JP2007119763A - Polymeric material and polymeric light emitting device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymeric material having a high light emitting efficiency with a low oxidation potential and a high reduction potential. <P>SOLUTION: The polymeric material having a light emitting property or charge transporting property, comprises a main chain containing at least one repeating units selected from a group comprising an arylene group, a divalent heterocyclic group, a divalent aromatic amine group and a side chain comprising at least one functional groups selected from a group comprising a hole injection transporting group, an electron injection transporting group and a light emitting group, wherein the functional side chain connects to the main chain through a -Rj- or a -Rj-X-, [Rj represents a group having a structure in which one or more carbon atoms constituting an alkylene group is substituted by nitrogen atoms, X represents O, S or N(R'), X connect to the main chain]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

High molecular weight light-emitting materials and charge transport materials, which are different from those having low molecular weight, are variously studied because they are soluble in a solvent and can form an organic layer in a light-emitting element by a coating method. As an example, a polymer compound having the following structure in which two benzene rings are condensed to a cyclopentadiene ring is known as a repeating unit (see, for example, Non-Patent Document 1 and Patent Document 1).

  In addition, polymer compounds having a functional substituent such as a hole injection / transport group, an electron injection / transport group, or a light-emitting group in a side chain of a conjugated main chain are known (for example, Patent Document 2, Patent Document 3, Non-Patent Document 2 and Non-Patent Document 3).

International Publication No. 99/54385 Pamphlet JP 2004-277568 A International Publication No. 2001-62822 Pamphlet Advanced Materials 1999 Vol. 9 No. 10 798 Advanced Material; 2002, 14 (11), 809-811. J. et al. Polymer Science, Part A; 2005, 43 (3), 859-869.

  When a polymer compound is used as a light-emitting material for a light-emitting element, in order to emit light with high efficiency, it is necessary that the polymer compound has good positive charge (hole) and negative charge (electron) injection properties. is there. Although the charge injection property is determined by various factors, it is expected that the highest occupied molecular orbital (HOMO) is increased and the hole injection property is improved when the oxidation potential of the polymer compound is lowered. Further, if the reduction potential of the polymer compound is increased, the lowest unoccupied molecular orbital (LUMO) is lowered and the electron injection property is expected to be improved. The above-mentioned known polymer compounds are not yet satisfactory in characteristics, and polymer compounds having a lower oxidation potential and polymer compounds having a higher reduction potential and a high luminous efficiency have been desired.

  An object of the present invention is to provide a polymer compound having a low oxidation potential and a polymer compound having a high reduction potential and high luminous efficiency.

  That is, the present invention has a main chain containing at least one selected from the group consisting of an arylene group, a divalent heterocyclic group and a divalent aromatic amine group as a repeating unit, a hole injection transport group, an electron injection A luminescent or charge transporting polymer compound having a functional side chain containing at least one functional group selected from the group consisting of a transport group and a luminescent group, wherein the functional side chain is -Rj- or- Rj—X— (Rj represents a group having one or more carbon atoms constituting an alkylene group replaced with a nitrogen atom (hereinafter also referred to as a nitrogen-substituted alkylene group), and the nitrogen-substituted alkylene group May have a substituent, X is O, S, or N (R ′), and is bonded to the main chain at X. R ′ is independently a hydrogen atom, an alkyl group, Aryl group, arylalkyl group, arylalkoxy And a high molecular weight compound, which is bonded to the main chain via a thio group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, or a monovalent heterocyclic group. is there.

The polymer compound of the present invention has an effect of high hole and / or electron injection and high luminous efficiency. For example, when the side chain has a hole injection / transport group, HOMO is increased and the hole injection property is improved. When the side chain has an electron injection / transport group, the LUMO is decreased and the electron transport property is improved. In the case of having a light emitting group, the luminous efficiency is improved, the HOMO is high, the LUMO is low, and the hole and / or electron injection properties are improved.
Therefore, the polymer LED containing the polymer compound of the present invention can be used for a curved or flat light source for a backlight or illumination of a liquid crystal display, a segment type display element, a dot matrix flat panel display, and the like.

  The polymer compound of the present invention contains at least one selected from the group consisting of an arylene group, a divalent heterocyclic group and a divalent aromatic amine group in the main chain.

An arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, having a condensed ring, or having two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene Is also included. The arylene group may have a substituent.
When the arylene group has a substituent, it may have an integer number of substituents selected from 0 to 4 in addition to the functional side chain, and the substituent is an alkyl group, an alkoxy group, an alkylthio group, an aryl group. Group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy A group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group, and a nitro group are preferable.

  The alkyl group may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms is usually about 1 to 20, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group. Octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group Etc. are exemplified.

  The alkoxy group may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms is usually about 1 to 20, specifically, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyl. Oxy 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.

  The alkylthio group may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms is usually about 1 to 20, specifically, methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio 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.

An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon and having a condensed ring, two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene. Also included. The aryl group usually has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include phenyl groups, C _{1 to} C ₁₂ alkoxyphenyl groups (C _{1 to} C ₁₂ are carbon numbers). indicates that 1-12. the same applies is less.), C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl, 2-naphthyl, 1-anthracenyl group, 9-anthracenyl group , pentafluorophenyl group and the like, C ₁ -C ₁₂ alkoxyphenyl group, is C ₁ -C ₁₂ alkylphenyl group are preferable. Specific examples C ₁ -C ₁₂ alkoxy, methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, Nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ specifically alkylphenyl group include a methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group, t -Butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group and the like are exemplified.

The aryloxy group usually has about 6 to 60 carbon atoms, preferably 7 to 48, and specific examples thereof include a phenoxy group, a C _{1 to} C ₁₂ alkoxyphenoxy group, and a C _{1 to} C ₁₂ alkylphenoxy group. , 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group and the like, and C ₁ -C ₁₂ alkoxyphenoxy group, C ₁ -C ₁₂ alkylphenoxy group are preferable.
Specific examples C ₁ -C ₁₂ alkoxy, methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, Nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
Specific examples C ₁ -C ₁₂ alkylphenoxy group, methylphenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-methylphenoxy group, methylethylphenoxy group, isopropylphenoxy group, butyl Examples include phenoxy group, isobutylphenoxy 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 may have a substituent on the aromatic ring, the number of carbon atoms is usually about 3 to 60, specifically, phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group, pentafluorophenylthio group, pyridylthio group, pyridazinylthio group, pyrimidylthio group, pyrazylthio group, etc. Toriajiruchio groups.

The arylalkyl group may have a substituent, the number of carbon atoms is usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl - C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl group exemplified Is done.

Arylalkoxy group may have a substituent, the number of carbon atoms is usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl -C ₁ -C ₁₂ alkoxy groups, 2-naphthyl -C ₁ -C ₁₂ alkoxy groups and the like The

The arylalkylthio group may have a substituent, the number of carbon atoms is usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl - C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group, 1-naphthyl -C ₁ -C ₁₂ alkylthio group, 2-naphthyl -C ₁ -C ₁₂ alkylthio group are exemplified Is done.

Arylalkenyl group has a carbon number of usually about 8 to 60, and examples thereof include phenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl group, 1-naphthyl -C ₂ -C ₁₂ alkenyl group, 2-naphthyl -C ₂ -C ₁₂ alkenyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl - C ₂ -C ₁₂ alkenyl group, C ₂ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkenyl groups are preferred.

Arylalkynyl group has a carbon number of usually about 8 to 60, and examples thereof include phenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group, 1-naphthyl -C ₂ -C ₁₂ alkynyl group, 2-naphthyl -C ₂ -C ₁₂ alkynyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl - C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferable.

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl The group or monovalent heterocyclic group may have a substituent. Carbon number of a substituted amino group is about 1-60 normally without including carbon number of this substituent, Preferably it is C2-48.
Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, t-butylamino group Pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, cyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group , pyrimidylamino group, Pirajiruamino group, triazyl amino group phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ ~ C ₁₂ alkylamino groups, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino groups, 1-naphthyl - C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ alkylamino groups.

Examples of the substituted silyl group include a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group. The substituted silyl group usually has about 1 to 60 carbon atoms, preferably 3 to 48 carbon atoms. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
Specifically, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, dimethylisopropylsilyl group, diethylisopropylsilyl group, t-butylsilyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyl dimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl - dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, a 3,7-- dimethylsilyl group, lauryldimethylsilyl group, a phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group, 1-naphthyl -C ₁ -C ₁₂ alkylsilyl group, 2-naphthyl -C ₁ C ₁₂ alkylsilyl group, a phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzylsilyl group, diphenylmethylsilyl group, t- butyl diphenyl silyl group, dimethylphenylsilyl Examples include groups.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The acyl group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, Examples include a fluoroacetyl group and a pentafluorobenzoyl group.

  The acyloxy group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, Examples include benzoyloxy group, trifluoroacetyloxy group, pentafluorobenzoyloxy group and the like.

The imine residue has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include groups represented by the following structural formulas.

  The amide group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group. And pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group, ditrifluoroacetamide group, dipentafluorobenzamide group and the like.

The acid imide group includes a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide, and has about 4 to 20 carbon atoms. Specific examples include the groups shown below. .

The monovalent heterocyclic group refers to a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms, preferably 4 to 20 carbon atoms. The carbon number of the heterocyclic group does not include the carbon number of the substituent. Here, the heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, etc. in the ring. Say. Specifically, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, piperidyl group, quinolyl group, isoquinolyl group and the like, a thienyl group , C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

  The substituted carboxyl group means a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and usually has about 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms. Specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyl group. Siloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl Trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group, etc. . The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The carbon number of the substituted carboxyl group does not include the carbon number of the substituent.

  Examples of the arylene group include a phenylene group (for example, the following formulas 1 to 3), a naphthalenediyl group (the following formulas 4 to 13), an anthracene-diyl group (the following formulas 14 to 19), and a biphenyl-diyl group (the following formulas 20 to 25). ), Fluorene-diyl group (formula 36-38), terphenyl-diyl group (formula 26-28), condensed ring compound group (formula 29-35), indenonaphthalene-diyl (formula GN) And the like. Of these, a phenylene group, a biphenylene group, a fluorene-diyl group, and an indenonaphthalene-diyl group are preferable.

  R in formulas 1-38 and G-N is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, aryl. Alkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic ring Represents a group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group.

  Alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, The acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, and substituted carboxyl group are the same as those exemplified above for the substituent.

The divalent heterocyclic group means an atomic group remaining after removing two hydrogen atoms from a heterocyclic compound, and the group may have a substituent.
Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic in the ring. Say things. Of the divalent heterocyclic groups, an aromatic heterocyclic group is preferable.
Examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, and a substituted amino group. , Silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group, and nitro group It is done. Carbon number of the part except the substituent in a bivalent heterocyclic group is about 3-60 normally. Moreover, the total carbon number including the substituent of a bivalent heterocyclic group is about 3-100 normally, Preferably it is 4-20. The carbon number of the heterocyclic group does not include the carbon number of the substituent. Divalent 6-membered monocyclic heterocyclic group [formula (1-1) to (1-6)], Divalent 5-membered monocyclic heterocyclic group [formula (1-7) to ( 1-11)] a heterocyclic group in which one 6-membered ring and one 5-membered ring are condensed [the following formulas (1-12) to (1-26)], two 6-membered rings are condensed Heterocyclic group [the following formulas (1-27) to (1-33)] a heterocyclic group in which two 6-membered rings and one 5-membered ring are condensed [the following formulas (1-34) to (1- 38)] and a heterocyclic group in which three 6-membered rings are condensed [the following formulas (1-39) to (1-51)] are exemplified.

In the above formulas (1-1) to (1-51), X _{1 to} X ₈₆ are each independently a nitrogen atom, a boron atom, -Si (R ¹ ) =, -P =, -P (R ² ) ( R ³ ) = and P (═O) =.

In the above formulas (1-1) to (1-51), Y _{1 to} Y ₂₉ are each independently an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, —N (R ⁴ ) —, —B (R ^{5 ) -, Si (R 6)} (R 7) -, - P (R 8) - and ^{P (= O) (R 9} ) - represents a.

R ^{1 to} R ⁹ each independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, or a monovalent heterocyclic group.

  The alkyl group, aryl group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group and monovalent heterocyclic group are the same as those exemplified in the above substituent.

  From the viewpoint of luminous efficiency, the divalent heterocyclic group includes a divalent 6-membered monocyclic heterocyclic group, a heterocyclic group in which one 6-membered ring and one 5-membered ring are fused, A heterocyclic group in which a 6-membered ring is condensed, a heterocyclic group in which two 6-membered rings and one 5-membered ring are condensed, and a heterocyclic group in which three 6-membered rings are condensed are preferable. A heterocyclic group in which a member ring and one 5-membered ring are condensed, a heterocyclic group in which two 6-membered rings are condensed, a heterocyclic group in which two 6-membered rings and one 5-membered ring are condensed, and A heterocyclic group in which three 6-membered rings are condensed is more preferable, a heterocyclic group in which two 6-membered rings are condensed, a heterocyclic group in which two 6-membered rings and one 5-membered ring are condensed, and More preferred is a heterocyclic group in which three 6-membered rings are condensed.

  Among the divalent 6-membered monocyclic heterocyclic groups from the viewpoint of luminous efficiency, the above formulas (1-1) to (1-5) are preferable, and the above formulas (1-1) to (1) -3) and (1-5) are more preferable, and the above formulas (1-1) to (1-3) are more preferable.

  Among the divalent 5-membered monocyclic heterocyclic groups from the viewpoint of luminous efficiency, the above formulas (1-7) to (1-10) are preferred, and (1-7) and (1-8) It is more preferable that

  Among the heterocyclic groups in which one 6-membered ring and one 5-membered ring are condensed from the viewpoint of luminous efficiency, the above formulas (1-12) to (1-16), (1-20), (1 −21), (1-24) and (1-25), and the above formulas (1-12), (1-16), (1-20), (1-21), (1- 24) and (1-25) are more preferable, and the above formulas (1-12), (1-16), (1-20) and (1-24) are more preferable.

  Among the heterocyclic groups in which two 6-membered rings are condensed from the viewpoint of luminous efficiency, the above formulas (1-27) to (1-32) are preferable, and the above formulas (1-27), (1 -28), (1-30) and (1-31) are more preferable, and the above formulas (1-28) and (1-30) are more preferable.

  Among the heterocyclic groups in which two 6-membered rings and one 5-membered ring are condensed from the viewpoint of luminous efficiency, the above formulas (1-34) to (1-36) are preferable. 1-34) and (1-35) are more preferable, and the above formula (1-34) is more preferable.

