

To the Receiving light emission in the form of a plate using a polymer LED of the present invention a plane Anode and a plane Advantageously, cathodes are mounted so that they overlap. There is an input for receiving light emission in the form of a pattern Method in which one equipped with windows in the form of a pattern Mask on the surface the above-mentioned light-emitting device in the mold a plate, a method in which a layer of a organic substance on a non-light-emitting part with extremely big Thickness is formed to produce substantially no light emission, a method in which either an anode or a cathode or both electrodes are formed in the form of a pattern. By Forming a pattern with one of these methods and laying several Electrodes, so that independent can be switched on / off, a display device of Get segment types that display numbers and letters and simple markings and the like. Is capable. Furthermore, it may be for Obtaining a dot matrix device may be advantageous in that both an anode as well as a cathode in the form of a strip formed and be placed so that they intersect. With a procedure of separate dyeing several light-emitting materials with different emission colors or a method of using a color filter or fluorescent exchange filter will it be possible to get a partial color display or multi-color display. The dot matrix device can be passive or active in combination with TFT and the like operate. These displays can act as a display of computer, Televisions, portable terminals, mobile phones, caravans, Viewers of video cameras and the like can be used.

The aforesaid light emitting device in the form of a area is thin of the self-emitting Type and may suitably be used as a surface light source for backlighting a liquid crystal display or a surface light source used for lighting. If a flexible base plate It can also be used as a light source or display used in the form of a curved surface become.

Examples are illustrative of the present invention below further shown in detail, however, the present invention not limited to them.

(Number average the molecular weight and weight average molecular weight)

Here are expressed as number average molecular weight and weight average molecular weight refers to polystyrene number average of Molecular weight and polystyrene weight average molecular weight with GPC (manufactured by Shimadzu Corporation; LC-10Avp). A polymer to be measured was in tetrahydrofuran solved, so as to obtain a concentration of about 0.5% by weight, and the solution obtained was in an amount of 50 μl injected in GPC. The mobile phase of the GPC was tetrahydrofuran used, and you left it at a flow rate of 0.6 ml / min. In terms of the columns became two pillars TSKgel Super HM-H (manufactured by Tosoh Corporation) and a TSKgel column Super H2000 (manufactured by Tosoh Corporation) connected in series. As a detector, a differential refractive index detector (manufactured from Shimadzu Corporation: RID-10A).

(Fluorescence spectrum)

The Measurement of the fluorescence spectrum was done by the following procedure carried out. A 0.8% by weight solution of a polymer was spin-coated on quartz to form a thin film of the polymer. This thin one Movie was at one wavelength of 350 nm and the fluorescence spectrum was used a fluorescence spectrophotometer (manufactured by Horiba Ltd .: Fluorol). To obtain the relative fluorescence intensity on the thin Film was the fluorescence spectrum in which wavenumbers against the intensity The Raman line of water are plotted as standard, in one Integrated measuring range of the spectrum, and assigned extinctions at excitation wavelengths, using a spectrophotometer (manufactured by Varian: Cary5E).

(HPLC measurement)

• Measuring device: Agilent 1100LC
• Measuring conditions: L-pillar ODS, 5 μm, 2.1 mm × 150 mm;
• liquid A: acetonitrile, liquid B: THF
• gradient
• liquid B:
• 0% (60 min) → 10 % Increase / min → 100 % (10 min)
• Sample concentration: 5.0 mg / ml (THF solution)
• Injection quantity: 1 μl
• Detection wavelength: 350 nm

Synthetic Example 1

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

Under an inert atmosphere 225 g of acetic acid in a 500 ml three-necked flask and to 24.3 g of 5-t-butyl-m-xylene. Subsequently, 31.2 g of bromine were added, then the solution became at 15 to 20 ° C for 3 hours implemented.

The reaction liquid was added to 500 ml of water, and the deposited precipitate was filtered. The precipitate was washed twice with 250 ml of water to give 34.2 g of white solid. <Synthesis of N, N'-diphenyl-N, N'-bis (4-t-butyl-2,6-dimethylphenyl) -1,4-penylenediamine>

Under an inert atmosphere 36 ml were deaerated dehydrated Toluene was added to a 100 ml three-necked flask and added thereto 0.63 g of tri (t-butyl) phosphine was added. Subsequently, 0.41 g of tris (dibenzylideneacetone) dipalladium, 9.6 g of 1-bromo-4-t-butyl-2,6-dimethylbenzene, 5.2 g of t-butoxysodium and 4.7 g of N, N'-diphenyl-1,4-phenylenediamine added, then the solution became at 100 ° C 3 hours implemented.

The reaction liquid was added to 300 ml of saturated saline and extracted with 300 ml of chloroform which had been heated to about 50 ° C. The solvent was distilled off, then 100 ml of toluene was added and the mixture was heated until the solid dissolved, and allowed to cool, then the resulting precipitate was filtered to obtain 9.9 g of white solid. <Synthesis of N, N'-bis (4-bromophenyl) -N, N'-bis (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine>

Under an inert atmosphere were drained 350 ml Introduced N, N-dimethylformamide into a 1000 ml three-necked flask, and 5.2 g of N'-diphenyl-N, N'-bis (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine solved, then an N-bromosuccinimide 3.5 g / N, N-dimethylformamide in an ice bath was dropped, and the resulting solution was reacted overnight and for one day.