  Among the heterocyclic groups in which three 6-membered rings are condensed from the viewpoint of luminous efficiency, the above formulas (1-39) to (1-41), (1-44), (1-45) and (1- 48) to (1-50), preferably (1-39) to (1-41), (1-44), (1-45), (1-48) and (1-49). More preferably, it is more preferably (1-39), (1-41), (1-44), (1-45) and (1-48).

From the viewpoint of ease of synthesis, X _{1 to} X ₈₆ are preferably a nitrogen atom, a boron atom, and —Si (R ¹ ) ═, more preferably a nitrogen atom and —Si (R ¹ ) ═, More preferably, it is a nitrogen atom.

From the viewpoint of ease of synthesis, Y ₁ to Y ₂₉ are an oxygen atom, a sulfur atom, —N (R ⁴ ) —, —B (R ⁵ ) —, —Si (R ⁶ ) (R ⁷ ) —, and —P. (R ⁸ ) — is preferred, and oxygen atoms, sulfur atoms, —N (R ⁴ ) —, —B (R ⁵ ) — and —Si (R ⁶ ) (R ⁷ ) — are more preferred. , Oxygen atom, sulfur atom, —N (R ⁴ ) —, and —Si (R ⁶ ) (R ⁷ ) — are more preferable.

  The divalent aromatic amine refers to the remaining atomic group obtained by removing two hydrogen atoms from the aromatic amine, and usually has about 5 to 100 carbon atoms, preferably 15 to 60 carbon atoms. The carbon number of the aromatic amine does not include the carbon number of the substituent.

（式中、Ａｒ₁、Ａｒ₂、Ａｒ₃及びＡｒ₄はそれぞれ独立にアリーレン基又は２価の複素環基を示す。Ａｒ₅、Ａｒ₆及びＡｒ₇はそれぞれ独立にアリール基又は１価の複素環基を示す。Ａｒ₁、Ａｒ₂、Ａｒ₃、Ａｒ₄及びＡｒ₅は置換基を有していてもよい。ｋ及びｌはそれぞれ独立に０以上の整数を示す。） Examples of the divalent aromatic amine include a group represented by the following formula (4).

(In the formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent an arylene group or a divalent heterocyclic group. Ar ₅ , Ar ₆ and Ar ₇ each independently represent an aryl group or a monovalent complex) A cyclic group, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ may have a substituent, k and l each independently represents an integer of 0 or more.)

  The arylene group referred to here may have a substituent. Carbon number of the part except the substituent in an arylene group is about 6-60 normally, Preferably it is 6-20. Moreover, the total carbon number including the substituent of an arylene group is about 6-100 normally.

  The divalent heterocyclic group represents the same group as described above.

  The aryl group and monovalent heterocyclic group are the same groups as described above.

When Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ have a substituent, the substituent is an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy Group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent A heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group, or a nitro group.

  Alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, The acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, and substituted carboxyl group are the same as those exemplified above for the substituent.

From the viewpoint of ease of synthesis, in the above formula (4), Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ are preferably each independently an arylene group, and are a divalent group of the above formulas 1 to 12. Are more preferred, groups of formulas 1, 2, 4, 7 and 12 are more preferred, and groups of formula 1 are most preferred.

From the viewpoint of ease of synthesis, in the above formula (4), Ar ₅ , Ar ₆ and Ar ₇ are preferably each independently an aryl group, more preferably a phenyl group which may have a substituent. A phenyl group having an alkyl group as a substituent is more preferable.

  From the viewpoint of luminous efficiency, in the above formula (4), k and l are each independently preferably an integer of 0 or more and 2 or less, more preferably an integer of 0 or more and 1 or less, and 0 or more and 1 or less. More preferably, it is an integer and 0 ≦ k + 1 ≦ 1.

  The polymer compound of the present invention has a functional side chain containing at least one functional group selected from the group consisting of a hole injecting and transporting group, an electron injecting and transporting group, and a light emitting group in the side chain.

  The functional side chain is more preferably bonded to the main chain via -Rj- or -Rj-X-.

  Examples of the hole injecting and transporting group include a monovalent group having a better hole injecting property than the main chain and a monovalent group having a better hole transporting property.

  The hole injection property generally depends on the value of the highest occupied molecular orbital (HOMO) of the polymer compound, and the smaller the absolute value of HOMO, the better the hole injection property.

  Examples of the monovalent group having a better hole injecting property than the main chain include a monovalent group having a smaller absolute value of HOMO than the main chain.

  The HOMO can be calculated, for example, by measuring the oxidation potential of the polymer compound using cyclic voltammetry (CV) and calculating the oxidation potential value. In the case of the polymer compound of the present invention, the lower the oxidation potential, the smaller the absolute value of HOMO and the better the hole injection property.

  The hole transport property generally depends on the hole mobility of the polymer compound, and the higher the hole mobility, the better the hole injection property.

  Examples of the monovalent group that has better hole transport than the main chain include monovalent groups that have higher hole mobility than the main chain.

  Although the measurement of the hole mobility is not particularly limited, for example, the hole mobility of the polymer compound can be measured using a Time-of-Flight (TOF) method.

  Examples of the electron injecting and transporting group include a monovalent group having a better electron injecting property than the main chain and a monovalent group having a better electron transporting property.

  The electron injecting property generally depends on the value of the lowest unoccupied molecular orbital (LUMO) of the polymer compound, and the larger the LUMO absolute value, the better the electron injecting property.

  Examples of the monovalent group having a better electron injection property than the main chain include a monovalent group having a larger LUMO absolute value than the main chain.

  For example, LUMO can be calculated from the value of the reduction potential by measuring the reduction potential of the polymer compound using cyclic voltammetry (CV). In the case of the polymer compound of the present invention, the reduction potential becomes a negative value, and the higher the reduction potential (the smaller the absolute value of the reduction potential), the larger the absolute value of LUMO and the more the electron injection property is improved.

  The electron transport property generally depends on the electron mobility of the polymer compound, and the higher the electron mobility, the better the electron injection property.

  Examples of the monovalent group that has better electron transport than the main chain include monovalent groups that have higher electron mobility than the main chain.

  Although the measurement of the electron mobility is not particularly limited, for example, the electron mobility of the polymer compound can be measured using a Time-of-Flight (TOF) method.

  The light emitting group is a monovalent group that gives an emission color having a wavelength different from that of the main chain.

  The measurement of HOMO and LUMO is the same as described above.

  The hole injection / transport group preferably contains one or more heteroatoms, and more preferably contains one or more nitrogen atoms.

  As the hole injecting and transporting group, a monovalent aromatic amine containing 2 or more nitrogen atoms, a monovalent carbazole derivative containing 2 or more nitrogen atoms, a monovalent metal complex containing 2 or more nitrogen atoms, 1 A monovalent group containing a nitrogen atom and a heteroatom other than one or more nitrogen atoms, a monovalent group containing a heteroatom other than a nitrogen atom, and a monovalent group containing only one nitrogen atom as a heteroatom Is mentioned.

  The monovalent aromatic amine containing two or more nitrogen atoms is represented by the following formulas (H-1) to (H-14), and the monovalent carbazole derivative containing two or more nitrogen atoms is represented by the following formula (H-15). ) To (H-19), monovalent metal complexes containing two or more nitrogen atoms are represented by the following formulas (H-20) to (H-22), other than one or more nitrogen atoms and one or more nitrogen atoms. As the monovalent group containing a hetero atom, the following formulas (H-23) to (H-25) are used. As the monovalent group containing a hetero atom other than a nitrogen atom, the following formulas (H-26) to (H- 29) As monovalent groups containing only one nitrogen atom as a heteroatom, the following residues (H-30) to (H-31) are obtained by removing one R or a hydrogen atom on R, respectively. Examples are groups.

  In the above formulas (H-1) to (H-31), R represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group. , Arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, It is preferably selected from a carboxyl group, a substituted carboxyl group, a cyano group, and a nitro group.

  Alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, An acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, and a substituted carboxyl group represent the same groups as those exemplified above.

  In the formulas (H-26) and (H-30), R ′ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, and a monovalent group. It is preferably one selected from a heterocyclic group.

  The alkyl group, aryl group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group and monovalent heterocyclic group represent the same groups as those exemplified above for the substituent.

（式中Ｒは、それぞれ独立に、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、シアノ基又はニトロ基を表し、Ｒ’は、それぞれ独立に、水素原子、アルキル基、アリール基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基又は１価の複素環基を表し、ａ、ｅ及びｈは０〜３から選ばれる整数を表し、ｂ、ｃ及びｄは０〜４から選ばれる整数を表し、ｆ及びｇは０〜５から選ばれる整数を表す。）
アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、置換アミノ基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、及び置換カルボキシル基は上記置換基の例示と同様の基を表す。 The hole injection / transport group may be an oligomer or a polymer.
Specifically, from the compound in which two or more of the same or two or more different compounds represented by the above formulas (H-1) to (H-31) are bonded to each other between R atoms, one R or Examples include a residue on R excluding a hydrogen atom.
From the viewpoint of improving hole transportability, the hole injection / transport group is preferably a group represented by the following formula (HA), (H-B), or (HC).

(In the formula, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl. Group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, Represents a cyano group or a nitro group, and each R ′ independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic ring. Represents a group, a, e and h are integers selected from 0 to 3; And b, c and d represent an integer selected from 0 to 4, and f and g represent an integer selected from 0 to 5).
Alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, An acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, and a substituted carboxyl group represent the same groups as those exemplified above.

  The electron injecting and transporting group preferably contains one or more heteroatoms, and more preferably contains one or more nitrogen atoms.

  As the electron injecting and transporting group, a monovalent metal complex of Al or Zn containing a hetero atom other than one or more nitrogen atoms, a hetero atom other than one or more nitrogen atoms, and the periodic table from the second to fourth periods Monovalent metal complexes of metals other than Al and Zn containing the selected element, monovalent groups containing one or more heteroatoms other than nitrogen atoms and one or more nitrogen atoms, one or more sulfur as heteroatoms Examples thereof include monovalent groups containing only atoms, monovalent groups containing only two or more nitrogen atoms as heteroatoms, and monovalent groups containing only one nitrogen atom as heteroatoms.

  As monovalent metal complexes of Al or Zn containing one or more hetero atoms other than nitrogen atoms, the following formulas (E-1) to (E-10), hetero atoms other than one or more nitrogen atoms and the periodic table And monovalent metal complexes of metals other than Al and Zn containing an element selected from the second to fourth periods are represented by the following formulas (E-11) to (E-16) and hetero atoms other than one or more nitrogen atoms. The monovalent group containing an atom and one or more nitrogen atoms is represented by the following formulas (E-17) to (E-28), and the monovalent group containing only one or more sulfur atoms as a hetero atom is represented by the following formula: (E-29) to (E-32), monovalent groups containing only two or more nitrogen atoms as heteroatoms are represented by the following formulas (E-33) to (E-41), As a monovalent group containing only a nitrogen atom, one R from the following formulas (E-42) to (E-45) The residue obtained by removing a hydrogen atom on R are exemplified.

  Examples of R in the above formulas (E-1) to (E-45) are the same as those shown in (H-1) to (H-29).

The electron injection / transport group may be an oligomer or a polymer.
Specifically, from the compound in which two or more of the same or two or more different compounds represented by the above formulas (E-1) to (E-45) are bonded to each other from R, one R or Examples include a residue on R excluding a hydrogen atom.

（式中Ｒは、それぞれ独立に、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、シアノ基又はニトロ基を表し、Ｒ''は、それぞれ独立に、水素原子、アルキル基、アリール基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基又は１価の複素環基を表し、ｉ及びｋは０〜４から選ばれる整数を表し、ｊ、ｌ及びｍは０〜５から選ばれる整数を表す。）
アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、置換アミノ基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、及び置換カルボキシル基は上記置換基の例示と同様の基を表す。 From the viewpoint of improving electron transport properties, the electron injection / transport group is preferably a group represented by the following formula (EA), (EB), or (EC).

(In the formula, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl. Group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, A cyano group or a nitro group, and each R ″ is independently a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group or a monovalent complex. Represents a cyclic group, and i and k represent an integer selected from 0 to 4. , J, l and m is an integer selected from 0-5.)
Alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, An acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, and a substituted carboxyl group represent the same groups as those exemplified above.

  Examples of the luminescent group include a monovalent condensed polycyclic aromatic hydrocarbon group, a monovalent group in which two or more condensed polycyclic aromatic hydrocarbon groups are bonded, one or more nitrogen atoms as heteroatoms, and / or Alternatively, a monovalent heterocyclic group containing only an oxygen atom and a monovalent heterocyclic group containing one or more sulfur atoms as a hetero atom can be mentioned.

  As monovalent condensed polycyclic aromatic hydrocarbon groups, the following formulas (L-1) to (L-5), and monovalent groups in which two or more condensed polycyclic aromatic hydrocarbon groups are bonded: The following formulas (L-6) to (L-8), and (L-23) to (L-26), monovalent heterocyclic groups containing only one or more nitrogen atoms and / or oxygen atoms as heteroatoms Are represented by the following formulas (L-9) to (L-15), and monovalent heterocyclic groups containing one or more sulfur atoms as heteroatoms are represented by the following formulas (L-16) to (L-22). Examples of R or a residue on which a hydrogen atom on R is removed are exemplified.

  Examples of R in the above formulas (L-1) to (L-26) are the same as those shown in (H-1) to (H-29).

  In the above formulas (L-9), (L-10), (L-19), (L-20) and (L-21), R ′ is represented by (H-26) and (H-30). The same thing is illustrated.

（式中Ｒは、それぞれ独立に、水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、シアノ基又はニトロ基を表し、Ｒ''は、それぞれ独立に、水素原子、アルキル基、アリール基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基又は１価の複素環基を表し、ｎ及びｐは０〜９から選ばれる整数を表し、ｏは０〜７から選ばれる整数を表す。）
アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、置換アミノ基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、及び置換カルボキシル基は上記置換基の例示と同様の基を表す。 The light emitting group may be an oligomer or a polymer.
Specifically, from the compound in which the same or two or more different compounds represented by the above formulas (L-1) to (L-26) are bonded to each other with two carbon atoms bonded to R, one R or Examples include a residue on R excluding a hydrogen atom.
From the viewpoint of improving luminous efficiency, the electron injecting / transporting group is preferably a group represented by the following formula (LA), (LB) or (LC).

(In the formula, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl. Group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, A cyano group or a nitro group, and each R ″ is independently a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group or a monovalent complex. Represents a cyclic group, and n and p represent an integer selected from 0 to 9. , O is an integer selected from 0-7.)
Alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, An acyl group, an acyloxy group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, and a substituted carboxyl group represent the same groups as those exemplified above.

  The functional side chain may be present alone or two or more different functional side chains may be present.

  From the viewpoint of improving hole transportability, the functional side chain is preferably a hole injection transport group, a monovalent aromatic amine containing two or more nitrogen atoms, and a monovalent aromatic containing two or more nitrogen atoms. It is more preferably a carbazole derivative, a monovalent metal complex containing two or more nitrogen atoms, and a monovalent group containing one or more nitrogen atoms and a hetero atom other than one or more nitrogen atoms. More preferably, they are monovalent aromatic amines containing at least one, monovalent carbazole derivatives containing two or more nitrogen atoms, and monovalent metal complexes containing two or more nitrogen atoms, and 1 containing two or more nitrogen atoms. Most preferably, it is a monovalent carbazole derivative containing a valent aromatic amine and two or more nitrogen atoms.

  From the viewpoint of improving electron transport properties, the functional side chain is preferably an electron injection transport group, and a monovalent metal complex of Al or Zn containing one or more heteroatoms other than nitrogen atoms, one or more A monovalent metal complex of a metal other than Al and Zn containing a heteroatom other than a nitrogen atom and an element selected from the second to fourth periods in the periodic table, a monovalent metal containing only one or more sulfur atoms as a heteroatom A monovalent group containing only two or more nitrogen atoms as a group and a hetero atom is more preferable, and a monovalent metal complex of Al or Zn containing a hetero atom other than one or more nitrogen atoms, as a hetero atom More preferably, it is a monovalent group containing only one or more sulfur atoms and a monovalent group containing only two or more nitrogen atoms as heteroatoms.

  From the viewpoint of improving luminous efficiency, the functional side chain is preferably a luminescent group, and a monovalent condensed polycyclic aromatic hydrocarbon group or two or more condensed polycyclic aromatic hydrocarbon groups are bonded to each other. A monovalent group and a monovalent heterocyclic group containing only one or more nitrogen atoms and / or oxygen atoms as heteroatoms are more preferable, and two or more condensed polycyclic aromatic hydrocarbon groups are bonded. The monovalent group and the monovalent heterocyclic group containing only one or more nitrogen atoms and / or oxygen atoms as heteroatoms are more preferable.

  In the polymer compound of the present invention, the functional side chain is —Rj— or —Rj—X— (where Rj is a group in which one or more carbon atoms constituting an alkylene group are replaced with nitrogen atoms). (Hereinafter also referred to as a nitrogen-substituted alkylene group), and the nitrogen-substituted alkylene group may have a substituent, and X is O, S, or N (R ′), and X is a main chain. R ′ each independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic group. )) To the main chain.

The side chain is bonded to the main chain via a nitrogen-substituted alkylene group -Rj- means that the atom at one end of the nitrogen-substituted alkylene group is bonded to the side chain and the atom at the other end is connected to the main chain. Indicates that it is bound to. Atoms bonded to the main chain, may be carbon, other -O -, - S -, - CO -, - CO 2 -, - SO -, - SO 2 -, - SiR 8 R ^It may be a group selected from the group consisting of ⁹ —, —NR ¹⁰ —, —BR ¹¹ —, —PR ¹² —, and —P (═O) (R ¹³ ) —.

The nitrogen-substituted alkylene group usually has about 1 to 12 carbon atoms, excluding the carbon number contained in the substituent, and examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, Arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imino group, amide Group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group and cyano group.
Preferred examples of the alkylene group include —C ₃ H ₆ —, —C ₄ H ₈ —, —C ₅ H ₁₀ —, —C ₆ H ₁₂ —, —C ₈ H ₁₆ —, —C ₁₀ H ₂₀ — and the like. Is mentioned.

Here, R ^{8 to} R ¹³ are the same as those described in R ^{1 to} R ⁷ .

The polymer compound of the present invention, from the viewpoint of the life characteristics of the device, it is preferable that the number average molecular weight in terms of polystyrene is 10 ³ to 10 ^8, more preferably 10 ³ to 10 ^7, 10 ⁴ ~ More preferably, it is 10 ⁷ .

The polymer compound of the present invention, from the viewpoint of the life characteristics of the device preferably has a weight average molecular weight in terms of polystyrene is 10 ³ to 10 ^8, and more preferably 10 ³ to 10 ^7.

  Here, the number average molecular weight and the weight average molecular weight can be determined as a number average molecular weight and a weight average molecular weight in terms of polystyrene by size exclusion chromatography (SEC).

  The preferable example of the high molecular compound in this invention is described here.

When the repeating unit in the main chain to which the functional side chain is bonded is a divalent heterocyclic group from the viewpoint of light emission efficiency, device durability, and ease of synthesis, the following formula (5-1) It is preferably ~ (5-15), and when it is a divalent arylene group, it is preferably the following formulas (5-16) to (5-41), and when it is a divalent aromatic amine group Is preferably the following formulas (5-42) to (5-46).
The following formulas (5-1) to (5-46) may have a substituent.
Examples of the substituent include the same as the substituent.

（式中Ｘ₈₇〜Ｘ₁₀₁は前記Ｘ₁〜Ｘ₈₆における例示と同じものを表し、Ｙ₃₀〜Ｙ₃₄は前記Ｙ₁〜Ｙ₂₉における例示と同じものを表し、Ｊは前記窒素置換アルキレン基Ｒｊを表し、Ｆｕｎは機能性側鎖を表し、Ｒ_W1〜Ｒ_W4及びＲ_X1〜Ｒ_X4は前記Ｒ_W〜Ｒ_Xにおける例示と同じものを表す。）

(In the formula, X _{87 to} X ₁₀₁ represent the same examples as in X _{1 to} X ₈₆ , Y _{30 to} Y ₃₄ represent the same examples as in Y _{1 to} Y ₂₉ , and J represents the nitrogen-substituted alkylene group. Rj is represented, Fun represents a functional side chain, and R _{W1 to} R _W4 and R _{X1 to} R _X4 represent the same examples as those in R _{W to} R _X. )

From the viewpoints of luminous efficiency, device durability, and ease of synthesis, X _{87 to} X _{101 in} the above formulas (5-1) to (5-46) are a nitrogen atom, a boron atom, and —Si (R ¹ ) =. It is preferable that there is a nitrogen atom and —Si (R ¹ ) ═, and more preferably a nitrogen atom.

From the viewpoints of luminous efficiency, device durability, and ease of synthesis, Y _{30 to} Y _{34 in} the above formulas (5-1) to (5-46) are oxygen atoms, sulfur atoms, —N (R ⁴ ) —. , —B (R ⁵ ) —, Si (R ⁶ ) (R ⁷ ) —, and —P (R ⁸ ) — are preferable, and oxygen atom, sulfur atom, —N (R ⁴ ) —, —B ( R ⁵ )-and Si (R ⁶ ) (R ⁷ )-are more preferable, and oxygen atoms, sulfur atoms, -N (R ⁴ )-and Si (R ⁶ ) (R ⁷ )-are preferable. Further preferred.

  From the viewpoints of luminous efficiency, device durability, and ease of synthesis, in the above formulas (5-1) to (5-46), when the nitrogen-substituted alkylene group represented by J has a substituent, J is: It is preferably an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, or a monovalent heterocyclic group. More preferably an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, a monovalent heterocyclic group, an alkyl group, an alkoxy group, an aryl group, It is more preferably a monovalent heterocyclic group, an alkyl group, an alkoxy group, or an aryl group. Rukoto is most preferable.

From the viewpoints of light emission efficiency, device durability, and ease of synthesis, the atoms bonded to the main chain in the nitrogen-substituted alkylene group may be carbon atoms or other atoms. When the atom is other than carbon, it is preferably —O—, —S—, —CO—, —, —SiR ⁸ R ⁹ —, —NR ¹⁰ —, —BR ¹¹ —, -, - S -, - SiR 8 R 9 -, - NR 10 - more preferably, -O -, - S -, - more preferably ^{from, -O - - NR 10, -} NR 10 -Is most preferred.

  From the viewpoint of luminous efficiency, device durability, and ease of synthesis, in the above formulas (5-1) to (5-46), when Fun is a hole injecting and transporting group, the above formula (H-1) It is preferably a residue obtained by removing one R or a hydrogen atom on R from (H-31), and the above formulas (H-1) to (H-3), (H-5), (H It is more preferably a residue obtained by removing one R or a hydrogen atom on R from -15) to (H-17), and the above formulas (H-1), (H-2), (H-15) And a residue obtained by removing one R or a hydrogen atom on R from (H-16).

  From the viewpoints of luminous efficiency, device durability, and ease of synthesis, in the above formulas (5-1) to (5-46), when Fun is an electron injecting and transporting group, the above formula (E-1) to It is preferably a residue obtained by removing one R or a hydrogen atom on R from (E-44), and the above formulas (E-1) to (E-10), (E-28) to (E- 31), (E-41) to (E-44), more preferably a residue obtained by removing one hydrogen atom on R or R, and the above formulas (E-1) and (E-2) , (E-4) to (E-6), (E-28), (E-31), (E-41), (E-42), one hydrogen atom on R or R was removed. More preferably, it is a residue, from (E-1), (E-2), (E-28), (E-31), (E-41), (E-42) to one R or Residue excluding hydrogen atom on R There it is most preferable.

  From the viewpoints of luminous efficiency, device durability, and ease of synthesis, in the above formulas (5-1) to (5-46), when Fun is a light emitting group, the above formulas (L-1) to (L It is preferably a residue obtained by removing one R or a hydrogen atom on R from -26), and the above formulas (L-6) to (L-8) and (L-9) to (L-16) It is more preferable that it is the residue remove | excluding the hydrogen atom on one R or R from said Formula (L-6), (L-7), (L-9)-(L-14) to 1 It is more preferable that it is the residue remove | excluding the hydrogen atom on R piece or R, and it is one piece from said Formula (L-6), (L-7), (L-9)-(L-14). Most preferred is R or a residue obtained by removing a hydrogen atom on R.

  From the viewpoints of luminous efficiency, device durability, and ease of synthesis, the above formulas (H-1) to (H-31), (E-1) to (E-44), and (L-1) to (L -26) wherein R is a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, 1 Preferably a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, a monovalent heterocyclic group. And more preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group. Kill group, an alkoxy group, and most preferably an aryl group.

  Among the above formulas (5-1) to (5-15) in which the repeating unit of the main chain is a divalent heterocyclic group, from the viewpoint of luminous efficiency, device durability, and ease of synthesis, (5-1) to (5-4), (5-7) to (5-9), (5-12), and (5-13) are preferable, and (5-1) and (5-2) ), (5-7) to (5-9), (5-12), and (5-13), more preferably (5-7), (5-8), and (5-13). More preferably it is.

  Among the above formulas (5-16) to (5-41), which are arylene groups, from the viewpoints of luminous efficiency, element durability, and ease of synthesis, the above formulas (5-16) to (5-19) , (5-22) to (5-25), (5-26), (5-27), (5-30), (5-32) to (5-34), (5-36) to ( 5-38) and (5-40), (5-16), (5-17), (5-22) to (5-25), (5-26), (5-27) It is more preferable that it is (5-23), (5-24) (5-30) to (5-34), and (5-35).

  Among the above formulas (5-42) to (5-46), which are divalent aromatic amines, from the viewpoints of light emission efficiency, device durability, and ease of synthesis, the above formulas (5-42) to ( 5-44) is most preferred.

  From the viewpoint of luminous efficiency, device durability, and ease of synthesis, when the groups represented by the above formulas (5-1) to (5-46) have a substituent, an alkyl group, an alkoxy group, an alkylthio group, an aryl Group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group, alkyl group, alkoxy group, alkylthio group, An aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, and a monovalent heterocyclic group are more preferable, and an alkyl group, an alkoxy group, an aryl group, and a monovalent heterocyclic group are preferable. More preferred are an alkyl group, an alkoxy group, and an aryl group.

The polymer compound of the present invention comprises a copolymer containing one or more other repeating units in addition to the above repeating units from the viewpoint of changing the emission wavelength, increasing the luminous efficiency, improving the heat resistance, and the like. preferable. As the repeating unit other than the repeating unit, a repeating unit represented by the following formula (8) is preferable.

—Ar ₈ — (8)

In the formula, each Ar ₈ independently represents a divalent group having a metal complex structure.

The divalent group having a metal complex structure in Ar ₁ is the remaining divalent group obtained by removing two hydrogen atoms from the organic ligand of the metal complex having an organic ligand.
The organic ligand usually has about 4 to 60 carbon atoms. Examples thereof include 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, and 2-phenyl-benzo. Examples include thiazole and its derivatives, 2-phenyl-benzoxazole and its derivatives, porphyrin and its derivatives.
Examples of the central metal of the complex include aluminum, zinc, beryllium, iridium, platinum, gold, europium, and terbium.
Examples of the metal complex having an organic ligand include a low-molecular fluorescent material, a metal complex known as a phosphorescent material, and a triplet light-emitting complex.

Specific examples of the divalent group having a metal complex structure include the following formulas 126 to 132.

  In the above formulas 126 to 132, R is the same as described above.

  The polymer compound of the present invention may be a random, block or graft copolymer, or may be a polymer having an intermediate structure thereof, such as a random copolymer having a block property. Good. From the viewpoint of obtaining a polymer light emitter having a high quantum yield of fluorescence or phosphorescence, a random copolymer having a block property and a block or graft copolymer are preferable to a complete random copolymer. A case in which the main chain is branched and there are three or more terminal portions and dendrimers are also included.

  In addition, since the terminal group of the polymer compound of the present invention may be protected with a stable group, if the polymerization active group is left as it is, there is a possibility that the light emission characteristics and life when the device is formed may be reduced. Good. The terminal group preferably has a conjugated bond continuous with the conjugated structure of the main chain, and examples thereof include a structure bonded to an aryl group or heterocyclic group via a carbon-carbon bond. Specific examples include substituents described in Chemical formula 10 of JP-A-9-45478.