150 ml of water was added to the reaction solution, and the deposited precipitate was filtered and washed with 50 ml of methanol twice to obtain 4.4 g of white solid.
¹ H-NMR (300 MHz / THF-d8):
δ (ppm) = 1.3 [s, 18H], 2.0 [s, 12H], 6.6 to 6.7 [d, 4H], 6.8 to 6.9 [br, 4H], 7 , 1 [s, 4H], 7.2 to 7.3 [d, 4H]
MS (FD ⁺ ) M ⁺ 738

Synthesis Example 2

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

Under an inert atmosphere were dehydrated 1660 ml Toluene was added to a 300 ml three-necked flask and added thereto 275.0 g of N, N'-diphenylbenzidine and 449.0 g of 4-t-butyl-2,6-dimethylbromobenzene. Subsequently were 7.48 g of tris (dibenzylideneacetone) dipalladium and 196.4 g of t-butoxysodium was added, then 5.0 g of tri (t-butyl) phosphine was added. After that became the obtained solution at 105 ° C 7 Hours implemented.

To the reaction liquid was added 2000 g of toluene, and the solution was filtered through celite, the filtrate was washed with 1000 ml of water three times, then concentrated to 700 ml. To this was added 1600 ml of a toluene / methanol (1: 1) solution, and the deposited crystals were filtered and washed with methanol. 479.4 g of white solid were obtained. <Synthesis of N, N'-bis (4-bromophenyl) -N, N'-bis (4-t-butyl-2,6-dimethylphenyl) benzidine>

Under an inert atmosphere In 4730 g of chloroform, 472.8 g of the above N, N'-diphenyl-N, N'-bis (4-t-butyl-2,6-dimethylphenyl) benzidine solved, then 281.8 g of N-bromosuccinimide was added in 12 divided portions with shielding light in an ice bath for 1 hour, and the solution was reacted for 3 hours.

1439 ml of chloroform was added to the reaction liquid and filtered, and a chloroform solution of the filtrate was washed with 2159 ml of 5% sodium thiosulfate, and toluene was distilled off to obtain white crystals. The obtained white crystals were recrystallized from toluene / ethanol to obtain 678.7 g of white crystals.
MS (APCI (+)): (M + H) ⁺ 815.2

Example 1 <Synthesis of Compound B>

(Verbindung A) (Synthesis of Compound A)

(Compound A)

Into a reaction vessel was placed 31 ml of internally exchanged water, and 29 g of sodium hydroxide (727 mmol) was added portionwise with stirring to achieve complete dissolution. The atmosphere in the system was purged with argon, and 30 ml of toluene and 5.0 g (24 mmol) of 1,2,3,10b-tetrahydrofluoroanthrene were introduced and dissolved with stirring. 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. Liquid separation in toluene and water was performed, the organic layer was extracted, then dried over sodium sulfate. The solvent was distilled off, then purification was performed with a silica gel column using hexane as the eluent to obtain 6.45 g of pale yellow crystals.
MS (APCI (+)) = 318 ([M + H] ⁺ )
¹ H-NMR (300 MHz / CDCl ₃₎ δ7,69 (1H, d), 7.50 (1H, d), 7.40
(1H, d), 7.34 to 7.22 (3H, m), 7.03 (1H, d), 3.07 to 2.96 (1H, m), 2.77 to 2.70 (1H , m), 2.37 to 2.18 (2H, m), 1.95 to 1.74 (3H, m), 1.27 to 1.04 (11H, m), 0.84 to 0.69 (5H, m)

(Verbindung B) (Synthesis of Compound B)

(Compound B)

Into an argon-purged reaction vessel was added 5.8 g (18 mmol) of the compound A and 115 ml of a mixed solvent of acetic acid: dichloromethane = 1: 1, and the mixture was stirred at room temperature to effect dissolution. Subsequently, 14 g (36 mmol) of benzyltrimethylammonium tribromide were added and zinc chloride was added with stirring until complete dissolution of benzyltrimethylammonium tribromide. While monitoring the reaction by HPLC, benzyltrimethylammonium tribromide and zinc chloride were appropriately added. After completion of the reaction, liquid separation was carried out in chloroform and water, the organic layer was extracted, washed twice with water, then neutralized with an aqueous potassium carbonate solution. After drying over sodium sulfate, the solvent was distilled off, and purification by a silica gel column was performed using hexane as the eluent, then from a mixed solvent of ethanol: hexane = 10: 1 to give 5.08 g of Compound B as a white powder.
MS (APPI (+)) 476 (M ⁺ )
¹ H-NMR (300 MHz / CDCl ₃₎ δ7,53 to 7.43 (4H, m), 7.33 (1H, d), 2.90 to 2.84 (2H, m), 2.33 to 2.22 (2H, m), 2.05 to 1.96 (1H, m), 1.83 to 1.64 (2H, m), 1.32 to 1.05 (13H, m), 0, 85 to 0.81 (3H, m)