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

Next, the manufacturing method of the high molecular compound of this invention is demonstrated.
That is, the present invention is a monomer having at least one selected from the group consisting of an arylene group, a divalent heterocyclic group, and a divalent aromatic amine group, and includes a hole injection transport group, an electron injection transport group, and A method for producing a light emitting or charge transporting polymer compound comprising polymerizing a raw material monomer containing the above monomer having at least one functional group selected from the group consisting of a light emitting group, the functional group Are —Rj— or —Rj—X— (Rj is a group having one or more carbon atoms constituting the alkylene group replaced with a nitrogen atom (hereinafter also referred to as a nitrogen-substituted alkylene group). The nitrogen-substituted alkylene group may have a substituent, X is O, S, or N (R ′), and is bonded to the main chain by X. R ′ is independently , Hydrogen atom, alkyl group, aryl group , An arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, or a monovalent heterocyclic group). .
For example, the polymer compound of the present invention can be produced by condensation polymerization using a compound represented by V ₁ -QV ₂ as one of raw material monomers. Here, Q represents an arylene group, a divalent heterocyclic group, or a divalent aromatic amine group that may contain a functional substituent in the side chain. V ₁ and V ₂ each independently represent a substituent capable of condensation polymerization.

  In addition, when the polymer compound of the present invention has a repeating unit other than -Q-, a raw material monomer is a compound having two substituents involved in condensation polymerization, which becomes a repeating unit other than -Q-. What is necessary is just to carry out condensation polymerization by coexisting.

Examples of the compound having two condensation-polymerizable substituents that are repeating units other than the repeating unit represented by -Q- include compounds of V ₃ -Ar ₈ -V ₄ (wherein Ar ₈ Is the same as defined above, and V ₃ and V ₄ each independently represent a substituent capable of condensation polymerization.
That is, the polymer compound of the present invention can also be produced by subjecting a compound represented by V ₃ -Ar ₈ -V ₄ to condensation polymerization in addition to a compound represented by V ₁ -QV ₂ .

In the production method of the present invention, the substituent involved in the condensation polymerization includes a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate ester group, a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, Examples thereof include a monohalogenated methyl group, —B (OH) ₂ , formyl group, cyano group, vinyl group and the like.

  Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkyl sulfonate group include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group. Examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group. Examples of the aryl sulfonate group include benzyl. Examples include sulfonate groups.

式中、Ｍｅはメチル基を、Ｅｔはエチル基を示す。 Examples of the borate group include groups represented by the following formula.

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

Examples of the sulfonium methyl group include groups represented by the following formula.
_{^{-CH 2 S + Me 2 X -}} , -CH 2 S + Ph 2 X -
(X represents a halogen atom, and Ph represents a phenyl group.)

Examples of the phosphonium methyl group include groups represented by the following formula.
_{^{-CH 2 P + Ph 3 X -}} (X represents a halogen atom.)

Examples of the phosphonate methyl group include groups represented by the following formula.
—CH ₂ PO (OR ′) ₂ (X represents a halogen atom, R ′ represents an alkyl group, an aryl group, or an arylalkyl group.)

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

The preferred substituents involved in the condensation polymerization vary depending on the type of polymerization reaction. For example, when using a zero-valent nickel complex such as a Yamamoto coupling reaction, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an aryl alkyl sulfonate. Groups. In the case of using a nickel catalyst or a palladium catalyst such as a Suzuki coupling reaction, an alkyl sulfonate group, a halogen atom, a borate group, -B (OH) _{2 and the} like can be mentioned.

  Specifically, in the production method of the present invention, a compound having a plurality of substituents involved in condensation polymerization, which is a monomer, is dissolved in an organic solvent as necessary. For example, using an alkali or a suitable catalyst, It can be carried out at a melting point of not less than the boiling point. For example, “Organic Reactions”, Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965, “Organic Synthesis”, Collective Volume 6. (Collective Volume VI), 407-411, John Wiley & Sons, Inc., 1988, Chemical Review (Chem. Rev.), 95, 2457 (1995), Journal of Organometallic. Chemistry (J. Organomet. Chem.), 576, 147 (1999), Macromolecular Chemistry Macro Rekyura Symposium (Makromol., Macromol.Symp.), Vol. 12, page 229 (1987) may be a known method described, for example.

  In the method for producing a polymer compound of the present invention, a known condensation reaction can be used as the condensation polymerization method depending on the substituent involved in the condensation polymerization.

For example, a method of polymerizing a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a Ni (0) complex, a method of polymerizing by an oxidizing agent such as FeCl ₃ , or electrochemically oxidative polymerization Or a method by decomposition of an intermediate polymer having an appropriate leaving group.

  Among these, the method of polymerizing by Suzuki coupling reaction, the method of polymerizing by Grignard reaction, and the method of polymerizing by nickel zero-valent complex are preferable because the structure can be easily controlled.

In the production method of the present invention, the substituents involved in the condensation polymerization are each independently selected from a halogen atom, an alkyl sulfonate group, an aryl sulfonate group or an arylalkyl sulfonate group, and the condensation polymerization is performed in the presence of a nickel zero-valent complex. A production method is preferred.
As raw material compounds, dihalogenated compounds, bis (alkyl sulfonate) compounds, bis (aryl sulfonate) compounds, bis (aryl alkyl sulfonate) compounds, halogen-alkyl sulfonate compounds, halogen-aryl sulfonate compounds, halogen-aryl alkyl sulfonate compounds, Examples thereof include alkyl sulfonate-aryl sulfonate compounds, alkyl sulfonate-aryl alkyl sulfonate compounds, and aryl sulfonate-aryl alkyl sulfonate compounds.

  In this case, for example, a halogen-alkyl sulfonate compound, a halogen-aryl sulfonate compound, a halogen-aryl alkyl sulfonate compound, an alkyl sulfonate-aryl sulfonate compound, an alkyl sulfonate-aryl alkyl sulfonate compound, or an aryl sulfonate-aryl alkyl sulfonate compound as a raw material compound. By using it, a method for producing a polymer compound with a controlled sequence can be mentioned.

In the production method of the present invention, the substituents involved in the condensation polymerization are each independently selected from a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a boric acid group, or a boric acid ester group. The total number of moles of halogen atoms, alkyl sulfonate groups, aryl sulfonate groups and aryl alkyl sulfonate groups (J), boric acid groups (—B (OH) ₂ ) and boric acid ester groups of all raw material compounds. A production method in which the ratio of the total number of moles (K) is substantially 1 (usually K / J is in the range of 0.7 to 1.2) and condensation polymerization using a nickel catalyst or a palladium catalyst is preferred.
Specific examples of the combination of raw material compounds include a combination of a dihalogenated compound, a bis (alkyl sulfonate) compound, a bis (aryl sulfonate) compound or a bis (aryl alkyl sulfonate) compound and a diboric acid compound or a diboric acid ester compound. .
Also, halogen-boric acid compounds, halogen-boric acid ester compounds, alkyl sulfonate-boric acid compounds, alkyl sulfonate-boric acid ester compounds, aryl sulfonate-boric acid compounds, aryl sulfonate-boric acid ester compounds, arylalkyl sulfonate-borates Examples include acid compounds, arylalkyl sulfonate-boric acid compounds, and arylalkyl sulfonate-boric acid ester compounds.

  In this case, for example, as a raw material compound, a halogen-boric acid compound, a halogen-boric acid ester compound, an alkyl sulfonate-boric acid compound, an alkyl sulfonate-boric acid ester compound, an aryl sulfonate-boric acid compound, an aryl sulfonate-boric acid ester compound, The method of manufacturing the polymeric compound which controlled the sequence by using an arylalkyl sulfonate-boric acid compound, an arylalkyl sulfonate-boric acid compound, and an arylalkyl sulfonate-boric acid ester compound is mentioned.

  The solvent varies depending on the compound and reaction to be used, but it is generally preferable that the solvent to be used is sufficiently deoxygenated and the reaction is allowed to proceed in an inert atmosphere in order to suppress side reactions. Moreover, it is preferable to perform a dehydration process for the same reason. However, this is not the case in the case of a two-phase reaction with water such as the Suzuki coupling reaction.

  Solvents include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, chloropentane and bromopentane. Halogenated saturated hydrocarbons such as chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, methanol, ethanol, propanol, isopropanol, butanol, t-butyl alcohol Alcohols such as formic acid, acetic acid, propionic acid, dimethyl ether, diethyl ether, methyl-t-butyl ether, tetra Ethers such as drofuran, tetrahydropyran, dioxane, trimethylamine, triethylamine, N, N, N ′, N′-tetramethylethylenediamine, amines such as pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N , N-diethylacetamide, amides such as N-methylmorpholine oxide, etc. are exemplified, and a single solvent or a mixed solvent thereof may be used. Of these, ethers are preferable, and tetrahydrofuran and diethyl ether are more preferable.

  In order to make it react, an alkali and a suitable catalyst are added suitably. These may be selected according to the reaction used. The alkali or catalyst is preferably one that is sufficiently dissolved in the solvent used in the reaction. As a method of mixing the alkali or catalyst, slowly add the alkali or catalyst solution while stirring the reaction solution under an inert atmosphere such as argon or nitrogen, or conversely, slowly add the reaction solution to the alkali or catalyst solution. And the method of adding.

  When the polymer compound of the present invention is used for a polymer LED or the like, its purity affects the performance of the device such as light emission characteristics. Therefore, after the monomer before polymerization is purified by a method such as distillation, sublimation purification, recrystallization, etc. It is preferable to polymerize. Further, after the polymerization, it is preferable to carry out a purification treatment such as reprecipitation purification and fractionation by chromatography.

Next, the use of the polymer compound of the present invention will be described.
The polymer compound of the present invention usually emits fluorescence or phosphorescence in a solid state and can be used as a polymer light emitter (high molecular weight light emitting material).
Further, the polymer compound has an excellent charge transport ability, and can be suitably used as a polymer LED material or a charge transport material. The polymer LED using the polymer light emitter is a high-performance polymer LED that can be driven with low voltage and high efficiency. Therefore, the polymer LED can be preferably used for a backlight of a liquid crystal display or a device such as a curved or flat light source for illumination, a segment type display element, a dot matrix flat panel display.
The polymer compound of the present invention can also be used as a material for conductive thin films such as laser dyes, organic solar cell materials, organic semiconductors for organic transistors, conductive thin films, and organic semiconductor thin films.
Furthermore, it can also be used as a light-emitting thin film material that emits fluorescence or phosphorescence.

（式中Ａｒ_aはアリール基、１価の複素環基又は１価の芳香族アミンを表す。）
を１級アミンの存在下で、還元剤と反応させて、
式（Ｍ−Ｂ）で示される化合物

（式中Ａｒ_aはアリール基、１価の複素環基又は１価の芳香族アミンを表し、Ｒ''は水素原子、アルキル基、アリール基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基又は１価の複素環基を表す。）
を製造し、
上記式（Ｍ−Ｂ）で示される化合物を塩基の存在下でＸ−Ｊ₁−Ｘ（式中Ｊ₁はアルキレン基を表し、Ｘはハロゲン原子を表す。）で示される化合物と反応させることを特徴とする、
式（Ｍ−Ｃ）で示される有機ＥＬ材料の中間体化合物

（式中Ａｒ_aはアリール基、１価の複素環基又は１価の芳香族アミンを表し、Ｒ''は水素原子、アルキル基、アリール基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基又は１価の複素環基を表し、Ｊ₁はアルキレン基を表し、Ｘはハロゲン原子を表す。）
の製造方法を提供するものである。 In addition, the present invention provides a compound represented by the following formula (MA)

(In the formula, Ar _a represents an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine.)
Is reacted with a reducing agent in the presence of a primary amine,
Compound represented by formula (MB)

(In the formula, Ar _a represents an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine, and R ″ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, Represents an arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic group.)
Manufacture and
Reacting the compound represented by the formula (MB) with a compound represented by XJ ₁ -X (wherein J ₁ represents an alkylene group and X represents a halogen atom) in the presence of a base. Characterized by the
Intermediate compound of organic EL material represented by formula (MC)

(In the formula, Ar _a represents an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine, and R ″ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic group, J ₁ represents an alkylene group, X represents a halogen atom.)
The manufacturing method of this is provided.

The aryl group, monovalent heterocyclic group and monovalent aromatic amine have the same meaning as described above.
The alkyl group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, halogen atom and alkylene group have the same meaning as described above.
Examples of the primary amine include aromatic amines and alkylamines. As the aromatic amine, aniline and 2-pyridylamine are preferable, and as the alkylamine, methylamine, propylamine, octylamine and the like are preferable.
The reducing agent is preferably a boron-containing compound or an aluminum-containing compound. Examples of the boron-containing compound include sodium borohydride. Examples of the aluminum-containing compound include lithium aluminum hydride.
As the base, inorganic bases and Lewis bases are preferable. Examples of the inorganic base include carbonates, hydrogen carbonates, and hydroxides. Examples of the carbonates include potassium carbonate and sodium carbonate. Examples of the hydrogen carbonates include hydrogen carbonate. Examples of the hydroxide include potassium and sodium bicarbonate, and examples of the hydroxide include potassium hydroxide and sodium hydroxide.
As the Lewis base, tertiary amines are more preferable. Examples thereof include tertiary amines such as trimethylamine, triethylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine; N, N, N ′, N ′ -Multidentate tertiary amines such as tetramethylethylenediamine; substituted pyridines such as pyridine and N, N-dimethylaminopyridine are exemplified.
Although the method of reaction is not particularly limited, it can be carried out in the presence of a solvent under an atmosphere of an inert gas such as nitrogen or argon. With respect to the reaction temperature, it can be -100 ° C to the boiling point of the solvent, and preferably -100 ° C to 10 ° C. The reaction time is about 30 minutes to 200 hours.
Solvents used in the reaction include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, dimethyl ether, diethyl ether, methyl t-butyl ether, tetrahydrofuran, Examples thereof include ethers such as tetrahydropyran and dioxane, and mixtures thereof.

（式中Ａｒ_bはアリーレン基、２価の複素環基又は２価の芳香族アミンを表す。Ｘ_aはハロゲン原子を表す。）
と反応させることにより、
式（Ｍ−Ｅ）又は式（Ｍ−Ｆ）で示される化合物

（式中Ａｒ_aはアリール基、１価の複素環基又は１価の芳香族アミンを表し、Ｒ''は水素原子、アルキル基、アリール基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基又は１価の複素環基を表し、Ｊ₁はアルキレン基、アルケニレン基、又はアルキニレン基を表し、Ｘ_aはハロゲン原子を表し、Ａｒ_cは３価の芳香族炭化水素基、３価の複素環基又は３価の芳香族アミンを表し、Ａｒ_dは４価の芳香族炭化水素基、４価の複素環基又は４価の芳香族アミンを表す。）
を合成し、
式（Ｍ−Ｅ）又は式（Ｍ−Ｆ）で示される化合物を重合することにより高分子化合物を合成する
ことを特徴とする高分子化合物の製造方法を提供するものである。 The present invention also provides a compound represented by the above formula (MC) in the presence of a base,
Compound represented by formula (MD)

(In the formula, Ar _b represents an arylene group, a divalent heterocyclic group or a divalent aromatic amine. X _a represents _a halogen atom.)
By reacting with
Compound represented by formula (ME) or formula (MF)

(In the formula, Ar _a represents an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine, R ″ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic group, J ₁ represents an alkylene group, an alkenylene group, or alkynylene group, X _a represents a halogen atom, Ar _c trivalent aromatic hydrocarbon Group represents a trivalent heterocyclic group or a trivalent aromatic amine, and Ar _d represents a tetravalent aromatic hydrocarbon group, a tetravalent heterocyclic group or a tetravalent aromatic amine.)
Synthesize
A polymer compound is synthesized by polymerizing a compound represented by the formula (ME) or the formula (MF) to provide a method for producing a polymer compound.

The arylene group, divalent heterocyclic group or divalent aromatic amine represents the same group as described above.
The trivalent aromatic hydrocarbon group is a group in which an arylene group has another bond and has three bonds. Specifically, it is a residue obtained by removing one R or one hydrogen atom on R exemplified as an arylene group.
A trivalent heterocyclic group is a group in which a divalent heterocyclic group further has another bond and has three bonds. Specifically, it is a residue obtained by removing one R or one hydrogen atom on R exemplified as a divalent heterocyclic group.
A trivalent aromatic amine is a group in which a divalent aromatic amine has another bond and has three bonds. Specifically, it is a residue obtained by removing one R or one hydrogen atom on R exemplified in the case of a divalent aromatic amine.
A tetravalent aromatic hydrocarbon group is a group in which an arylene group has two more bonds and four bonds. Specifically, it is a residue obtained by removing two of the two R atoms exemplified for the arylene group or two hydrogen atoms on R.
A tetravalent heterocyclic group is a group in which a divalent heterocyclic group has two more bonds and four bonds. Specifically, it is a residue obtained by removing two Rs or two hydrogen atoms on R exemplified in the divalent heterocyclic group.
A tetravalent aromatic amine is a group in which a divalent aromatic amine has two more bonds and four bonds. Specifically, it is a residue obtained by removing two Rs or two hydrogen atoms on R exemplified in the case of a divalent aromatic amine.
As the base, inorganic bases and Lewis bases are preferable. Examples of the inorganic base include carbonates, hydrogen carbonates, and hydroxides. Examples of the carbonates include potassium carbonate and sodium carbonate. Examples of the hydrogen carbonates include hydrogen carbonate. Examples of the hydroxide include potassium and sodium bicarbonate, and examples of the hydroxide include potassium hydroxide and sodium hydroxide.
As the Lewis base, tertiary amines are more preferable. Examples thereof include tertiary amines such as trimethylamine, triethylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine; N, N, N ′, N ′ -Multidentate tertiary amines such as tetramethylethylenediamine; substituted pyridines such as pyridine and N, N-dimethylaminopyridine are exemplified.

Although the method of reaction is not particularly limited, it can be carried out in the presence of a solvent under an atmosphere of an inert gas such as nitrogen or argon. With respect to the reaction temperature, it can be -100 ° C to the boiling point of the solvent, and preferably -100 ° C to 10 ° C. The reaction time is about 30 minutes to 200 hours.
Solvents used in the reaction include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, dimethyl ether, diethyl ether, methyl t-butyl ether, tetrahydrofuran, Examples thereof include ethers such as tetrahydropyran and dioxane, and mixtures thereof.
The method of polymerizing the compound is not particularly limited, but the method of polymerizing by the above-described Suzuki coupling reaction, the method of polymerizing by the Grignard reaction, the method of polymerizing by Ni (0) complex, the method of polymerizing by an oxidizing agent such as FeCl ₃ , Examples thereof include a method of chemically oxidative polymerization or a method of decomposing an intermediate polymer having an appropriate leaving group.

（式中Ｒ'''は、それぞれ独立に、水素原子、アルキル基、アリール基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基又は１価の複素環基を表し、Ｊ２はアルキレン基を表し、Ｘはハロゲン原子を表す。）
アルキル基、アリール基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、１価の複素環基、アルキレン基及びハロゲン原子は前記と同様の意味を表す。 Furthermore, the present invention provides a compound having a partial structure represented by the following formula (MG).

Wherein R ′ ″ each independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic group. , J2 represents an alkylene group, and X represents a halogen atom.)
The alkyl group, aryl group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group, alkylene group and halogen atom have the same meanings as described above.

Further, the above formula (MG) includes three compounds (MG1) to (MG4) having one carbazole skeleton, two compounds (MG5) to (MG7) having two carbazole skeletons, The compound (M-G8) having the above carbazole skeleton is exemplified, and a compound having one or two carbazole skeletons is preferable from the viewpoint of light emission efficiency.

R in the above formulas (M-G1) to (M-G8) is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy. Group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent Represents a heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group.
In the above formulas (M-G1) to (M-G8), R ′ ″ is independently a hydrogen atom, alkyl group, aryl group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl. An alkynyl group or a monovalent heterocyclic group is represented, J ₂ represents an alkylene group, and X represents a halogen atom.
Alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, The acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, substituted carboxyl group, halogen atom, and alkylene group are the same as the examples of the substituent.
From the viewpoint of organic synthesis, X _b is preferably a chlorine atom, a bromine atom, or an iodine atom, and more preferably a bromine atom or an iodine atom.

（式中Ｊ_３はアルキレン基を表し、Ｘはハロゲン原子を表す。）
アルキレン基及びハロゲン原子は前記と同様の意味を表す。
本発明はまた、アリーレン基、２価の複素環基及び２価の芳香族アミン基からなる群から選ばれる少なくとも１つを有するモノマーであって、正孔注入輸送基、電子注入輸送基及び発光基からなる群から選ばれる少なくとも一つの機能性基を有する上記モノマーを含む原料モノマーを重合することを含む、発光性又は電荷輸送性の高分子化合物の製造方法であって、該機能性基が、−Ｒｊ−又は−Ｒｊ−Ｘ−（Ｒｊは、アルキレン基を構成する１個以上の炭素原子が、窒素原子で置き換えられた構成を有する基（以下、窒素置換アルキレン基ともいう。）を表し、該窒素置換アルキレン基は置換基を有していてもよい。ＸはＯ、Ｓ、又はＮ(Ｒ’)であり、Ｘで主鎖に結合している。Ｒ'は、それぞれ独立に、水素原子、アルキル基、アリール基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基又は１価の複素環基を表す。）を介して該モノマーに結合していることを特徴とする上記製造方法を提供するものである。
本発明はまた、−Ｒｊ−又は−Ｒｊ−Ｘ−（Ｒｊは、アルキレン基を構成する１個以上の炭素原子が、窒素原子で置き換えられた構成を有する基（以下、窒素置換アルキレン基ともいう。）を表し、該窒素置換アルキレン基は置換基を有していてもよい。ＸはＯ、Ｓ、又はＮ(Ｒ’)であり、Ｘで主鎖に結合している。Ｒ'は、それぞれ独立に、水素原子、アルキル基、アリール基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基又は１価の複素環基を表す。）を介して機能性側鎖を主鎖に結合させることを特徴とする高分子化合物の主鎖への機能性側鎖の導入方法を提供するものである。 From the viewpoint of organic synthesis, R ′ ″ is preferably an alkyl group, an aryl group or an arylalkyl group, and most preferably an alkyl group.
Furthermore, the present invention provides a compound represented by the following formula (M-H).

(Wherein J ₃ represents an alkylene group, and X represents a halogen atom.)
An alkylene group and a halogen atom represent the same meaning as described above.
The present invention is also a monomer having at least one selected from the group consisting of an arylene group, a divalent heterocyclic group, and a divalent aromatic amine group, wherein the hole injection transport group, the electron injection transport group, and the light emission A method for producing a light emitting or charge transporting polymer compound comprising polymerizing a raw material monomer containing the above monomer having at least one functional group selected from the group consisting of groups, wherein the functional group is , -Rj- or -Rj-X- (Rj represents a group having one or more carbon atoms constituting the alkylene group substituted with a nitrogen atom (hereinafter also referred to as a nitrogen-substituted alkylene group). The nitrogen-substituted alkylene group may have a substituent, X is O, S, or N (R ′), and is bonded to the main chain at X. R ′ is independently A hydrogen atom, an alkyl group, an aryl group, An arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, or a monovalent heterocyclic group), which is bonded to the monomer. To do.
In the present invention, -Rj- or -Rj-X- (Rj is a group having one or more carbon atoms constituting an alkylene group substituted with a nitrogen atom (hereinafter also referred to as a nitrogen-substituted alkylene group). The nitrogen-substituted alkylene group may have a substituent, X is O, S, or N (R ′), and is bonded to the main chain by X. R ′ is Each independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic group). The present invention provides a method for introducing a functional side chain into a main chain of a polymer compound, characterized in that is bonded to the main chain.

Next, the polymer LED of the present invention will be described.
The polymer LED of the present invention has an organic layer between electrodes composed of an anode and a cathode, and the organic layer contains the polymer compound of the present invention.
The organic layer may be any of a light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, an interlayer layer, and the like, but the organic layer is preferably a light emitting layer.
Here, the light emitting layer refers to a layer having a function of emitting light, the hole transport layer refers to a layer having a function of transporting holes, and the electron transport layer is a layer having a function of transporting electrons. Say. The interlayer layer is adjacent to the light emitting layer between the light emitting layer and the anode, and serves to isolate the light emitting layer and the anode or the light emitting layer from the hole injection layer or the hole transport layer. It is a layer that has. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. The electron injection layer and the hole injection layer are collectively referred to as a charge injection layer. Two or more light emitting layers, hole transport layers, hole injection layers, electron transport layers, and electron injection layers may be used independently.
When the organic layer is a light emitting layer, the light emitting layer that is an organic layer may further contain a hole transporting material, an electron transporting material, or a light emitting material. Here, the light-emitting material refers to a material that exhibits fluorescence and / or phosphorescence.

When the polymer compound of the present invention and the hole transporting material are mixed, the mixing ratio of the hole transporting material is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt%, based on the entire mixture. It is. When the polymer material of the present invention and the electron transporting material are mixed, the mixing ratio of the electron transporting material is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt% with respect to the entire mixture. Further, when the polymer compound of the present invention and the luminescent material are mixed, the mixing ratio of the luminescent material is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt% with respect to the entire mixture. When the polymer compound of the present invention is mixed with a light emitting material, a hole transporting material and / or an electron transporting material, the mixing ratio of the light emitting material is 1 wt% to 50 wt% with respect to the entire mixture. , Preferably 5 wt% to 40 wt%, and the total of the hole transport material and the electron transport material is 1 wt% to 50 wt%, preferably 5 wt% to 40 wt%. Therefore, the content of the polymer compound of the present invention is 98 wt% to 1 wt%, preferably 90 wt% to 20 wt%.
As the hole transporting material, the electron transporting material, and the light emitting material to be mixed, known low molecular compounds, triplet light emitting complexes, or high molecular compounds can be used, but high molecular compounds are preferably used.
As the hole transport material, electron transport material, and light emitting material of the polymer compound, WO99 / 13692, WO99 / 48160, GB2340304A, WO00 / 53656, WO01 / 19834, WO00 / 55927, GB23448316, WO00 / 46321, WO00 / 06665, WO99 / 54943, WO99 / 54385, US5777070, WO98 / 06773, WO97 / 05184, WO00 / 35987, WO00 / 53655, WO01 / 34722, WO99 / 24526, WO00 / 22027, WO00 / 22026, WO98 / 27136, US573636 , WO98 / 21262, US5741921, WO97 / 09394, WO96 / 29356, WO96 / 10617, EP07070. 0, WO95 / 07955, JP 2001-181618, JP 2001-123156, JP 2001-3045, JP 2000-351967, JP 2000-303066, JP 2000-299189, JP 2000-252065, JP 2000-252065, JP 2000-136379, JP 2000-104057, JP 2000-80167, JP 10-324870, JP 10-114891, JP 9-111233, JP 9-45478, and the like, and derivatives thereof And copolymers, polyarylenes, derivatives and copolymers thereof, polyarylene vinylenes, derivatives and copolymers thereof, (co) polymers of aromatic amines and derivatives thereof.
Examples of the fluorescent material of the low molecular weight compound include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine-based, xanthene-based, coumarin-based, cyanine-based pigments, 8-hydroxyquinoline or a derivative thereof. A complex, an aromatic amine, tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used.
Specifically, for example, known ones such as those described in JP-A-57-51781 and 59-194393 can be used.

Examples of triplet light-emitting complexes include Ir (ppy) ₃ , Btp ₂ Ir (acac) having iridium as a central metal, PtOEP having platinum as a central metal, Eu (TTA) ₃ phen having a central metal as europium, and the like. Can be mentioned.

  Specific examples of the triplet light-emitting complex include, 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. MoI. 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. et al. Appl. Phys. 34, 1883 (1995).

The composition of the present invention contains at least one material selected from a hole transport material, an electron transport material, and a light emitting material and the polymer compound of the present invention, and can be used as a light emitting material or a charge transport material.
The content ratio of the polymer compound of the present invention and at least one material selected from the hole transport material, the electron transport material, and the light emitting material may be determined according to the use, but in the case of the use of the light emitting material, The same content ratio as in the above light emitting layer is preferable.
The film thickness of the light emitting layer of the polymer LED of the present invention varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate values. For example, it is 1 nm to 1 μm, preferably Is 2 nm to 500 nm, more preferably 5 nm to 200 nm.
Examples of the method for forming the light emitting layer include a method by film formation from a solution. As a film forming method from a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, Application methods such as a flexographic printing method, an offset printing method, and an ink jet printing method can be used. Printing methods such as a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method are preferable in that pattern formation and multicolor coating are easy.
The ink composition used in the printing method or the like only needs to contain at least one polymer compound of the present invention. Besides the polymer compound of the present invention, a hole transport material, an electron transport material, a light emitting material, Additives such as solvents and stabilizers may be included.
The ratio of the polymer compound of the present invention in the ink composition is usually 20 wt% to 100 wt%, preferably 40 wt% to 100 wt%, with respect to the total weight of the composition excluding the solvent.
When the ink composition contains a solvent (hereinafter, this ink composition may be simply referred to as a solution or a solution of the present invention), the ratio of the solvent is 1 wt% to 99.99% with respect to the total weight of the composition. 9 wt%, preferably 60 wt% to 99.5 wt%, more preferably 80 wt% to 99.0 wt%.
The viscosity of the ink composition varies depending on the printing method, but when the ink composition passes through a discharge device such as an ink jet printing method, the viscosity is 1 to 20 mPa at 25 ° C. in order to prevent clogging and flight bending at the time of discharge. -It is preferable that it is the range of s.