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, to which solution was added bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.156 g) under a nitrogen atmosphere, and the mixture was heated up to 60 ° C and reacted for 3 hours. This reaction liquid was cooled to room temperature and dropped into a mixed solution of 25% ammonia water 1 ml / methanol 19 ml / ion exchanged water 19 ml, and the mixture was stirred for 1 hour, then the deposited 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. The polystyrene-reduced number average molecular weight was 2.9 × 10 ^4, and the polystyrene-based 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 The 2'-bipyridyl (0.548 g) was dissolved in 140 ml of dehydrated tetrahydrofuran, then bubbled with argon to purge the atmosphere in the system with nitrogen. The solution was warmed up to 60 ° C, then bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.965 g) was added to this solution under a nitrogen atmosphere, and the mixture was stirred and 3 Hours implemented. This reaction liquid was cooled to room temperature and dropped into a mixed solution of 25% ammonia water 5 ml / methanol 140 ml / ion exchanged water 140 ml, and the mixture was stirred for 1 hour, then the deposited precipitate was filtered and dried under reduced pressure and poured into Dissolved 40 ml of toluene. After dissolution, 1.6 g of radiolite was added, and the mixture was stirred for 30 minutes, and the insoluble matters were filtered. The resulting filtrate was purified while passing through an alumina column. Next, 80 ml of 5.2% hydrochloric acid-water was added, and the mixture was stirred for 3 hours, then the aqueous phase was removed. Then, 80 ml of 4% ammonia water was added, and the mixture was stirred for 2 hours, then the aqueous phase was removed. Further, about 80 ml of internally exchanged water was added to the organic layer, and the mixture was stirred for 1 hour, then the aqueous phase was removed. Thereafter, the organic layer was poured into 160 ml of methanol, and the mixture was stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 2) was 0.33 g. The polystyrene-reduced number-average molecular weight and the polystyrene-reduced weight-average molecular weight were Mn = 1.6 × 10 ⁴ and Mw = 8.7 × 10 ^4, respectively.

Example 4

(Synthesis of Polymer Compound 3)

Compound B (0.433 g), N, N'-bis (4-bromophenyl) -N, N'-bis (4-t-butyl-2,6-dimethylphenyl) benzidine (0.318 g) and 2,2'-bipyridyl (0.548 g) was dissolved in 140 ml of dehydrated tetrahydrofuran, then argon was bubbled through to purge the atmosphere in the system with nitrogen. The solution was warmed up to 60 ° C, then bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.965 g) was added to this solution under a nitrogen atmosphere, and the mixture was stirred and 3 Hours implemented. This reaction liquid was cooled to room temperature and dropped into a mixed solution of 25% ammonia water 5 ml / methanol 140 ml / ion exchanged water 140 ml, and the mixture was stirred for 1 hour, then the deposited precipitate was filtered and dried under reduced pressure and poured into Dissolved 40 ml of toluene. After dissolution, 1.6 g of radiolite was added, and the mixture was stirred for 30 minutes, and the insoluble matters were filtered. The resulting filtrate was purified while passing through an alumina column. Next, 80 ml of 5.2% hydrochloric acid-water was added, and the mixture was stirred for 3 hours, then the aqueous phase was removed. Subsequently, 80 ml of 4% were Ammonia water was added, and the mixture was stirred for 2 hours, then the aqueous layer was removed. Further, about 80 ml of ion exchanged water was added to the organic layer, and the mixture was stirred for 1 hour, then the aqueous phase was removed. Thereafter, the organic layer was poured into 160 ml of methanol, and the mixture was stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 3) was 0.46 g. The polystyrene-reduced number-average molecular weight and the polystyrene-reduced weight-average molecular weight were Mn = 1.0 × 10 ⁴ and Mw = 6.1 × 10 ^4, respectively.

Example 5

(Synthesis of Polymer Compound 4)

Compound B (0.588 g), N, N'-bis (4-bromophenyl) -N, N'-bis (4-t-butyl-2,6-dimethylphenyl) benzidine (0.053 g) and 2,2'-bipyridyl (0.548 g) was dissolved in 140 ml of dehydrated tetrahydrofuran, then argon bubbled through to purge the atmosphere in the system with nitrogen. The solution was warmed up to 60 ° C, then bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.965 g) was added to this solution under a nitrogen atmosphere, and the mixture was stirred and 3 Hours implemented. This reaction liquid was cooled to room temperature and dropped into a mixed solution of 25% ammonia water 5 ml / methanol 140 ml / ion exchanged water 140 ml, and the mixture was stirred for 1 hour, then the deposited precipitate was filtered and dried under reduced pressure and poured into Dissolved 40 ml of toluene. After dissolution, 1.6 g of radiolite was added, and the mixture was stirred for 30 minutes, and the insoluble matters were filtered. The resulting filtrate was purified while passing through an alumina column. Next, 80 ml of 5.2% hydrochloric acid-water was added, and the mixture was stirred for 3 hours, then the aqueous phase was removed. Then, 80 ml of 4% ammonia water was added, and the mixture was stirred for 2 hours, then the aqueous phase was removed. Further, about 80 ml of ion exchanged water was added to the organic layer, and the mixture was stirred for 1 hour, then the aqueous phase was removed. Thereafter, the organic layer was poured into 160 ml of methanol, and the mixture was stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 4) was 0.31 g. The polystyrene-reduced number-average molecular weight and the polystyrene-reduced weight-average molecular weight were Mn = 2.5 × 10 ⁴ and Mw = 1.2 × 10 ^5, respectively.