The solution of the present invention may contain an additive for adjusting viscosity and / or surface tension in addition to the polymer compound of the present invention. As the additive, a high molecular weight polymer compound (thickener) for increasing the viscosity, a poor solvent, a low molecular weight compound for decreasing the viscosity, a surfactant for decreasing the surface tension, and the like are appropriately combined. Use it.
The high molecular weight polymer compound may be any compound that is soluble in the same solvent as the polymer compound of the present invention and does not inhibit light emission or charge transport. For example, high molecular weight polystyrene, polymethyl methacrylate, or a polymer compound of the present invention having a large molecular weight can be used. The weight average molecular weight is preferably 500,000 or more, and more preferably 1,000,000 or more.
A poor solvent can also be used as a thickener. That is, the viscosity can be increased by adding a small amount of a poor solvent for the solid content in the solution. When a poor solvent is added for this purpose, the type and addition amount of the solvent may be selected as long as the solid content in the solution does not precipitate. Considering the stability during storage, the amount of the poor solvent is preferably 50 wt% or less, more preferably 30 wt% or less with respect to the entire solution.
The solution of the present invention may contain an antioxidant in addition to the polymer compound of the present invention in order to improve storage stability. The antioxidant is not particularly limited as long as it is soluble in the same solvent as the polymer compound of the present invention and does not inhibit light emission or charge transport, and examples thereof include phenol-based antioxidants and phosphorus-based antioxidants.
Although there is no restriction | limiting in particular as a solvent used as an ink composition, The thing which can melt | dissolve or disperse | distribute materials other than the solvent which comprises this ink composition is preferable. Chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, and aromatic solvents such as toluene and xylene. Hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, cyclohexanone, etc. Ketone solvents, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane Polyhydric alcohols such as propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and derivatives thereof, alcohol solvents such as methanol, ethanol, propanol, isopropanol, cyclohexanol, dimethyl sulfoxide, etc. And amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents can be used alone or in combination.
Of these, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ester solvents, ketone solvents are preferred from the viewpoint of solubility of polymer compounds, uniformity during film formation, viscosity characteristics, and the like. Toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, s-butylbenzene, anisole, ethoxybenzene, 1-methylnaphthalene, cyclohexane, cyclohexanone, cyclohexylbenzene, biphenyl Cyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, 2-propylcyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2 Decanone, dicyclohexyl ketone are preferred, xylene, anisole, cyclohexylbenzene, and it is more preferable to contain at least one of bicyclohexyl.
The number of solvents in the solution is preferably two or more, more preferably two to three, and even more preferably two from the viewpoints of film formability and device characteristics.
When two kinds of solvents are contained in the solution, one of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, one type of solvent is preferably a solvent having a boiling point of 180 ° C. or higher, and the other one type of solvent is preferably a solvent having a boiling point of 180 ° C. or lower. More preferably, the solvent is a solvent having a boiling point of 180 ° C. or lower. From the viewpoint of viscosity, it is preferable that 1 wt% or more of the high molecular compound is dissolved at 60 ° C. in one of the two solvents, and one solvent out of the two types of solvent contains 1 wt% or more at 25 ° C. It is preferable that the polymer compound is dissolved.
When three types of solvents are contained in the solution, one or two of them may be in a solid state at 25 ° C. From the viewpoint of film formability, at least one of the three solvents is preferably a solvent having a boiling point of 180 ° C. or higher, and at least one solvent is preferably a solvent having a boiling point of 180 ° C. or lower. At least one of the types of solvents is a solvent having a boiling point of 200 ° C. or more and 300 ° C. or less, and at least one of the solvents is more preferably a solvent having a boiling point of 180 ° C. or less. From the viewpoint of viscosity, it is preferable that 1 wt% or more of the polymer compound is dissolved in two of the three types of solvents at 60 ° C., and one type of the three types of solvents is preferable. It is preferable that 1 wt% or more of the polymer compound dissolves at 25 ° C.
When two or more kinds of solvents are contained in the solution, the solvent having the highest boiling point is preferably 40 to 90 wt% of the weight of the total solvent in the solution from the viewpoint of viscosity and film formability, and 50 to 90 wt%. % Is more preferable, and 65 to 85 wt% is still more preferable.
The polymer compound of the present invention contained in the solution may be one type or two or more types, and may contain a polymer compound other than the polymer compound of the present invention as long as device characteristics and the like are not impaired.
The solution of the present invention may contain water, a metal and a salt thereof in the range of 1 to 1000 ppm. Specific examples of the metal include lithium, sodium, calcium, potassium, iron, copper, nickel, aluminum, zinc, chromium, manganese, cobalt, platinum, iridium and the like. Moreover, silicon, phosphorus, fluorine, chlorine, bromine may be included in a range of 1 to 1000 ppm.

Using the solution of the present invention, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic method A thin film can be produced by a printing method, an offset printing method, an inkjet printing method, or the like. Especially, it is preferable to use the solution of this invention for the use which forms into a film by the screen printing method, the flexographic printing method, the offset printing method, or the inkjet printing method, and it is more preferable to use it for the use which forms into a film by the inkjet method.
When a thin film is produced using the solution of the present invention, since the glass transition temperature of the polymer compound contained in the solution is high, it can be baked at a temperature of 100 ° C. or higher, and baked at a temperature of 130 ° C. However, the deterioration of the device characteristics is very small. Depending on the type of the polymer compound, baking at a temperature of 160 ° C. or higher is also possible.
Examples of thin films that can be produced using the solution of the present invention include luminescent thin films, conductive thin films, and organic semiconductor thin films.
The conductive thin film of the present invention preferably has a surface resistance of 1 kΩ / □ or less. The electrical conductivity can be increased by doping the thin film with a Lewis acid, an ionic compound, or the like. The surface resistance is more preferably 100Ω / □ or less, and further preferably 10Ω / □ or less.
In the organic semiconductor thin film of the present invention, the higher one of the electron mobility and the hole mobility is preferably 10 ⁻⁵ cm ² / V / second or more. More preferably, it is 10 ^<-3 > cm < ² > / V / second or more, More preferably, it is 10 ^<-1 > cm < ² > / V / second or more.
An organic transistor can be formed by forming the organic semiconductor thin film on a Si substrate on which an insulating film such as SiO ₂ and a gate electrode are formed, and forming a source electrode and a drain electrode with Au or the like.

  The polymer LED of the present invention includes a polymer LED having an electron transport layer provided between a cathode and a light emitting layer, a polymer LED having a hole transport layer provided between an anode and a light emitting layer, and a cathode. Examples thereof include a polymer LED in which an electron transport layer is provided between the light emitting layer and a hole transport layer is provided between the anode and the light emitting layer.

For example, the following structures a) to d) are specifically exemplified.
a) Anode / light emitting layer / cathode b) Anode / hole transport layer / light emitting layer / cathode c) Anode / light emitting layer / electron transport layer / cathode d) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (Here, / indicates that each layer is laminated adjacently. The same shall apply hereinafter.)
Further, for each of these structures, the following structure in which an interlayer layer is provided adjacent to the light emitting layer between the light emitting layer and the anode is also exemplified.
a ′) Anode / interlayer layer / light emitting layer / cathode b ′) Anode / hole transport layer / interlayer layer / light emitting layer / cathode c ′) Anode / interlayer layer / light emitting layer / electron transport layer / cathode d ′ ) Anode / hole transport layer / interlayer layer / light emitting layer / electron transport layer / cathode

  When the polymer LED of the present invention has a hole transport layer, the hole transport material used is polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, polysiloxane having an aromatic amine in a side chain or a main chain. Derivatives, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5- Thienylene vinylene) or a derivative thereof.

  Specifically, as the hole transporting material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, and JP-A-2-209988 are disclosed. Examples described in JP-A-3-37992 and JP-A-3-152184 are exemplified.

  Among these, as a hole transporting material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, a polyaniline or a derivative thereof , Polythiophene or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, or a polymer hole transporting material such as poly (2,5-thienylene vinylene) or a derivative thereof, and more preferably polyvinyl carbazole or a derivative thereof A derivative, polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in a side chain or main chain.

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

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

  Polyvinylcarbazole or a derivative thereof is obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.

  Examples of the polysilane or derivatives thereof include compounds described in Chem. Rev. 89, 1359 (1989), GB 2300196 published specification, and the like. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.

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

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

  As a solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing a hole transporting material is preferable. Chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, and aromatic solvents such as toluene and xylene. Hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, cyclohexanone, etc. Ketone solvents, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane Polyhydric alcohols such as propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and derivatives thereof, alcohol solvents such as methanol, ethanol, propanol, isopropanol, cyclohexanol, dimethyl sulfoxide, etc. And amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents can be used alone or in combination.

  Examples of film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  The film thickness of the hole transport layer differs depending on the material used and may be selected so that the drive voltage and the light emission efficiency are appropriate, but at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the film thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  When the polymer LED of the present invention has an electron transporting layer, known materials can be used as the electron transporting material, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or Derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline Or a derivative thereof, polyfluorene or a derivative thereof, and the like are exemplified.

  Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992, The thing etc. which are described in the same 3-152184 gazette are illustrated.

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

  There are no particular restrictions on the method for forming the electron transport layer, but for low molecular weight electron transport materials, vacuum deposition from powder or film deposition from a solution or melted state is preferred for polymer electron transport materials. Or the method by the film-forming from a molten state is illustrated, respectively. When forming a film from a solution or a molten state, the above polymer binder may be used in combination.

  As a solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing an electron transport material and / or a polymer binder is preferable. Chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, and aromatic solvents such as toluene and xylene. Hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, cyclohexanone, etc. Ketone solvents, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane Polyhydric alcohols such as propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and derivatives thereof, alcohol solvents such as methanol, ethanol, propanol, isopropanol, cyclohexanol, dimethyl sulfoxide, etc. And amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents can be used alone or in combination.

  Examples of film formation methods from a solution or a molten state include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen. Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  The film thickness of the electron transport layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are moderate values, but at least a thickness that does not cause pinholes is required. If the thickness is too thick, the drive voltage of the element becomes high, which is not preferable. Therefore, the thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  Further, among the charge transport layers provided adjacent to the electrodes, those having a function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element are particularly charge injection layers (hole injection layers). , An electron injection layer).

Further, in order to improve adhesion with the electrode and charge injection from the electrode, the charge injection layer or an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode, and the adhesion at the interface may be improved. In order to prevent mixing, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.
The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

In the present invention, a polymer LED provided with a charge injection layer (electron injection layer, hole injection layer) includes a polymer LED provided with a charge injection layer adjacent to the cathode, and a charge injection layer adjacent to the anode. The provided polymer LED is mentioned.
For example, the following structures e) to p) are specifically mentioned.
e) Anode / charge injection layer / light emitting layer / cathode f) Anode / light emitting layer / charge injection layer / cathode g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode h) Anode / charge injection layer / hole Transport layer / light emitting layer / cathode i) anode / hole transport layer / light emitting layer / charge injection layer / cathode j) anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode k) anode / charge Injection layer / light emitting layer / electron transport layer / cathode l) anode / light emitting layer / electron transport layer / charge injection layer / cathode m) anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode n) anode / Charge injection layer / hole transport layer / light emitting layer / electron transport layer / cathode o) anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode p) anode / charge injection layer / hole transport Layer / light emitting layer / electron transport layer / charge injection layer / cathode For each one of these structures, the light emitting layer is adjacent to the light emitting layer between the light emitting layer and the anode. A structure in which an interlayer is provided is also exemplified. In this case, the interlayer layer may also serve as a hole injection layer and / or a hole transport layer.

  Specific examples of the charge injection layer include a layer containing a conductive polymer, an intermediate between the anode material and the hole transporting material included in the hole transporting layer, provided between the anode and the hole transporting layer. A layer containing a material having an ionization potential of the value, a material provided between the cathode and the electron transport layer, and a material having an electron affinity of an intermediate value between the cathode material and the electron transport material contained in the electron transport layer Examples include layers.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ or less, and the leakage current between the light emitting pixels is reduced. In order to achieve this, 10 ⁻⁵ S / cm to 10 ² is more preferable, and 10 ⁻⁵ S / cm to 10 ¹ is more preferable.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less. in order to reduce the current, more preferably less 10 ^-5 S / cm or more and 10 ² S / cm, more preferably less 10 ^-5 S / cm or more and 10 ¹ S / cm.
Usually, in order to make the electric conductivity of the conductive polymer 10 ⁻⁵ S / cm or more and 10 ³ or less, the conductive polymer is doped with an appropriate amount of ions.

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

  The material used for the charge injection layer may be appropriately selected in relation to the material of the electrode and the adjacent layer. Polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene And derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanines (such as copper phthalocyanine), and carbon .

  An insulating layer having a thickness of 2 nm or less has a function of facilitating charge injection. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. As the polymer LED provided with the insulating layer having a thickness of 2 nm or less, the polymer LED provided with the insulating layer having a thickness of 2 nm or less adjacent to the cathode, or the insulating layer having a thickness of 2 nm or less provided adjacent to the anode. Polymer LED is mentioned.

Specific examples include the following structures q) to ab).
q) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / cathode r) Anode / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode s) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / film thickness 2 nm Insulating layer / cathode t) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / cathode u) Anode / hole transporting layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode v) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode w) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / cathode x) anode / Light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode y) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode z) anode / film Insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / cathode aa) anode / hole transport layer / light emitting layer / electron transport Layer / insulating layer having a thickness of 2 nm or less / cathode ab) anode / insulating layer having a thickness of 2 nm or less / hole transporting layer / light emitting layer / electron transporting layer / insulating layer having a thickness of 2 nm or less / cathode Is also exemplified by a structure in which an interlayer is provided adjacent to the light emitting layer between the light emitting layer and the anode. In this case, the interlayer layer may also serve as a hole injection layer and / or a hole transport layer.

Regarding the structure in which the interlayer layer is applied to the above structures a) to ab), the interlayer layer is provided between the anode and the light emitting layer, and the anode, the hole injection layer or the hole transport layer, and the light emitting layer. It is preferably composed of a material having an ionization potential intermediate to that of the polymer compound constituting
Examples of materials used for the interlayer layer include polymers containing aromatic amines such as polyvinyl carbazole or derivatives thereof, polyarylene derivatives having aromatic amines in the side chain or main chain, arylamine derivatives, and triphenyldiamine derivatives. .
Although there is no restriction | limiting in the film-forming method of an interlayer layer, For example, when using a polymeric material, the method by the film-forming from a solution is illustrated.

  As a solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing a hole transporting material is preferable. Chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, and aromatic solvents such as toluene and xylene. Hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, cyclohexanone, etc. Ketone solvents, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane Polyhydric alcohols such as propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and derivatives thereof, alcohol solvents such as methanol, ethanol, propanol, isopropanol, cyclohexanol, dimethyl sulfoxide, etc. And amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents can be used alone or in combination.

  Examples of film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  The thickness of the interlayer layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. For example, it is 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  When the interlayer layer is provided adjacent to the light emitting layer, particularly when both layers are formed by a coating method, the materials of the two layers are mixed to adversely affect the characteristics of the device. There is. When the light emitting layer is formed by the coating method after the interlayer layer is formed by the coating method, as a method for reducing the mixing of the materials of the two layers, the interlayer layer is formed by the coating method, and then the interlayer layer is formed. A method of forming a light emitting layer after heating to insolubilize in an organic solvent used for forming a light emitting layer is mentioned. The heating temperature is usually about 150 ° C. to 300 ° C., and the time is usually about 1 minute to 1 hour. In this case, in order to remove components that have not been insolubilized by heating, the interlayer layer can be removed by rinsing with a solvent used for forming the light emitting layer after heating and before forming the light emitting layer. When solvent insolubilization is sufficiently performed by heating, rinsing with a solvent can be omitted. In order to sufficiently insolubilize the solvent by heating, it is preferable to use a polymer compound containing at least one polymerizable group in the molecule as the polymer compound used in the interlayer layer. Furthermore, the number of polymerizable groups is preferably 5% or more with respect to the number of repeating units in the molecule.

  The substrate on which the polymer LED of the present invention is formed may be any substrate that does not change when the electrode is formed and the organic layer is formed, and examples thereof include glass, plastic, polymer film, and silicon substrate. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

Usually, at least one of the anode and the cathode of the polymer LED of the present invention is transparent or translucent. The anode side is preferably transparent or translucent.
As the material of the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film made of conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Further, as the anode, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used.
The film thickness of the anode can be appropriately selected in consideration of light transmittance and electric conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. is there.
In order to facilitate charge injection on the anode, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like. A layer may be provided.

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

  As a method for manufacturing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression-bonded, or the like is used. In addition, a layer made of a conductive polymer or a layer having an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided between the cathode and the organic material layer. A protective layer for protecting the polymer LED may be attached. In order to stably use the polymer LED for a long period of time, it is preferable to attach a protective layer and / or protective cover in order to protect the element from the outside.

  As the protective layer, a polymer compound, metal oxide, metal fluoride, metal boride and the like can be used. Further, as the protective cover, a glass plate, a plastic plate having a low water permeability treatment on the surface, or the like can be used, and a method of sealing the cover by bonding it to the element substrate with a heat effect resin or a photo-curing resin is preferable. Used for. If the space is maintained by using the spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, the cathode can be prevented from being oxidized, and moisture adsorbed in the manufacturing process by installing a desiccant such as barium oxide in the space. It is easy to suppress damage to the element. Among these, it is preferable to take one or more measures.

The polymer LED of the present invention can be used as a backlight for a planar light source, a segment display device, a dot matrix display device, and a liquid crystal display device.
In order to obtain planar light emission using the polymer LED of the present invention, the planar anode and cathode may be arranged so as to overlap each other. In addition, in order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element, an organic layer of a non-light-emitting portion is formed extremely thick and substantially non-light-emitting. There are a method of emitting light and a method of forming either one or both of an anode and a cathode in a pattern. By forming a pattern by any of these methods and arranging several electrodes so that they can be turned on and off independently, a segment type display element capable of displaying numbers, letters, simple symbols and the like can be obtained. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multicolor display are possible by a method of separately coating a plurality of types of polymeric fluorescent substances having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix element can be driven passively or may be driven actively in combination with TFTs. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

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

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

アルゴン雰囲気下、１００ｍＬ四つ口フラスコ中でＣＢＰ（０．１２ｍｍｏｌ）、ＰＯＣｌ₃（１．３ｍｍｏｌ）、ＤＭＦ（２．０ｍｍｏｌ）、及びジクロロメタンを混合し、４時間、８０℃に加熱した。反応終了後、水酸化ナトリウム水溶液でクエンチし、クロロホルムで抽出し、有機層を濃縮した後、シリカゲルカラムクロマトグラフィー（ベンゼン：ヘキサン＝１：３）で精製することにより、化合物Ｍ−１を得た。 (Synthesis Example 1)
Synthesis of Compound M-1

Under an argon atmosphere, CBP (0.12 mmol), POCl ₃ (1.3 mmol), DMF (2.0 mmol), and dichloromethane were mixed in a 100 mL four-necked flask and heated to 80 ° C. for 4 hours. After completion of the reaction, the reaction mixture was quenched with an aqueous sodium hydroxide solution, extracted with chloroform, the organic layer was concentrated, and purified by silica gel column chromatography (benzene: hexane = 1: 3) to obtain compound M-1. .

アルゴン雰囲気下、１００ｍＬ四つ口フラスコ中で化合物Ｍ−１、イソブチルアミン、及び脱水エタノールを混合し、１２時間還流した。反応溶液を室温まで冷却した後、水素化ホウ素ナトリウムを加え、４時間撹拌した。炭酸水素ナトリウムでクエンチした後、酢酸エチルで抽出し、有機層を濃縮することにより化合物Ｍ−２を得た。 (Synthesis Example 2)
Synthesis of compound M-2

Under an argon atmosphere, Compound M-1, isobutylamine, and dehydrated ethanol were mixed in a 100 mL four-necked flask and refluxed for 12 hours. After the reaction solution was cooled to room temperature, sodium borohydride was added and stirred for 4 hours. After quenching with sodium bicarbonate, extraction with ethyl acetate was performed, and the organic layer was concentrated to obtain compound M-2.

アルゴン雰囲気下、１００ｍＬ−三つ口フラスコ中で、化合物Ｍ−２、大過剰の１，８−ジブロモオクタン、炭酸カリウム、及びトルエンを混合し、１２時間還流を行った。反応溶液を室温まで冷却した後、クエンチし、酢酸エチルで抽出し、有機層を濃縮乾固した。得られた固体をシリカゲルカラムクロマトグラフィー（酢酸エチル）で２回精製することにより化合物Ｍ−３を得た。
¹Ｈ−ＮＭＲ；δ０．９０（３Ｈ，ｔ），１．２４−１．４０（１０Ｈ，ｍ），１．５８（８Ｈ，ｍ），３．３９（２Ｈ，ｔ），３．７７（２Ｈ，ｓ），７．２９−７．３６（３Ｈ，ｍ），７．４１−７．５３（８Ｈ，ｍ），７．７１（４Ｈ，ｄｄ），７．９２（４Ｈ，ｄｄ），８．１０−８．１９（４Ｈ，ｍ）．ＦＡＢ−ＭＳ；ｍ／ｚ ７４６．８（Ｍ⁺）． (Synthesis Example 3)
Synthesis of compound M-3

Under an argon atmosphere, Compound M-2, a large excess of 1,8-dibromooctane, potassium carbonate, and toluene were mixed in a 100 mL three-necked flask and refluxed for 12 hours. The reaction solution was cooled to room temperature, then quenched, extracted with ethyl acetate, and the organic layer was concentrated to dryness. The obtained solid was purified twice by silica gel column chromatography (ethyl acetate) to obtain Compound M-3.
¹ H-NMR; δ 0.90 (3H, t), 1.24-1.40 (10H, m), 1.58 (8H, m), 3.39 (2H, t), 3.77 (2H , S), 7.29-7.36 (3H, m), 7.41-7.53 (8H, m), 7.71 (4H, dd), 7.92 (4H, dd), 8. 10-8.19 (4H, m). FAB-MS; m / z 746.8 (M +).

アルゴン雰囲気下、２当量の化合物Ｍ−３、１当量の化合物Ｍ−４、１０当量の炭酸カリウム、及び溶媒量のトルエンを混合し還流させることで反応を進行させる。反応終了後に、有機層を水で洗い、シリカゲルカラムクロマトグラフィーで精製することにより化合物Ｍ−５を得ることができる。
なお化合物Ｍ−４はＥＰ１３４４７８８記載の方法で合成できる。 (Synthesis Example 4)
Synthesis of compound M-5

Under an argon atmosphere, 2 equivalents of Compound M-3, 1 equivalent of Compound M-4, 10 equivalents of potassium carbonate, and a solvent amount of toluene are mixed and refluxed to allow the reaction to proceed. After completion of the reaction, the organic layer is washed with water and purified by silica gel column chromatography to obtain compound M-5.
Compound M-4 can be synthesized by the method described in EP 1344788.

アルゴン雰囲気下、２当量の化合物Ｍ−３、１当量の化合物Ｍ−６、１０当量の炭酸カリウム、及び溶媒量のトルエンを混合し、還流させることで反応を進行させる。反応終了後に、有機層を水で洗い、シリカゲルカラムクロマトグラフィーで精製することにより化合物Ｍ−７を得ることができる。 (Synthesis Example 5)
Synthesis of compound M-7

Under an argon atmosphere, 2 equivalents of Compound M-3, 1 equivalent of Compound M-6, 10 equivalents of potassium carbonate, and a solvent amount of toluene are mixed and refluxed to allow the reaction to proceed. After completion of the reaction, the organic layer is washed with water and purified by silica gel column chromatography to obtain compound M-7.

アルゴン雰囲気下、１００ｍＬ三つ口フラスコの中でM-8（６８μmol）、６０％水素化ナトリウム（０．４７mmol）、１，５−ジヨードペンタン（０．７mmol）、THFを混合し、室温で4日間攪拌した。水を加えてクエンチした後、クロロホルムで抽出した。有機層を濃縮して得られた油状物をシリカゲルカラムクロマトグラフィー（ベンゼン：ヘキサン＝１：１）で精製することにより、化合物M-9を得た。
¹H−NMR ；δ １．５２−１．５５（２H，ｍ），１．６８（２H，ｑｕｉnｔ），１．８７（２H，ｑｕｉnｔ），３．２０（２H，ｔ），３．５５（２H，ｔ），４．７１（２H，ｓ），７．３１−７．３５（３H，ｍ），７．４４−７．５５（８H，ｍ），７．６８−７．７５（４H，ｍ），７．９０−７．９４（４H，ｍ），８．１５−８．２１（４H，ｍ）．ＦＡＢ−ＭＳ；ｍ/ｚ 710（Ｍ⁺）． (Synthesis Example 6)
Synthesis of Compound M-9

Under argon atmosphere, M-8 (68 μmol), 60% sodium hydride (0.47 mmol), 1,5-diiodopentane (0.7 mmol), and THF were mixed in a 100 mL three-necked flask at room temperature. Stir for 4 days. After quenching by adding water, the mixture was extracted with chloroform. The oil obtained by concentrating the organic layer was purified by silica gel column chromatography (benzene: hexane = 1: 1) to obtain compound M-9.
¹ H-NMR; δ 1.52-1.55 (2H, m), 1.68 (2H, quint), 1.87 (2H, quint), 3.20 (2H, t), 3.55 ( 2H, t), 4.71 (2H, s), 7.31-7.35 (3H, m), 7.44-7.55 (8H, m), 7.68-7.75 (4H, m), 7.90-7.94 (4H, m), 8.15-8.21 (4H, m). FAB-MS; m / z 710 (M ⁺ ).

アルゴン雰囲気下、５０ｍＬ三つ口フラスコの中でM-8（０．１６mmol）、６０％水素化ナトリウム（１．６mmol）、１，５−ジブロモペンタン（１．６mmol）とTHFを混合し、室温で３日間攪拌した。水を加えてクエンチした後、クロロホルムで抽出した。有機層を濃縮して得られた油状物をシリカゲルカラムクロマトグラフィー（ベンゼン：ヘキサン＝２：１）で精製することにより、化合物M-10を得た。
¹H−NMR ；δ １．５５−１．６４（２H，ｍ），１．７１（２H，ｑｕｉnｔ），１．９２（２H，ｑｕｉnｔ），３．４４（２H，ｔ），３．５７（２H，ｔ），４．７３（２H，ｓ），
７．３２−７．３７（３H，ｍ），７．４４−７．５７（８H，ｍ），７．６９−７．７６（４H，ｍ），７．９１−７．９５（４H，ｍ），８．１５−８．２３（４H，ｍ）．ＦＡＢ−ＭＳ；ｍ/ｚ ６６２（Ｍ⁺for ⁷⁹Br）． (Synthesis Example 7)
Synthesis of Compound M-10

Under argon atmosphere, M-8 (0.16 mmol), 60% sodium hydride (1.6 mmol), 1,5-dibromopentane (1.6 mmol) and THF were mixed in a 50 mL three-necked flask at room temperature. For 3 days. After quenching by adding water, the mixture was extracted with chloroform. The oil obtained by concentrating the organic layer was purified by silica gel column chromatography (benzene: hexane = 2: 1) to give compound M-10.
¹ H-NMR: δ 1.55-1.64 (2H, m), 1.71 (2H, quint), 1.92 (2H, quint), 3.44 (2H, t), 3.57 ( 2H, t), 4.73 (2H, s),
7.32-7.37 (3H, m), 7.44-7.57 (8H, m), 7.69-7.76 (4H, m), 7.91-7.95 (4H, m ), 8.15-8.23 (4H, m). FAB-MS; m / z 662 (M ⁺ for ⁷⁹ Br).