Example 6 <Production and Performance of EL Device>

(Preparation of the solution)

The Polymer compound 2 obtained above was dissolved in toluene, whereby a toluene solution was obtained with a polymer concentration of 1.8 wt .-%.

(Production of the EL device)

On a glass substrate carrying an ITO film having a thickness of 150 nm formed by a sputtering method, a solution obtained by filtering a suspension of poly (3,4) ethylenedioxythiophene / polystyrenesulfonic acid (manufactured by Bayer, Baytron P AI4083) was obtained. spin-coated through a 0.2 μm membrane filter to form a thin film having a thickness of 70 nm and dried on a hot plate at 200 ° C for 10 minutes. Next, the toluene solution obtained above was spin-coated at a revolution number of 3400 rpm to form a film. The thickness after film formation was about 95 nm. Further, it was dried at 80 ° C. for 1 hour under reduced pressure, then lithium fluoride was vapor-deposited to a thickness of about 4 nm, and as a cathode, calcium was vapor-deposited to a thickness of about 5 nm, then Aluminum was vapor-deposited to a thickness of about 80 nm to prepare an EL device. After the degree of vacuum reached 1 × 10 ^-4 Pa or less, vapor deposition of a metal was started.

(Power of the EL device)

By applying voltage to the obtained device, an EL light emission having a peak at 485 nm was obtained from this device. When the EL emitted color is represented by the CIE chromatic coordinate value, x = 0.150 and y = 0.128, showing very good blue color. In the The intensity of EL light emission was approximately proportional to the current density. This device showed a start of light emission of 5.2 V. The light emission efficiency was monotonously increased in the range of the measured applied voltage (0 V to 12 V), however, showed a relatively high efficiency of 1.02 cd / m ² at 12 V.

Example 7 <Production and Performance of EL Device>

(Preparation of the solution)

The Polymer compound 4 obtained above and those obtained above Polymer compound 3 was used in a ratio of 90% by weight to 10% by weight. dissolved in toluene, wherein a toluene solution was obtained with a polymer concentration of 1.8 wt .-%.

(Production of the EL device)

A EL device was prepared in the same manner as in Example 6, except that the toluene solution obtained above was used. The number of revolutions when spin coating the polymer solution was 3300 rpm and the Thickness of the polymer membrane after film formation was 95 nm.

(Power of the EL device)

Upon application of voltage to the obtained device, an EL light emission having a peak at 425 nm was obtained from this device. When the EL emitted color is represented by the CIE chromatic coordinate value, x = 0.155 and y = 0.072, showing very good blue color. The intensity of EL light emission was approximately proportional to the current density. This device showed a start of light emission from 5.5 V. The light emission efficiency was monotonously increased in the range of the measured applied voltage (0 V to 12 V), however, showed a relatively high efficiency of 0.22 cd / m ² at 12 V.

Example 8 <Production and Performance of EL Device>

(Preparation of the solution)

The Polymer compound 4 obtained above was dissolved in toluene, whereby a toluene solution was obtained with a polymer concentration of 1.8 wt .-%.

(Production of the EL device)

A EL device was prepared in the same manner as in Example 6, except that the toluene solution obtained above was used. The number of revolutions when spin coating the polymer solution was 2500 rpm and the Thickness of the polymer membrane after film formation was 90 nm.

(Power of the EL device)

Upon application of voltage to the obtained device, an EL light emission having a peak at 425 nm was obtained from this device. When the EL emitted color is represented by the CIE chromatic coordinate value, x = 0.155 and y = 0.074, showing very good blue color. The intensity of EL light emission was approximately proportional to the current density. This device showed onset of light emission above 5.8 V. The light emission efficiency increased monotonically in the range of the measured applied voltage (0 V to 12 V), but exhibited a relatively high efficiency of 0.57 cd / m ² at 12 V.

Example 9 <Synthesis of Compound D>

(Verbindung C) (Synthesis of Compound C)

(Compound C)

Into a reaction vessel was placed 31 ml of internally exchanged water, and 29 g of sodium hydroxide (727 mmol) was added portionwise with stirring to achieve complete dissolution. The atmosphere in the system was purged with argon, and 30 ml of toluene and 5.0 g (24 mmol) of 1,2,3,10b-tetrahydrofluoranthene were introduced and dissolved with stirring. Subsequently, 2.3 g (7.3 mmol) of tetrabutylammonium bromide and 9.4 g (48 mmol) of 2-ethylhexylbromide were added and reacted at 40 ° C for 3 hours. Liquid separation in toluene and water was performed, the organic layer was extracted, then dried over sodium sulfate. The solvent was distilled off, then purification was performed with a silica gel column using hexane as the eluent to obtain 6.88 g of a yellow oil.
MS (APPI (+)): 318 ([M + H] ⁺ )
¹ H-NMR (300 MHz / CDCl ₃₎ δ7,69 (1H, d), 7.50 (1H, d), 7.40 (1H, d), 7.33 to 7.22 (3H, m) , 7.02 (1H, d), 3.07 to 2.96 (1H, m), 2.79 to 2.71 (1H, m), 2.36 to 2.22 (2H, m), 2 , 10 to 1.99 (1H, m), 1.93 to 1.76 (2H, m), 1.24 to 1.15 (11H, m), 0.88 to 0.37 (9H, m)

(Verbindung D) (Synthesis of Compound D)

(Compound D)

Into an argon-purged reaction vessel were charged 6.8 g (21 mmol) of the compound C, 6.7 g (49 mmol) of zinc chloride and 134 ml of a mixed solvent of acetic acid: dichloromethane = 1: 1, and the mixture became at room temperature touched. Subsequently, 18 g (47 mmol) of benzyltrimethylammonium tribromide were dissolved in 150 ml of dichloromethane and added dropwise. After completion of the dropping, the solution was reacted at room temperature for 2 hours, then at 40 ° C and 50 ° C for 30 minutes each, then chloroform and a 5% aqueous sodium hydrogen sulfite solution were added to terminate the reaction. Liquid separation in chloroform and water was performed, the organic layer was extracted, washed twice with water, then neutralized with an aqueous potassium carbonate solution. After drying over sodium sulfate, the solvent was distilled off, and purification was carried out 3 times with a silica gel column using hexane as the eluent to obtain 1.73 g of Compound D as a yellow oil (when allowed to stand at room temperature, it slowly changed in white crystals).
MS (APPI (+)) 476 (M ⁺ )
¹ H-NMR (300 MHz / CDCl ₃₎ δ7,52 to 7.42 (4H, m), 7.33 (1H, d), 3.00 to 2.80 (2H, m), 2.40 to 2.20 (2H, m), 2.02 to 1.89 (2H, m), 1.75 to 1.70 (1H, m), 1.31 to 1.15 (2H, m), 0, 96 to 0.39 (8H, m)

Example 10

(Synthesis of Polymer Compound 5)

Under a nitrogen atmosphere, Compound D (0.476 g) and 2,2'-bipyridyl (0.422 g) were dissolved in 72 ml of dehydrated tetrahydrofuran, then dissolved by stirring. To this solution was added bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.743 g), and the mixture was stirred and reacted at 60 ° C for 3 hours puts. This reaction liquid was cooled to room temperature and dropped into a mixed solution of 25% ammonia water 4 ml / methanol 72 ml / in-exchanged water 72 ml, and the mixture was stirred for 1 hour, then the deposited precipitate was filtered and dried under reduced pressure and placed in 20 ml Toluene dissolved. After dissolution, 1.6 g of radiolite was added and the mixture was stirred for 30 minutes and the insoluble substances were filtered. The resulting filtrate was purified while passing through an alumina column. Next, 40 ml of 5.2% hydrochloric acid-water was added, and the mixture was stirred for 3 hours, then the aqueous phase was removed. Subsequently, 40 ml of 4% ammonia water was added, and the mixture was stirred for 2 hours, then the aqueous phase was removed. Further, about 40 ml of ion exchanged water was added to the organic layer, and the mixture was stirred for 1 hour, then the aqueous phase was removed. Thereafter, the organic layer was poured into 80 ml of methanol, and the mixture was stirred for 1 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 5) was 0.17 g. The polystyrene-reduced number-average molecular weight and the polystyrene-reduced weight-average molecular weight were Mn = 1.1 × 10 ⁵ and Mw = 3.2 × 10 ^5, respectively.

Comparative Example 1

(Synthesis of Polymer Compound 6)

0.22 g (0.40 mmol) 2,7-dibromo-9,9-dioctylfluorene, 0.20 g (0.27 mmol) (N, N'-bis (4-bromophenyl) -N, N'-bis (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine and 0.24 g (1.5 mmol) of 2,2'-bipyridyl were in a reaction vessel introduced, then the atmosphere in the reaction system with Purged nitrogen gas. To this was added 20 ml of tetrahydrofuran (dehydrated solvent) previously was deaerated by blowing with argon gas. Next were to this mixed solution 0.42 g (1.5 mmol) of bis (1,5-cyclooctadiene) nickel (0), and the Mixture was at 60 ° C 3 hours implemented. The reaction was carried out in a nitrogen gas atmosphere. To the reaction was cooled, then in a mixed solution of 25% ammonia water 10 ml / methanol 120 ml / ion exchanged Water 50 ml, and the mixture was stirred for about 1 hour. Then The precipitate formed was recovered by filtration. This precipitate was washed with ethanol, then under reduced pressure Pressure dried for 2 hours. Then this precipitation became 50 ml of toluene dissolved, and 50 ml of 1N hydrochloric acid were added, and the mixture was stirred for 1 hour, and the watery Layer was removed and 50 ml of 4% ammonia water became of the organic layer, and the resulting mixture became Stirred for 1 hour, then the watery Layer removed. The organic layer was dissolved in 120 ml of methanol was added dropwise and the resulting mixture was stirred for 1 hour, and the deposited precipitate was filtered and concentrated under reduced pressure Dried for 2 hours and dissolved in 40 ml of toluene. After that was a cleaning while passing through an alumina column (amount of alumina: 20 g), and the recovered toluene was dropped into 120 ml of methanol, and the resulting mixture became Stirred for 1 hour, and the deposited precipitate was filtered and concentrated under reduced pressure Dried for 2 hours. The yield of the obtained polymer compound 6 was 0.094 g.

The polymer compound 6 had a polystyrene-reduced number-average molecular weight of 2.0 × 10 ⁴ and a polystyrene-reduced weight-average molecular weight of 1.1 × 10 ⁵ .

Comparative example 2 <Production and performance of EL device>

(Preparation of the solution)

The Polymeric compound 6 obtained above was dissolved in chloroform, whereby a chloroform solution was obtained with a polymer concentration of 1.8 wt .-%.

(Production of the EL device)

On a glass substrate containing an ITO film having a thickness of 150 nm, formed with a sputtering process, wore a solution of Poly (ethylenedioxythiophene) / polystyrenesulfonic acid (manufactured by Bayer, Baytron P), wherein a film having a thickness of 50 nm, and on a hot plate at 200 ° C for 10 minutes dried. Next became the chloroform solution prepared above at one revolution spin-coated at 2500 rpm to form a film.

The thickness was about 100 nm. Further, it was at 80 ° C for 1 hour ge under reduced pressure Then, LiF having a thickness of about 4 nm was vapor-deposited as a cathode buffer layer, and calcium was vapor-deposited to a thickness of about 5 nm, in which aluminum was vapor-deposited to a thickness of about 80 nm as a cathode to prepare an EL device. After the degree of vacuum reached 1 × 10 ^-4 Pa or less, vapor deposition of a metal was started.

(Power of the EL device)

Under Applying voltage to the obtained device became an EL Received light emission with a peak at 448 nm. When the EL emitted Color by the C.I.E. chromatic coordinate value shown is, x = 0.155 and y = 0.133. The device showed a maximum efficiency of light emission at about 10 V and be Value was 0.14 cd / A.

Industrial applicability

The Polymer compound of the present invention when used as material for an electronic device provides an electronic device which has excellent performance.

The Polymer compound of the present invention usually emits Fluorescence or phosphorescence in the solid state and may be considered polymeric Light emitter (high molecular weight light emitting material) be used.

The Polymer compound has excellent charge transportability on, and may suitably be used as a polymeric LED material or Charge transport material can be used. The polymer LED under Use of the polymeric light emitter is a high power polymer LED, which are operated at low voltage with high efficiency can. Thus, the polymer LED preferably as a backlight of liquid crystal displays or in curved or flat light sources for illumination, display devices of the segment type, dot matrix type flat panel displays, and the like become.

The Polymer compound of the present invention can also be used as a coloring substance for one Laser, a material for an organic solar battery or a conductive material thin films, such as organic semiconductors, electroconductive thin films, organic thin semiconductor films and the like for organic transistors are used.

Further For example, the polymer compound of the present invention may also be used as a Material for luminescent thin Film materials used include fluorescence or phosphorescence demonstrate.

Summary

Formel 1 (wobei Ring A, Ring B und Ring C jeweils unabhängig einen aromatischen Ring oder nicht aromatischen Ring darstellen, der gegebenenfalls einen Substituenten aufweist, Z₁, Z₂, Z₃, Z₄ und Z₅ jeweils unabhängig C-(Q)_z oder ein Stickstoffatom darstellen, Q einen Substituenten oder ein Wasserstoffatom darstellt, z 0 oder 1 darstellt, der Ring A und der Ring B sich neben Z₅ ein Atom teilen können das jeden Ring bildet, und ein oder mehrere oder zwei oder weniger der Ringe A, B und C nicht aromatische Ringe sind).A polymer compound comprising at least one of the groups of compounds of the following formula (1):

Formula 1 (wherein Ring A, Ring B and Ring C each independently represent an aromatic ring or non-aromatic ring optionally having a substituent, Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z _{5 are} each independently C- (Q) _{z represents} a nitrogen atom, Q represents a substituent or a hydrogen atom, z represents 0 or 1, the ring A and the ring B may share, besides Z _5, one atom forming each ring, and one or more or two or less of the rings A, B and C are not aromatic rings).

Claims (34)

Polymer compound comprising at least one of the radicals of compounds of the following formula (1):

Formula 1 (wherein Ring A, Ring B and Ring C each independently represent an aromatic ring or non-aromatic ring optionally having a substituent, Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z _{5 are} each independently C- (Q) _{z represents} a nitrogen atom, Q represents a substituent or a hydrogen atom, z represents 0 or 1, the ring A and the ring B may share, besides Z _5, one atom forming each ring, and one or more or two or less of Rings A, B and C are not aromatic rings). A polymer compound comprising a repeating unit represented by the following formula (1-1), (1-2) or (1-3):

(wherein Ring A, Ring B and Ring C each independently represent an aromatic ring or non-aromatic ring optionally having a substituent; Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z _{5 are} each independently C- (Q) _z or represents a nitrogen atom, Q represents a substituent or a hydrogen atom, z represents 0 or 1, the ring A and the ring B may share an atom besides Z ₅ , the substituents on the rings may be bonded to each other, further forming a ring and one or more rings having no linking bond between rings A, B and C are not aromatic rings). A polymer compound according to claim 1 or 2, in which the ring-forming atoms of rings A, B and C all carbon atoms are. A polymer compound according to claim 2 or 3, wherein the repeating unit of the above-described formula (1-1) is a repeating unit represented by the following formula (2-1):

Formula (2-1) (wherein R ₁ and R ₂ each independently represent a substituent, ring D represents a non-aromatic ring optionally having a substituent, a represents an integer of 0 to 2, b represents an integer of 0 to 3, and when two or more R _1, or two or more R ₂ are present, they may be the same or different and R ₁ and R _{2 may} be joined together to form a ring, R ₁ and / or R ₂ may be connected to ring D, forming a ring, and Q and Z represent the same meanings as described above). A polymer compound according to claim 2 or 3, wherein the repeating unit of the above-described formula (2-1) is a repeating unit represented by the following formula (3-1):

Formula (3-1) (wherein R ₁ , R ₂ , Ring D, Q, Z, a and b have the same meanings as described above). A polymer compound according to claim 5, wherein the repeating unit of the formula (3-1) is a repeating unit of the following formula (4-1), (4-2), (4-3) or (4-4):

(wherein R _1a , R _1b , R _2a to R _2c and R _3a to R _3g each independently represents a hydrogen atom or a substituent. In the formulas (4-1) to (4-3), R _2c and R _{3g may be} bonded together to form a ring In the formula (4-4), R _2c and R _{3e may be} bonded together to form a ring). A polymer compound according to any one of claims 1 to 6, which further comprises a repeating unit of the following formula (5), formula (6), formula (7) or formula (8): -Ar ₁ - (5) - (Ar ₂ -X ₁ ) _ff -Ar ₃ (6) -Ar ₄ -X ₂ - (7) -X ₃ - (8) (wherein Ar _{1 ,} Ar ₂ , Ar ₃ and Ar ₄ each independently represent an arylene radical, divalent heterocyclic radical or divalent radical 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, aryl group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group, aryl group, monovalent heterocyclic group, arylalkyl group or substituted amino group. Ff represents 1 or 2. m represents an integer of 1 to 12 two or more R ₉ , two or more R ₁₀ , two or more R ₁₁ , two or more R _12, or two or more R ₁₃ are present, they may be the same or different). A polymer compound according to any one of claims 1 to 6, which further comprises a repeating unit of the following formula (9), formula (10), formula (11), formula (12), formula (13) or formula (14):

(wherein R _{14 is} alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkoxy, arylalkylthio, arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halogen, acyl, acyloxy, imino, amide An acid group, an acid group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group, n represents an integer of 0 to 4. When two or more R ₁₄ are present, they may be the same or different).

(wherein R ₁₅ and R _{16 are} each independently alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkoxy, arylalkylthio, arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halogen, acyl, acyloxy And imine, an amide group, an acidimide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group, o and p each independently represent an integer of 0 to 3. When two or more R ₁₅ and two or more R ₁₆ are present are, they may be the same or different).

(wherein R ₁₇ and R _{20 are} each independently alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkoxy, arylalkylthio, arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halogen, acyl, acyloxy represents an imine residue, an amide group, an acidimide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group Each of q and r independently represents an integer of 0 to 4 R ₁₈ and R ₁₉ each independently represent a hydrogen atom, an alkyl group , Aryl, monovalent heterocyclic group, carboxyl group, substituted carboxyl group or cyano group. When two or more R ₁₇ and two or more R ₂₀ are present, they may be the same or different).

(wherein R _{21 is} alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkoxy, arylalkylthio, arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halo, acyl, acyloxy, imino, an imino, S represents an integer of 0 to 2. Ar ₁₃ and Ar ₁₄ each independently represent an arylene group, divalent heterocyclic group or divalent metal complex group. ss and tt each independently represent 0 or 1. X ₄ represents O, S, SO, SO _2, Sc or Te. When two or more R ₂₁ are present, they may be the same or different).

(wherein R ₂₂ and R _{25 are} each independently alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkoxy, arylalkylthio, arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halogen, acyl, acyloxy represent 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, 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 each independently represent N or CR _27. R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ each independently represent a hydrogen atom, an alkyl group, aryl group, arylalkyl group or monovalent one heterocyclic group. When two or more R ₂₂ , two or more R ₂₃ and two or more R ₂₇ are present, they may be the same or different).

(wherein R ₂₈ and R _{33 are} each independently alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkoxy, arylalkylthio, arylalkenyl, arylalkynyl, amino, substituted amino, silyl, substituted silyl, halogen, acyl, acyloxy represent an imine residue, an amide group, an acidimide group, a monovalent heterocyclic group, a carboxyl group, substituted carboxyl group, cyano group or nitro group, v and w each independently represent an integer of 0 to 4. R ₂₉ , R ₃₀ , R ₃₁ and R Each of ₃₂ independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group or a cyano group. Ar ₅ represents an arylene group, a divalent heterocyclic group or a divalent metal complex group. When two or more R ₂₈ and two or more more R ₃₃ are available, you can be the same or different). A polymer compound according to any one of claims 1 to 6, which further comprises a repeating unit of the following formula (15):

(wherein Ar ₆ , Ar ₇ , Ar ₈ and Arg each independently represent an arylene group or divalent heterocyclic group. Ar ₁₀ , Ar ₁₁ and Ar ₁₂ each independently represent an arylene group or monovalent heterocyclic group. Ar ₆ , Ar ₇ , Ar ₈ , Arg and Ar ₁₀ may have a substituent, x and y are each independently 0 or 1 and 0 ≤ x + y ≤ 1). A process for producing a polymer compound according to any one of claims 1 to 9, which comprises polymerizing at least one compound represented by the following formula (16-1), (16-2) or (16-3) as a starting material:

(wherein Ring A, Ring B, Ring C, and Z ₁ to Z _{5 have} the same meanings as described above.) Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y _5, and Y ₆ each independently represent a substituent represented by the polymerization is related). The production method according to claim 10, wherein the compound of the above-described formula (16-1) is a compound represented by the following formula (17-1):

(wherein R ₁ , R ₂ , a, b, ring D, Q, z, Y ₁ and Y _{2 have} the same meanings as described above). The production method according to claim 11, wherein the compound of the above-described formula (17-1) is a compound of the following formula (18-1), (18-2), (18-3) or (18-4):

(wherein R _1a , R _1b , R _2a to R _2c , R _3a to R _3g , Y ₁ and Y _{2 have} the same meanings as described above). The production process according to claim 10, wherein the compound of the above-described formula (16-2) is a compound of the following formula (17-2):

(wherein Ring B, Ring C, Z ₂ , Z ₃ , Z ₄ , Y ₃ and Y _{4 have} the same meanings as described above.) Z ₆ , Z ₇ and Z ₈ each independently represent C- (Q) _z or a nitrogen atom Z _1a , Z _5a and Z ₉ each independently represent a carbon atom Q and z have the same meanings as described above R ₄ represents a substituent. e represents an integer of 0 to 2 more R ₄ exist, they may be the same or different. The R ₄ may be joined together to form a ring is formed). The production process according to claim 10, wherein the compound of the above-described formula (16-3) is a compound represented by the following formula (17-3):

(wherein Ring A, Ring B, Z ₁ , Z ₄ , Z ₅ , Y ₅ and Y _{6 have} the same meanings as described above.) Z ₁₀ , Z ₁₁ , Z ₁₂ and Z ₁₃ each independently represent C- (Q) _z Z _2a and Z _3a each independently represent a carbon atom Q and z have the same meanings as described above R ₅ represents a substituent f represents an integer of 0 to 2 When two or two more R ₅ are present, they may be the same or different. The R ₅ may be joined together to form a ring is formed). A production process according to any one of claims 10 to 14, which comprises polymerizing a compound of at least one of the following formulas (19) to (22) as a starting substance in addition to the compound of the above-described formula (16-1), (16-2) or (16- 3): Y 7 -ar 1 -Y 8th (19) Y ₉ - (Ar ₂ -X _{1) ff r3} -A -Y ₁₀ (20) Y ₁₁ -Ar ₄ -X ₂ -Y ₁₂ (21) Y ₁₃ -X ₃ -Y ₁₄ (22) (wherein Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , ff, X ₁ , X ₂ and X _{3 have} the same meanings as described above. Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Y ₁₃ and Y ₁₄ each independently represent a substituent related to the polymerization). A production process according to any one of claims 10 to 15, wherein when polymerizing a compound of formula (16-1), (16-2) or (16-3) individually or together with at least one selected from the compounds of formulas (19) to (22), 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 each independently represent a halogen atom, represents an alkylsulfonate residue, arylsulfonate residue or arylalkylsulfonate residue, and condensation polymerization is carried out in the presence of a zerovalent nickel complex. A production process according to any one of claims 10 to 15, wherein in the polymerization at least one selected from the formulas (16-1), (16-2) and (16-3), individually or together with at least one selected from the formulas ( 19) to (22), Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ , Y ₉ , Y ₁₀ , Y ₁₁ , Y ₁₂ , Y ₁₃ and Y _{14 are} each independently represents a halogen atom, an alkylsulfonate residue, an arylsulfonate residue, an arylalkylsulfonate residue, -B (OH) ₂ or a borate group, the ratio of the sum of the moles of the halogen atoms, alkylsulfonate residues, arylsulfonate residues and arylalkylsulfonate residues to the sum of the moles of -B (OH) ₂ and borate groups in the formula Is substantially 1 and the condensation polymerization is carried out using a nickel or palladium catalyst. Compound of the above-described formula (17-1). Compound of the above-described formula (18-1), (18-2), (18-3) or (18-4). Compound of the above-described formula (16-2) or (16-3). Compound of the above-described formula (17-2) or (17-3). Composition comprising at least one material, selected from hole transporting materials, electron transporting Materials and light-emitting materials, and the polymer compound as in any of the claims 1 to 9 described. An ink composition comprising the polymer compound as in any of the claims 1 to 9 and a solvent. The ink composition of claim 23, wherein the viscosity at 25 ° C 1 to 20 mPa · s is. A luminescent thin film comprising the polymer compound as in any of the claims 1 to 9 described. An electrically conductive thin film comprising the polymer compound as in any of the claims 1 to 9 described. Organic thinner A semiconductor film comprising the polymer compound as in any of claims 1 to 9 described. Polymer light-emitting device with a organic layer between the electrodes, composed of a Anode and a cathode, wherein the organic layer, the polymer compound as in any of the claims 1 to 9. Polymer light-emitting device according to claim 28, wherein the organic layer is a light-emitting layer is. Polymer light-emitting device according to claim 29, wherein the light emitting layer further comprises a hole transporting Material, electron-transporting material or light-emitting Material includes. Area light source, comprising the polymeric light-emitting device as in one of claims 28 to 30 described Segmental display comprising the polymeric light-emitting Apparatus as described in any one of claims 28 to 30. Dot matrix display comprising the polymeric light emitting Apparatus as described in any one of claims 28 to 30. Liquid crystal display, comprising the polymeric light-emitting device as in one the claims 28 to 30 described.