Example 1
Synthesis of Polymer Compound P-1 Compound M-5, 2,2′-bipyridyl is dissolved in dehydrated tetrahydrofuran previously bubbled with argon under an inert atmosphere. Next, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } is added and stirred, and this solution is heated to 60 ° C. and reacted for 3 hours. The reaction solution is cooled to room temperature, dropped into 25% aqueous ammonia 1 mL / methanol / ion exchange water mixed solution and stirred for 1 hour, and then the deposited precipitate is filtered and dried under reduced pressure. Subsequently, after dissolving in toluene, adding radiolite and stirring, filtering insoluble matter, the filtrate is purified through an alumina column. Next, 4% aqueous ammonia is added, and after stirring, the aqueous layer is removed. Further, after adding ion-exchanged water to the organic layer and stirring, the aqueous layer is removed. Thereafter, the organic layer is concentrated under reduced pressure, poured into methanol and stirred. And the high molecular compound P-1 is compoundable by filtering the depositing deposit and drying under reduced pressure.

(Example 2)
Synthesis of Polymer Compound P-2 Compound M-5,2,2′-bipyridyl is dissolved in dehydrated tetrahydrofuran previously bubbled with argon under an inert atmosphere. Next, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } is added and stirred, and this solution is heated to 60 ° C. and reacted for 3 hours. The reaction solution is cooled to room temperature, dropped into 25% aqueous ammonia 1 mL / methanol / ion exchange water mixed solution and stirred for 1 hour, and then the deposited precipitate is filtered and dried under reduced pressure. Subsequently, after dissolving in toluene, adding radiolite and stirring, filtering insoluble matter, the filtrate is purified through an alumina column. Next, 4% aqueous ammonia is added, and after stirring, the aqueous layer is removed. Further, after adding ion-exchanged water to the organic layer and stirring, the aqueous layer is removed. Thereafter, the organic layer is concentrated under reduced pressure, poured into methanol and stirred. And the high molecular compound P-2 is compoundable by filtering the depositing deposit and drying under reduced pressure.

  For the measurement of HOMO and LUMO, cyclic voltammetry (manufactured by BAS: ALS600) can be used, and the measurement can be performed in an acetonitrile solvent containing 0.1 wt% tetrabutylammonium tetrafluoroborate. The polymer compound can be dissolved in chloroform so as to be about 0.2 wt%, 1 mL of a chloroform solution of the polymer compound can be applied on the working electrode, and the chloroform can be vaporized to form a polymer compound thin film. The measurement can be performed in a glove box using a silver / silver ion electrode as a reference electrode, a glassy carbon electrode as a working electrode, and a platinum electrode as a counter electrode, and substituted with nitrogen. Both potential sweep rates can be measured at 50 mV / s.

<Measurement of oxidation potential>
(Example 3)
The high molecular compound P-1 can measure an oxidation potential by the above-mentioned method, and can obtain HOMO. The polymer compound P-1 is expected to have a lower absolute value of HOMO than a polymer compound having no side chain group.

Example 4
The high molecular compound P-2 can measure an oxidation potential by the above-mentioned method, and can obtain HOMO. The high molecular compound P-2 is expected to have a lower absolute value of HOMO than the high molecular compound having no side chain group.

(Example 5)
Preparation of Solution The polymer compound P-1 obtained above is dissolved in toluene to prepare a toluene solution having a polymer concentration of 1.2% by weight.
Production of EL element A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer, BaytronP AI4083) is 0.2 μm on a glass substrate on which an ITO film is formed with a thickness of 150 nm by sputtering. A thin film having a thickness of 70 nm is formed by spin coating using the liquid filtered through a membrane filter, and dried on a hot plate at 200 ° C. for 10 minutes. Next, using the toluene solution obtained above, a film is formed at a rotational speed of 1000 rpm by spin coating. Furthermore, this is dried at 80 ° C. under reduced pressure for 1 hour, lithium fluoride is deposited by about 4 nm, calcium is deposited by about 5 nm as a cathode, and then aluminum is deposited by about 72 nm, whereby an EL device can be produced. The metal deposition is started after the degree of vacuum reaches 1 × 10 ⁻⁴ Pa or less.
EL device performance By applying a voltage to the obtained device, EL light emission can be observed from this device.

(Example 6)
Preparation of Solution The polymer compound P-2 obtained above is dissolved in toluene to prepare a toluene solution having a polymer concentration of 1.2% by weight.
Production of EL element A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer, BaytronP AI4083) is 0.2 μm on a glass substrate on which an ITO film is formed with a thickness of 150 nm by sputtering. A thin film having a thickness of 70 nm is formed by spin coating using the liquid filtered through a membrane filter, and dried on a hot plate at 200 ° C. for 10 minutes. Next, using the toluene solution obtained above, a film is formed at a rotational speed of 1000 rpm by spin coating. Furthermore, this is dried at 80 ° C. under reduced pressure for 1 hour, lithium fluoride is deposited by about 4 nm, calcium is deposited by about 5 nm as a cathode, and then aluminum is deposited by about 72 nm, whereby an EL device can be produced. The metal deposition is started after the degree of vacuum reaches 1 × 10 ⁻⁴ Pa or less.
EL device performance By applying a voltage to the obtained device, EL light emission can be observed from this device.

Claims (45)

  A main chain containing at least one selected from the group consisting of an arylene group, a divalent heterocyclic group and a divalent aromatic amine group as a repeating unit, a hole injection transport group, an electron injection transport group, and a light emitting group A light-emitting or charge transporting polymer compound having a functional side chain containing at least one functional group selected from the group consisting of: -Rj- or -Rj-X- ( Rj represents a group having a configuration in which one or more carbon atoms constituting an alkylene group are replaced with a nitrogen atom (hereinafter also referred to as a nitrogen-substituted alkylene group), and the nitrogen-substituted alkylene group has a substituent. X is O, S, or N (R ′), and is bonded to the main chain by X. R ′ is independently a hydrogen atom, an alkyl group, an aryl group, or an arylalkyl. Group, arylalkoxy group, aryl An alkylthio group, an arylalkenyl group, an arylalkynyl group, or a monovalent heterocyclic group), which is bonded to the main chain.   A main chain containing at least one selected from the group consisting of an arylene group, a divalent heterocyclic group and a divalent aromatic amine group as a repeating unit, a hole injection transport group, an electron injection transport group, and a light emitting group A light-emitting or charge-transporting polymer compound having a functional side chain containing at least one functional group selected from the group consisting of: -Rj- (Rj is an alkylene group) A group having one or more constituent carbon atoms replaced with a nitrogen atom (hereinafter also referred to as a nitrogen-substituted alkylene group), and the nitrogen-substituted alkylene group may have a substituent. The polymer compound according to claim 1, wherein the polymer compound is bonded to the main chain via   The polymer compound according to claim 1, wherein the functional side chain has a hole injection / transport group as a functional group.   The polymer compound according to claim 3, wherein the hole injecting and transporting group contains one or more heteroatoms.   The polymer compound according to claim 4, wherein the hole injecting and transporting group contains one or more nitrogen atoms.   The polymer compound according to claim 5, wherein the hole injection / transport group has a carbazole skeleton. 6. The polymer compound according to claim 5, wherein the hole injection / transport group is a group represented by the following formula (HA), (H-B), or (HC).

(In the formula, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl. Group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, Represents a cyano group or a nitro group, and each R ′ independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic ring. Represents a group, a, e and h are integers selected from 0 to 3; And b, c and d represent an integer selected from 0 to 4, and f and g represent an integer selected from 0 to 5).   The polymer compound according to claim 1, wherein the functional side chain has an electron injection / transport group as a functional group.   The polymer compound according to claim 8, wherein the electron injection / transport group contains one or more heteroatoms.   The polymer compound according to claim 9, wherein the electron injecting and transporting group contains one or more nitrogen atoms. The polymer compound according to claim 10, wherein the electron injecting and transporting group is a group represented by the following formula (EA), (EB), or (EC).

(In the formula, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl. Group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, Represents a cyano group or a nitro group, and each R ′ independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic ring. I and k represent an integer selected from 0 to 4 , J, l and m represent an integer selected from 0 to 5).   The polymer compound according to claim 1, wherein the functional side chain has a light emitting group as a functional group.   The polymer compound according to claim 12, wherein the light emitting group contains a heterocyclic ring or a condensed polycyclic aromatic hydrocarbon. The polymer compound according to claim 13, wherein the electron injecting and transporting group is a group represented by the following formula (LA), (LB), or (LC).

(In the formula, each R is independently a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl. Group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, Represents a cyano group or a nitro group, and each R ′ independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic ring. Represents a group, and n and p represent an integer selected from 0 to 9 And o represents an integer selected from 0 to 7).   The polymer compound according to claim 1, wherein the polymer compound has an HOMO absolute value of 5.6 eV or less.   The absolute value of LUMO of a high molecular compound is 2.2 eV or more, The high molecular compound as described in any one of Claims 1-15. The number average molecular weight of polystyrene conversion is 10 < ³ > -10 < ⁸ >, The high molecular compound as described in any one of Claims 1-16.   It contains at least one material selected from the group consisting of a hole transport material, an electron transport material, and a light-emitting material and at least one polymer compound according to any one of claims 1 to 17, Composition.   A composition comprising at least two kinds of the polymer compound according to any one of claims 1 to 17.   A solution comprising the polymer compound according to claim 1.   A solution comprising the composition according to any one of claims 18 to 19.   The solution according to claim 20 or 21, comprising two or more kinds of organic solvents.   The solution according to any one of claims 20 to 22, which has a viscosity of 1 to 20 mPa · s at 25 ° C.   A light-emitting thin film comprising the polymer compound according to claim 1.   The luminescent thin film according to claim 24, wherein the quantum yield of light emission is 50% or more.   A conductive thin film comprising the polymer compound according to claim 1.   An organic semiconductor thin film comprising the polymer compound according to claim 1.   An organic transistor comprising the organic semiconductor thin film according to claim 27.   The method for forming a thin film according to any one of claims 24 to 27, wherein an inkjet method is used.   It has an organic layer containing the high molecular compound as described in any one of Claims 1-17, or the composition as described in any one of Claims 18-19 between the electrodes which consist of an anode and a cathode. A polymer light emitting device.   The polymer light emitting device according to claim 30, wherein the organic layer is a light emitting layer.   32. The polymer light emitting device according to claim 31, wherein the light emitting layer further contains a hole transport material, an electron transport material or a light emitting material.   It has a light emitting layer and a charge transport layer between the electrodes which consist of an anode and a cathode, and this charge transport layer is either the high molecular compound as described in any one of Claims 1-17, or any one of Claims 18-19. The polymer light-emitting device according to claim 30, comprising the composition according to claim 1.   It has a light emitting layer and a charge transport layer between the electrodes which consist of an anode and a cathode, has a charge injection layer between this charge transport layer and an electrode, and this charge injection layer is any one of Claims 1-17. The polymer light-emitting device according to claim 30, comprising the polymer compound according to claim 1 or the composition according to any one of claims 18 to 19.   A planar light source comprising the polymer light-emitting device according to any one of claims 30 to 34.   A segment display device comprising the polymer light emitting device according to any one of claims 30 to 34.   A dot matrix display device comprising the polymer light emitting device according to any one of claims 30 to 34.   35. A liquid crystal display device comprising the polymer light-emitting device according to any one of claims 30 to 34 as a backlight. Compound represented by the following formula (MA)

(In the formula, Ar _a represents an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine.)
Is reacted with a reducing agent in the presence of a primary amine,
Compound represented by formula (MB)

(In the formula, Ar _a represents an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine, and R ″ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, Represents an arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic group.)
Manufacture and
Reacting the compound represented by the formula (MB) with a compound represented by XJ ₁ -X (wherein J ₁ represents an alkylene group and X represents a halogen atom) in the presence of a base. Characterized by the
Intermediate compound of organic EL material represented by formula (MC)

(In the formula, Ar _a represents an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine, and R ″ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic group, J ₁ represents an alkylene group, X represents a halogen atom.)
Manufacturing method. In the presence of a base, the compound represented by the above formula (MC) is
Compound represented by formula (MD)

(In the formula, Ar _b represents an arylene group, a divalent heterocyclic group, or a divalent aromatic amine. X represents a halogen atom.)
By reacting with
Compound represented by formula (ME) or formula (MF)

(In the formula, Ar _a represents an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine, R ″ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic group, J ₁ represents an alkylene group, an alkenylene group, or alkynylene group, X represents a halogen atom, Ar _c trivalent aromatic hydrocarbon group A trivalent heterocyclic group or a trivalent aromatic amine is represented, and Ar _d represents a tetravalent aromatic hydrocarbon group, a tetravalent heterocyclic group or a tetravalent aromatic amine.)
Synthesize
A method for producing a polymer compound, comprising synthesizing a polymer compound by polymerizing a compound represented by formula (ME) or formula (MF). A compound having a partial structure represented by the following formula (MG).

Wherein R ′ ″ each independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic group. , J2 represents an alkylene group, and X represents a halogen atom.) An intermediate compound represented by the following formula (M-H).

(Wherein J ₃ represents an alkylene group, and X represents a halogen atom.)   Use of the compound according to claim 41 as a functional side chain of a functional polymer compound.   A monomer having at least one selected from the group consisting of an arylene group, a divalent heterocyclic group, and a divalent aromatic amine group, and comprising a hole injection transport group, an electron injection transport group, and a light emitting group A method for producing a light emitting or charge transporting polymer compound comprising polymerizing a raw material monomer containing the above monomer having at least one selected functional group, wherein the functional group is -Rj- or -Rj-X- (Rj represents a group having one or more carbon atoms constituting the alkylene group substituted with a nitrogen atom (hereinafter also referred to as a nitrogen-substituted alkylene group), and the nitrogen-substituted alkylene The group may have a substituent, X is O, S, or N (R ′), and is bonded to the main chain at X. R ′ is independently a hydrogen atom or an alkyl group. , Aryl group, arylal Group, arylalkoxy group, arylalkylthio group, arylalkenyl group, the manufacturing method characterized by an aryl alkynyl group or monovalent heterocyclic group.) Through bonded to said monomer.   -Rj- or -Rj-X- (Rj represents a group having one or more carbon atoms constituting the alkylene group replaced with a nitrogen atom (hereinafter also referred to as a nitrogen-substituted alkylene group); The nitrogen-substituted alkylene group may have a substituent, X is O, S, or N (R ′), and is bonded to the main chain at X. R ′ is independently hydrogen. A functional side chain is bonded to the main chain via an atom, alkyl group, aryl group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group or monovalent heterocyclic group. A method for introducing a functional side chain into a main chain of a polymer compound characterized by comprising: