JP2010171230A - Electronic element, and polymer compound having bipyridinium skeleton useful for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electronic element excelling in conversion efficiency. <P>SOLUTION: The electronic element includes: a first electrode; a second electrode; a luminescent layer or a charge separation layer arranged between the first electrode and second electrode; and a charge injection layer arranged between the luminescent layer or the charge separation layer and the first electrode or the second electrode, and containing a polymer compound having a structure represented by formula (I). In the formula (I), each of X<SP>1</SP>and X<SP>2</SP>is each independently an ion of F<SP>-</SP>, OH<SP>-</SP>, R<SP>a</SP>SO<SB>3</SB><SP>-</SP>, R<SP>a</SP>COO<SP>-</SP>, ClO<SP>-</SP>, SCN<SP>-</SP>, CN<SP>-</SP>, NO<SB>3</SB><SP>-</SP>, HSO<SB>4</SB><SP>-</SP>, H<SB>2</SB>PO<SB>4</SB><SP>-</SP>, BF<SB>4</SB><SP>-</SP>, BR<SP>a</SP><SB>4</SB><SP>-</SP>or PF<SB>6</SB><SP>-</SP>; R<SP>a</SP>is one group selected from a group comprising 1-30C alkyl group, 6-50C aryl group and 2-50C univalent heterocyclic group; the alkyl group, aryl group and univalent heterocyclic group may have each a substituted group; and * is a binding site to another structure. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an electronic device, and more particularly, to an electronic device including two electrodes, a light emitting layer or a charge separation layer, and a charge injection layer.

  In order to improve the characteristics of an electronic device such as an electroluminescent device or a photoelectric conversion device, various layers are inserted between the light emitting layer and the electrode of the electroluminescent device or between the charge separation layer and the electrode of the photoelectric conversion device. Is being considered.

For example, as an electronic device in which a layer made of a polymer compound is inserted, Japanese Patent Publication No. 2003-530676 (Patent Document 1) discloses an ether chain, Na ⁺ , SO ₃ ^{−, and the} like between an electrode and a light emitting layer. COO for forming a counter ion and ionic bonds - have been disclosed ^(NH _{3) 4} ⁺ ions and the organic / polymer electroluminescent inserting a layer made of a polymer containing in the main chain or side chain (EL) element . However, the organic / polymer electroluminescent (EL) element described in Patent Document 1 has not been sufficient in terms of conversion efficiency.

Special table 2003-530676 gazette

  The present invention has been made in view of the above-described problems of the prior art, and an object thereof is to provide an electronic device having excellent conversion efficiency.

  As a result of intensive studies to achieve the above object, the present inventors have found that a polymer compound having a 4,4′-bipyridinium skeleton is excellent in charge injection property, and further emits light between two electrodes. In an electronic device including a layer or a charge separation layer, conversion is performed by inserting a charge injection layer containing a polymer compound having a 4,4′-bipyridinium skeleton between the electrode and the light emitting layer or the charge separation layer. The inventors have found that an electronic device having excellent efficiency can be obtained, and have completed the present invention.

  That is, the electronic device of the present invention includes a first electrode, a second electrode, a light emitting layer or a charge separation layer disposed between the first electrode and the second electrode, and the light emitting layer. Or disposed between the charge separation layer and the first electrode or the second electrode, and the following formula (I):

(In the formula (I), X ¹ and X ² are each independently F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^a SO ₃ ⁻ , R ^a COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , One selected from the group consisting of ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ , BR ^a ₄ ⁻ and PF ₆ ⁻ R ^a represents one group selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 50 carbon atoms, and a monovalent heterocyclic group having 2 to 50 carbon atoms. And the alkyl group, aryl group and monovalent heterocyclic group may have a substituent, and * represents a bonding site with another structure.)
And a charge injection layer including a polymer compound having a structure represented by the formula:

  In the electronic device of the present invention, the polymer compound may have a divalent aromatic group which may have a substituent, an alkylene group which may have a substituent, or a substituent. A compound further having at least one group selected from the group consisting of an oxyalkylene group and an optionally substituted dioxyalkylene group is preferred, and has the following formula (II):

(In the formula (II), X ³ and X ⁴ each independently represent F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^b SO ₃ ⁻ , R ^b COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , One selected from the group consisting of ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ , BR ^b ₄ ⁻ and PF ₆ ^{− Rb} represents one group selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 50 carbon atoms, and a monovalent heterocyclic group having 2 to 50 carbon atoms. The alkyl group, aryl group and monovalent heterocyclic group each may have a substituent, Ar ¹ represents a divalent aromatic group which may have a substituent, R ¹ and R ² each independently represents an alkylene group having 1 to 20 carbon atoms, * represents other And n ¹ and n ² are each independently an integer of 1 to 20.)
A compound having a structure represented by is particularly preferred.

The molecular weight of the polymer compound is preferably 1 × 10 ³ or more and 1 × 10 ⁸ or less.

  The electroluminescent element and the photoelectric conversion element of the present invention are characterized by comprising the electronic element of the present invention, wherein the former is a light emitting layer and the latter is between the first electrode and the second electrode. A charge separation layer is disposed.

  The polymer compound of the present invention has the following formula (II):

(In the formula (II), X ³ and X ⁴ each independently represent F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^b SO ₃ ⁻ , R ^b COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , One selected from the group consisting of ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ , BR ^b ₄ ⁻ and PF ₆ ^{− Rb} represents one group selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 50 carbon atoms, and a monovalent heterocyclic group having 2 to 50 carbon atoms. The alkyl group, aryl group and monovalent heterocyclic group each may have a substituent, Ar ¹ represents a divalent aromatic group which may have a substituent, R ¹ and R ² each independently represents an alkylene group having 1 to 20 carbon atoms, * represents other And n ¹ and n ² are each independently an integer of 1 to 20.)
It has the structure represented by these.

  According to the present invention, an electronic device having excellent conversion efficiency can be obtained. The polymer compound of the present invention is useful for the electronic device of the present invention.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  First, the electronic device of the present invention will be described. The electronic device of the present invention includes a first electrode, a second electrode, a light emitting layer or a charge separation layer disposed between the first electrode and the second electrode, the light emitting layer or the charge. Arranged between the separation layer and the first electrode or the second electrode, the following formula (I):

And a charge injection layer including a polymer compound having a structure represented by the formula:

  In the formula (I), * represents a binding site with another structure. In the polymer compound, a hydrogen atom in the aromatic ring in the formula (I) may be substituted with a substituent such as an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

  Further, when there are a plurality of structures represented by the formula (I), they may be the same or different. In the electronic device of the present invention, since the conversion efficiency is further improved, the polymer compound preferably contains a plurality of structures represented by the formula (I), and those containing a plurality in the main chain. More preferred.

X ¹ and X ² in the formula (I) are each independently F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^a SO ₃ ⁻ , R ^a COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , One selected from the group consisting of ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ , BR ^a ₄ ⁻ and PF ₆ ⁻ Represents an ion. As R ^a , an alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a nonyl group and a dodecyl group, a phenyl group, a 1-naphthyl group, C6-C50 aryl group such as naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidyl group, quinolyl group, isoquinolyl group, imidazolyl group Represents a monovalent heterocyclic group having 2 to 50 carbon atoms such as a group; These alkyl group, aryl group and monovalent heterocyclic group may have a substituent. Examples of such substituents include alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkoxy groups, arylalkylthio groups, arylalkenyl groups, arylalkynyl groups, amino groups, Substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, hydroxy group, carboxyl group, substituted oxycarbonyl group, cyano A group, a nitro group, and the like, and when a plurality of the substituents are present, they may be the same or different.

  The alkyl group as the substituent may be linear or branched, and may be a cycloalkyl group. Carbon number of an alkyl group is 1-20 normally, and 1-10 are preferable. Such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, and octyl. , Nonyl group, decyl group, lauryl group and the like. A hydrogen atom in the alkyl group may be substituted with a halogen atom such as a fluorine atom. Examples of the alkyl group substituted with a halogen atom (halogenated alkyl group) include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.

  The alkoxy group as the substituent may be linear or branched, and may be a cycloalkyloxy group. Moreover, you may have a substituent. Carbon number of an alkoxy group is 1-20 normally, and 1-10 are preferable. Such alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyl Examples thereof include an oxy group, an octyloxy group, a nonyloxy group, a decyloxy group, and a lauryloxy group. The hydrogen atom in the alkoxy group may be substituted with a halogen atom such as a fluorine atom. Examples of the alkoxy group substituted with a halogen atom (halogenated alkoxy group) include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group. Moreover, the hydrogen atom in the alkoxy group may be substituted with an alkoxy group. Examples of the alkoxy group substituted with an alkoxy group include a methoxymethyloxy group and a 2-methoxyethyloxy group.

  The alkylthio group as the substituent may be linear or branched, and may be a cycloalkylthio group. Moreover, you may have a substituent. Carbon number of an alkylthio group is 1-20 normally, and 1-10 are preferable. Examples of such an alkylthio group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, s-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group. Octylthio group, nonylthio group, decylthio group, laurylthio group and the like. The hydrogen atom in the alkylthio group may be substituted with a halogen atom such as a fluorine atom. Examples of the alkylthio group substituted with a halogen atom (halogenated alkylthio group) include a trifluoromethylthio group.

The aryl group as the substituent is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon and having a condensed ring, or two or more independent benzene rings or condensed rings are directly or a group such as vinylene. Also included are those combined by. The aryl group may have a substituent such as an alkoxy group. Carbon number of an aryl group is 6-60 normally, and 7-48 are preferable. Examples of such aryl groups include phenyl _group, C 1 _{-C 12} alkoxyphenyl group _(C 1 _{-C 12} is also shown. Hereinafter it is 1 to 12 carbon _atoms.), C 1 -C ₁₂ alkylphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group and the like can be mentioned. The hydrogen atom in the aryl group may be substituted with a halogen atom such as a fluorine atom. Examples of the aryl group substituted with a halogen atom (halogenated aryl group) include a pentafluorophenyl group. Among these aryl groups, a C _{1 to} C ₁₂ alkoxyphenyl group and a C _{1 to} C ₁₂ alkylphenyl group are preferable.

As the C ₁ -C ₁₂ alkoxyphenyl group is an aryl group, methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, isopropoxyphenyl group, butoxyphenyl group, isobutoxyphenyl group, s- butoxyphenyl, t- Butoxyphenyl group, pentyloxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group, 3,7- Examples thereof include a dimethyloctyloxyphenyl group and a lauryloxyphenyl group.

The C ₁ -C ₁₂ alkylphenyl group are mentioned aryl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, trimethylphenyl group, methylethylphenyl group, isopropylphenyl group, butylphenyl group, isobutyl Examples thereof include a phenyl group, a t-butylphenyl group, a pentylphenyl group, an isoamylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, a nonylphenyl group, a decylphenyl group, and a dodecylphenyl group.

The aryloxy group as the substituent is a group in which the aforementioned aryl group is bonded to an oxy group (—O—). Moreover, you may have a substituent. The carbon number of the aryloxy group is usually 6 to 60, preferably 7 to 48. Such an aryloxy group, a phenoxy _group, C 1 _{-C 12} alkoxy phenoxy _group, C 1 _{-C 12} alkylphenoxy group, 1-naphthyloxy group, and a 2-naphthyloxy group. The hydrogen atom in the aryloxy group may be substituted with a halogen atom such as a fluorine atom. Examples of the aryloxy group (halogenated aryloxy group) substituted with a halogen atom include a pentafluorophenyloxy group. Of these aryloxy _groups, C 1 _{-C 12} alkoxy phenoxy _group, a C 1 _{-C 12} alkylphenoxy group are preferable.

As the C ₁ -C ₁₂ alkoxy phenoxy group or an aryloxy group, methoxyphenoxy group, ethoxyphenoxy group, propoxy phenoxy group, isopropoxycarbonyl phenoxy group, butoxyphenoxy group, isobutoxyphenoxy phenoxy group, s- butoxyphenoxy group, t -Butoxyphenoxy group, pentyloxyphenoxy group, hexyloxyphenoxy group, cyclohexyloxyphenoxy group, heptyloxyphenoxy group, octyloxyphenoxy group, 2-ethylhexyloxyphenoxy group, nonyloxyphenoxy group, decyloxyphenoxy group, 3,7 -A dimethyloctyloxyphenoxy group, a lauryloxyphenoxy group, etc. are mentioned.

Examples of the C ₁ -C ₁₂ alkylphenoxy group as the aryloxy group include a methylphenoxy group, an ethylphenoxy group, a dimethylphenoxy group, a propylphenoxy group, a 1,3,5-trimethylphenoxy group, a methylethylphenoxy group, and an isopropylphenoxy group. Group, butylphenoxy group, isobutylphenoxy group, s-butylphenoxy group, t-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group, And dodecylphenoxy group.

The arylthio group as the substituent is a group in which the above-mentioned aryl group is bonded to a thio group (—S—). Moreover, you may have a substituent. Carbon number of an arylthio group is 6-60 normally, and 6-30 are preferable. Such an arylthio group, a phenylthio _group, C 1 _{-C 12} alkoxyphenyl-thio _group, C 1 _{-C 12} alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group. The hydrogen atom in the arylthio group may be substituted with a halogen atom such as a fluorine atom. Examples of the arylthio group (halogenated arylthio group) substituted with a halogen atom include a pentafluorophenylthio group.

The arylalkyl group as the substituent is a group in which a hydrogen atom in the alkyl group is substituted with the aryl group. Moreover, you may have a substituent. The carbon number of the arylalkyl group is usually 7 to 60, preferably 7 to 30. Examples of such aryl alkyl group, a 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, and the like. The hydrogen atom in the arylalkyl group may be substituted with a halogen atom such as a fluorine atom.

The arylalkoxy group as the substituent is a group in which a hydrogen atom in the aforementioned alkoxy group is substituted with the aforementioned aryl group. Moreover, you may have a substituent. The carbon number of the arylalkoxy group is usually 7 to 60, preferably 7 to 30. Such an arylalkoxy group, a 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 group 1-naphthyl-C ₁ -C ₁₂ alkoxy group, 2-naphthyl-C ₁ -C ₁₂ alkoxy group, and the like. The hydrogen atom in the arylalkoxy group may be substituted with a halogen atom such as a fluorine atom.

The arylalkylthio group as the substituent is a group in which a hydrogen atom in the alkylthio group is substituted with the aryl group. Moreover, you may have a substituent. The carbon number of the arylalkylthio group is usually 7 to 60, preferably 7 to 30. Such an arylalkylthio group, a 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, and the like. A hydrogen atom in the arylalkylthio group may be substituted with a halogen atom such as a fluorine atom.

The arylalkenyl group as the substituent is a group in which a hydrogen atom in the alkenyl group is substituted with the aforementioned aryl group. Moreover, you may have a substituent. Carbon number of an aryl alkenyl group is 8-60 normally, and 8-30 are preferable. Such an arylalkenyl group, a 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 group, and the like. A hydrogen atom in the arylalkenyl group may be substituted with a halogen atom such as a fluorine atom. Among these arylalkenyl _group, C 1 _{-C 12} alkoxyphenyl _-C 2 _{-C 12} alkenyl _group, a C 2 _{-C 12} alkylphenyl _-C 2 _{-C 12} alkenyl group are preferred.

The arylalkynyl group as the substituent is a group in which a hydrogen atom in the alkynyl group is substituted with the aforementioned aryl group. Moreover, you may have a substituent. Carbon number of an aryl alkynyl group is 8-60 normally, and 8-30 are preferable. Such an arylalkynyl group, a 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 group, and the like. A hydrogen atom in the arylalkynyl group may be substituted with a halogen atom such as a fluorine atom. Among these arylalkynyl _group, C 1 _{-C 12} alkoxyphenyl _-C 2 _{-C 12} alkynyl _group, a C 1 _{-C 12} alkylphenyl _-C 2 _{-C 12} alkynyl group are preferred.

The substituted amino group as the substituent is one or two hydrogen atoms by one or two groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. A substituted amino group is preferred. Carbon number of a substituted amino group is 1-60 normally, and 2-48 are preferable. The alkyl group, aryl group, arylalkyl group and monovalent heterocyclic group may have a substituent, but the carbon number does not include the carbon number of the substituent. Examples of such substituted amino groups include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, s -Butylamino 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, lauryl group, a cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl 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, 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 group, 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, and a 2-naphthyl _-C 1 _{-C 12} alkylamino group The hydrogen atom in the substituted amino group may be substituted with a halogen atom such as a fluorine atom. Examples of the substituted amino group substituted with a halogen atom (halogenated substituted amino group) include a ditrifluoromethylamino group and a pentafluorophenylamino group.

The substituted silyl group as the substituent is substituted with 1 to 3 hydrogen atoms by 1 to 3 groups selected from the group consisting of alkyl groups, aryl groups, arylalkyl groups and monovalent heterocyclic groups. Silyl group formed. Carbon number of a substituted silyl group is 1-60 normally, and 3-48 are preferable. The alkyl group, aryl group, arylalkyl group and monovalent heterocyclic group may have a substituent, but the carbon number does not include the carbon number of the substituent. Examples of such substituted silyl groups include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-isopropylsilyl group, dimethyl-isopropylsilyl group, diethyl-isopropylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group. Hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, phenyl _-C 1 _{-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, diphenylmethyl Examples thereof include a silyl group, t-butyldiphenylsilyl group, and dimethylphenylsilyl group.

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

  Examples of the acyl group as the substituent include those having 2 to 20 carbon atoms, and those having 2 to 18 carbon atoms are preferable. Examples of such an acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, and a benzoyl group. The hydrogen atom in the acyl group may be substituted with a halogen atom such as a fluorine atom. Examples of the acyl group substituted with a halogen atom (halogenated acyl group) include a trifluoroacetyl group and a pentafluorobenzoyl group.

  Examples of the acyloxy group as the substituent include those having 2 to 20 carbon atoms, and those having 2 to 18 carbon atoms are preferable. Examples of such an acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a benzoyloxy group. A hydrogen atom in the acyloxy group may be substituted with a halogen atom such as a fluorine atom. Examples of the acyloxy group (halogenated acyloxy group) substituted with a halogen atom include a trifluoroacetyloxy group and a pentafluorobenzoyloxy group.

  The imine residue as the substituent is an imine compound (an organic compound having a group represented by the formula: -N = C- in the molecule, and aldimine, ketimine, and hydrogen atoms on these N atoms are alkyl groups. And the like is a residue obtained by removing one hydrogen atom from the above. Carbon number of an imine residue is 2-20 normally, and 2-18 are preferable. Examples of such an imine residue include those represented by the following formula (wherein, * represents a binding site with another structure).

  As an amide group which is the said substituent, a C2-C20 thing is mentioned normally, A C2-C18 thing is preferable. Examples of such an amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a diformamide group, a diacetamido group, a dipropioamide group, a dibutyroamide group, and a dibenzamide group. The hydrogen atom in the amide group may be substituted with a halogen atom such as a fluorine atom. Examples of the amide group (halogenated amide group) substituted with a halogen atom include a trifluoroacetamide group, a pentafluorobenzamide group, a ditrifluoroacetamide group, and a dipentafluorobenzamide group.

  The acid imide group as the substituent is a residue obtained by removing a hydrogen atom bonded to a nitrogen atom from an acid imide. The acid imide group usually has 4 to 20 carbon atoms, preferably 4 to 18 carbon atoms. Examples of such acid imide groups include those represented by the following formula (wherein * represents a bonding site with another structure).

The monovalent heterocyclic group as the substituent is a heterocyclic compound (among organic compounds having a cyclic structure, not only a carbon atom but also an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a boron atom, etc. It is a remaining atomic group obtained by removing one hydrogen atom from a compound containing a heteroatom in the ring. The carbon number of the monovalent heterocyclic group is usually 4 to 60, and 4 to 20 is preferable. The monovalent heterocyclic group may have a substituent, but the carbon number does not include the carbon number of the substituent. Examples of such a monovalent heterocyclic group include a thienyl group, a C _{1 to} C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a C _{1 to} C ₁₂ alkyl pyridyl group, a piperidyl group, a quinolyl group, and an isoquinolyl group. Etc. The hydrogen atom in the monovalent heterocyclic group may be substituted with a halogen atom such as a fluorine atom. Among these monovalent heterocyclic groups, a thienyl group, a C _{1 to} C ₁₂ alkyl thienyl group, a pyridyl group, and a C _{1 to} C ₁₂ alkyl pyridyl group are preferable.

  Examples of the substituted oxycarbonyl group as the substituent include those in which one group selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group is bonded to an oxycarbonyl group. . Carbon number of a substituted oxycarbonyl group is 2-60 normally, and 2-48 are preferable. The alkyl group, aryl group, arylalkyl group and monovalent heterocyclic group may have a substituent, but the carbon number does not include the carbon number of the substituent. Examples of such a substituted oxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, an s-butoxycarbonyl group, a t-butoxycarbonyl group, and pentyloxy. Carbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, Examples include dodecyloxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, and pyridyloxycarbonyl group. The hydrogen atom in the substituted oxycarbonyl group may be substituted with a halogen atom such as a fluorine atom. Examples of the substituted oxycarbonyl group substituted with a halogen atom include a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a perfluorobutoxycarbonyl group, a perfluorohexyloxycarbonyl group, and a perfluorooctyloxycarbonyl group.

  In addition, the polymer compound according to the present invention includes a divalent aromatic group which may have a substituent, an alkylene group which may have a substituent, and an oxy which may have a substituent. It is preferable to further have at least one group selected from the group consisting of an alkylene group and an optionally substituted dioxyalkylene group.

  Examples of the divalent aromatic group that may have a substituent include a divalent aromatic hydrocarbon group and a divalent aromatic heterocyclic group. Examples of such divalent aromatic groups include a benzene ring, a pyridine ring, a 1,2-diazine ring, a 1,3-diazine ring, a 1,4-diazine ring, a 1,3,5-triazine ring, and a furan ring. A divalent group obtained by removing two hydrogen atoms from a monocyclic aromatic ring such as a pyrrole ring, a thiophene ring, a pyrazole ring, an imidazole ring, an oxazole ring, an oxadiazol ring, an azadiazol ring, and the like. A divalent group obtained by removing two hydrogen atoms from a condensed polycyclic aromatic ring in which two or more aromatic rings each independently selected from the group consisting of aromatic rings are condensed, from the group consisting of the monocyclic aromatic rings A divalent group in which two hydrogen atoms are removed from a linked polycyclic aromatic ring in which two or more independently selected aromatic rings are connected by a single bond, ethenylene group or ethynylene group, the monocyclic aromatic ring Independently selected from the group consisting of The divalent aromatic ring in which two hydrogen atoms are removed from a bridged polycyclic aromatic ring having a structure in which the two aromatic rings are bridged with a divalent group such as a methylene group, an ethylene group, a carbonyl group, or an imino group. And the like.

  In the condensed polycyclic aromatic ring, the number of monocyclic aromatic rings to be condensed is preferably 2 to 4, more preferably 2 to 3, and still more preferably 2 from the viewpoint of the solubility of the polymer compound. In the linked polycyclic aromatic ring, the number of monocyclic aromatic rings to be linked is preferably 2 to 4, more preferably 2 to 3, and even more preferably 2 from the viewpoint of solubility. In the bridged polycyclic aromatic ring, the number of monocyclic aromatic rings to be bridged is preferably 2 to 4, more preferably 2 to 3, more preferably 2 from the viewpoint of the solubility of the polymer compound. preferable.

  Examples of the monocyclic aromatic ring include those represented by the following formulas (1) to (16).

  Examples of the condensed polycyclic aromatic ring include those represented by the following formulas (17) to (36).

  Examples of the linked polycyclic aromatic ring include those represented by the following formulas (37) to (47).

  Examples of the bridged polycyclic aromatic ring include those represented by the following formulas (48) to (57).

  Among such aromatic rings, from the viewpoint of electron and / or hole acceptability of the polymer compound, the formulas (1) to (16), the formulas (17) to (27), and the formula (33) to (36), those represented by the formulas (47) to (48), the formulas (50) to (51), and the formula (53) are preferable, and the formulas (1) to (6), the formula ( 15) to (16), the formula (33), the formula (36), the formulas (47) to (48), and the formulas (50) to (51) are more preferable.

  Moreover, as carbon number of the alkylene group contained in the said high molecular compound concerning this invention, an oxyalkylene group, and a dioxyalkylene group, 1-50 are preferable. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptalene group, a nonalene group, a decylene group, and a dodecylene group. Examples of the oxyalkylene group include an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxypentylene group, an oxyhexylene group, an oxyheptalene group, an oxynonalene group, an oxydecylene group, and an oxide decylene group. Can be mentioned. Examples of the dioxyalkylene group include a dioxymethylene group, a dioxyethylene group, a dioxypropylene group, a dioxybutylene group, a dioxypentylene group, a dioxyhexylene group, a dioxyheptalene group, a dioxynonalene group, and a dioxydecylene group. And a dioxydecylene group. The alkylene group, oxyalkylene group and dioxyalkylene group may have a substituent.

  Among such polymer compounds, in the electronic device of the present invention, the following formula (II):

A compound having a structure represented by is more preferable. In the formula (II), X ³ and X ⁴ are each independently F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^b SO ₃ ⁻ , R ^b COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , One selected from the group consisting of ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ , BR ^b ₄ ⁻ and PF ₆ ⁻ Represents an ion. Among these ions, F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^b SO ₃ ⁻ , R ^b COO ⁻ , BF ₄ ⁻ , BR are used from the viewpoint of easy synthesis of the polymer compound. ^b ₄ ^- and PF ₆ ^- are preferred. R ^b has the same meaning as R ^a in formula (I). Ar ¹ represents a divalent aromatic group which may have a substituent, R ¹ and R ² each independently represent an alkylene group having 1 to 20 carbon atoms, and * represents a bonding site with another structure N ¹ and n ² are each independently an integer of 1 to 20. As the n ¹ and n ^2, from the viewpoint of ease of synthesis of the polymer compound, preferably an integer of from 2 to 10.

The divalent aromatic group which may have a substituent represented by Ar ¹ in the formula (II) is exemplified as a group which may be further contained in the polymer compound according to the present invention. And a divalent aromatic group which may have a substituent such as the divalent aromatic hydrocarbon group or the divalent aromatic heterocyclic group. Among these divalent aromatic groups, from the viewpoint of charge injection properties of the polymer compound, the formulas (1) to (36), the formulas (41) to (44), the formulas (47) to ( 51) and those represented by the formulas (53) to (54) are particularly preferable.

Examples of the alkylene group represented by R ¹ and R ² in the formula (II) include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a heptalene group. R ¹ and R ² may be the same or different. Among these alkylene groups, a methylene group, an ethylene group, a propylene group, and a butylene group are particularly preferable from the viewpoint of solubility of the polymer compound.

The molecular weight of the polymer compound according to the present invention, 1 × preferably 10 ³ or more 1 × 10 ⁸ or less from the viewpoint of film forming property due to coating, more preferably 1 × 10 ³ or more 1 × 10 ⁷ or less, 1 × 10 ³ or more and 1 × 10 ⁶ or less are more preferable. In addition, the molecular weight of the polymer compound can be obtained by performing ¹ H-NMR measurement and converting it with a proton ratio (integration ratio).

  Examples of the structure represented by the formula (II) include structures represented by the following formulas (58) to (65). Moreover, as a high molecular compound of this invention, the high molecular compound which contains the structure represented by following formula (58)-(65) as a repeating unit is mentioned.

  Next, the manufacturing method of the said high molecular compound concerning this invention is demonstrated. As a suitable method for producing the polymer compound, the following formula (III):

And 4,4′-bipyridyl (wherein the hydrogen atom of the aromatic ring may be substituted with a substituent) is subjected to condensation polymerization with a polymerizable compound. The polymerizable compound may be any compound having two or more polymerizable functional groups, and from the viewpoint of ease of condensation polymerization, the following formula (IV):
Y ¹ -Q ¹ -Y ² (IV)
(In Formula (IV), Y ¹ and Y ² represent a polymerizable functional group, and Q ¹ has a single bond or a divalent aromatic group which may have a substituent, or a substituent. It is a group containing at least one selected from the group consisting of an alkylene group which may be substituted, an oxyalkylene group which may have a substituent, and a dioxyalkylene group which may have a substituent.
The compound represented by these is preferable.

  Examples of the polymerizable functional group include a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an arylalkyl sulfonate group, and a sulfonium methyl group.

  Examples of the halogen atom that is the polymerizable functional group 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 group include a benzyl sulfonate group.

Examples of the divalent aromatic group which may have a substituent contained in Q ¹ in the formula (IV) are exemplified as groups which may be further contained in the polymer compound according to the present invention. Examples thereof include a divalent aromatic group which may have a substituent such as the divalent aromatic hydrocarbon group or the divalent aromatic heterocyclic group. Among these divalent aromatic groups, from the viewpoint of charge injection properties of the polymer compound, the formulas (1) to (36), the formulas (41) to (44), the formulas (47) to ( 51) and those represented by the formulas (53) to (54) are particularly preferable.

Further, an alkylene group, an oxy As the alkylene group and di- oxyalkylene group, exemplified alkylene group as the further included which may be based on the polymer compound of the present invention contained in to Q ¹ in the formula (IV) , An oxyalkylene group and a dioxyalkylene group. The alkylene group, oxyalkylene group and dioxyalkylene group may have a substituent. Of these divalent groups, an oxyalkylene group and a dioxyalkylene group are particularly preferable from the viewpoint of solubility of the polymer compound.

  In the case of producing the polymer compound according to the present invention, for example, 4,4′-bipyridyl and the polymerizable compound are dissolved in an organic solvent as necessary, and then an alkali or a suitable catalyst is used as appropriate. A polymerization method in which the reaction is carried out at a temperature not lower than the melting point of the organic solvent and not higher than the boiling point can be employed. Examples of such a polymerization method include J. Org. Polym. Sci. Part A: Polymer Chemistry, 40, 659 (2002), and Org. Biomol. Chem. , Volume 1, p. 2661 (2003), etc., can be appropriately employed.

  Examples of the organic solvent used in the polymerization method include saturated hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene, and xylene, methanol, ethanol, propanol, isopropanol, Alcohols such as butanol and t-butyl alcohol, carboxylic acids such as formic acid, acetic acid and propionic acid, ethers such as dimethyl ether, diethyl ether, methyl-t-butyl ether, tetrahydrofuran, tetrahydropyran and dioxane, trimethylamine, triethylamine, N, N, N ′, N′-tetramethylethylenediamine, amines such as pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethyl Acetamide, amides such as N- methylmorpholine oxide. These organic solvents may be used alone or in combination of two or more. Of these organic solvents, amides are preferable, and N, N-dimethylformamide, N, N-dimethylacetamide, and N, N-diethylacetamide are more preferable.

  The polymer compound obtained by such a polymerization method may be used as it is in the electronic device of the present invention, or may undergo an ion exchange reaction with a metal salt. The metal salts used at this time include metal halides, metal hydroxides, sulfonic acid metal salts, carboxylic acid metal salts, hypochlorite metal salts, chlorite metal salts, chlorate metal salts, and metal perchlorates. Salts, metal thiocyanate, metal cyanide, metal nitrate, metal sulfate, metal phosphate, metal borate and the like.

  Next, a method for forming a charge injection layer containing the polymer compound will be described. A preferred method for forming the charge injection layer containing the polymer compound includes a film forming method using a solution containing the polymer compound.

As the solvent used in the solution containing the polymer compound, a solvent having a solubility parameter of 9.3 or more excluding water is preferable. Such solvents include methanol (12.9), ethanol (11.2), 2-propanol (11.5), 1-butanol (9.9), t-butyl alcohol (10.5), acetonitrile. (11.8), 1,2-ethanediol (14.7), N, N-dimethylformamide (11.5), dimethyl sulfoxide (12.8), acetic acid (12.4), nitrobenzene (11.1) ), Nitromethane (11.0), 1,2-dichloroethane (9.7), dichloromethane (9.6), chlorobenzene (9.6), bromobenzene (9.9), dioxane (9.8), carbonic acid Examples include propylene (13.3), pyridine (10.4), carbon disulfide (10.0), and mixed solvents thereof. In addition, the numerical value in the said parenthesis represents the value of the solubility parameter of the said solvent. For example, the solubility parameter (δ _m ) of the mixed solvent of the solvent 1 and the solvent 2 is represented by the following formula:
δ _m = δ ₁ × φ ₁ + δ ₂ × φ ₂
(In the formula, δ ₁ represents the solubility parameter of solvent 1, φ ₁ represents the volume fraction of solvent 1, δ ₂ represents the solubility parameter of solvent 2, and φ ₂ represents the volume fraction of solvent 2.)
It can ask for.

  Examples of the film forming method include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, cap coating, and spray coating. Method, screen printing method, flexographic printing method, offset printing method, inkjet printing method, nozzle coating method and the like.

  In the electronic device of the present invention, the charge injection layer containing the polymer compound needs to have a thickness that does not cause pinholes, but the optimum value differs depending on the polymer compound used. It is preferable to appropriately select the voltage and the light emission efficiency so as to have appropriate values. Such a film thickness is preferably 1 nm to 1 μm, more preferably 2 nm to 500 nm, and still more preferably 2 nm to 200 nm. When the thickness of the charge injection layer containing the polymer compound is less than the lower limit, pinholes tend to occur, and when the thickness exceeds the upper limit, the driving voltage of the electronic device tends to increase.

<Electronic element>
Next, the electronic device of the present invention will be described. The electronic device of the present invention includes a first electrode, a second electrode, a light emitting layer or a charge separation layer disposed between the first electrode and the second electrode, the light emitting layer or the light emitting layer. And a charge injection layer including the polymer compound disposed between the charge separation layer and the first electrode or the second electrode.

  The electronic device of the present invention can be used as an electroluminescent device when a light emitting layer is disposed between the first electrode and the second electrode, and between the first electrode and the second electrode. In the case where a charge separation layer is disposed on the substrate, it can be used as a photoelectric conversion element.

  Since the polymer compound according to the present invention is excellent in charge injection property, an electronic device having excellent conversion efficiency can be formed by using a layer containing such a polymer compound as a charge injection layer. As a result, when the electronic element is an electroluminescent element, an element that emits light with high luminance is obtained. When the electronic element is a photoelectric conversion element, an element with high photoelectric conversion efficiency is obtained.

<Electroluminescent device>
The case where the electronic device of the present invention is an electroluminescent device (hereinafter referred to as “electroluminescent device of the present invention”) will be described. The electroluminescent device of the present invention includes a cathode, an anode, a light emitting layer disposed between the cathode and the anode, and between the cathode and the light emitting layer or between the anode and the light emitting layer. And a charge injection layer including the polymer compound according to the present invention. The electroluminescent device of the present invention may further comprise a substrate, on which the cathode, the anode, the light emitting layer, a charge injection layer containing the polymer compound, and other materials as necessary. Layers are arranged.

  An aspect of the electroluminescent device of the present invention includes an anode disposed on a substrate, a light emitting layer disposed thereon, and a cathode disposed thereon, and the anode, the light emitting layer, And a device having a charge injection layer containing the polymer compound between or between the cathode and the light emitting layer. Moreover, as another aspect, it is equipped with the cathode arrange | positioned on a board | substrate, the light emitting layer arrange | positioned on it, and the anode arrange | positioned on it further, Between the said cathode and the said light emitting layer, or the said Examples include a device including a charge injection layer containing the polymer compound between an anode and the light emitting layer. The electroluminescent device of the present invention is a charge injection layer (hereinafter referred to as “other charge injection layer”) that does not contain the polymer compound between the cathode and the light emitting layer or between the anode and the light emitting layer. ) May be further provided. In these electroluminescent devices, the charge injection layer disposed between the anode and the light emitting layer functions as a hole injection layer, and the charge injection layer disposed between the cathode and the light emitting layer functions as an electron injection layer. To do. Moreover, the electroluminescent element of this invention may be provided with the layer which has other functions, such as a protective layer, a buffer layer, and a reflection layer.

  The electroluminescent element of the present invention may further include one or more layers of an interlayer and a hole transport layer between the anode and the light emitting layer. In particular, when a hole injection layer is present, it is preferable that one or more of an interlayer and a hole transport layer are disposed between the light emitting layer and the hole injection layer.

  In addition, the electroluminescent device of the present invention may further include one or more of an electron transport layer and a hole blocking layer between the cathode and the light emitting layer. In particular, when an electron injection layer is present, it is preferable that one or more of an electron transport layer and a hole blocking layer be disposed between the light emitting layer and the electron injection layer.

  Here, the anode supplies holes to a hole injection layer, a hole transport layer, an interlayer, a light emitting layer, etc., and the cathode serves as an electron injection layer, an electron transport layer, a hole blocking layer, a light emitting layer. To supply electrons.

  The light-emitting layer has a function of receiving holes from a layer adjacent to the anode side and receiving electrons from a layer adjacent to the cathode side when an electric field is applied, and the received charges (electrons and holes) by the force of the electric field. A layer having a function of moving, a function of providing a field for recombination of electrons and holes and connecting it to light emission.

  The electron injection layer is a layer mainly having a function of receiving electrons from the cathode and further having a function of transporting electrons as needed or a function of blocking holes injected from the anode. The electron transport layer refers to a layer mainly having a function of transporting electrons and further having a function of receiving electrons from the cathode or blocking holes injected from the anode as necessary. The hole blocking layer mainly refers to a layer having a function of blocking holes injected from the anode, and further having a function of receiving electrons from the cathode or a function of transporting electrons as necessary.

  The hole injection layer mainly has a function of receiving holes from the anode, and further transports holes as necessary, a function of supplying holes to the light emitting layer, or a barrier to electrons injected from the cathode. A layer having a function. The hole transport layer mainly has a function of transporting holes, and further receives holes from the anode as needed, functions to supply holes to the light emitting layer, or barriers electrons injected from the cathode. The layer which has the function to do.

  The interlayer has at least one of a function of receiving holes from the anode, a function of transporting holes, a function of supplying holes to the light emitting layer, and a function of blocking electrons injected from the cathode. In general, it is a layer that is disposed adjacent to the light emitting layer and has a role of separating the light emitting layer and the anode, or the light emitting layer and the hole injection layer or the hole transport layer.

  In the present invention, the electron transport layer and the hole transport layer are collectively referred to as a charge transport layer, and the electron injection layer and the hole injection layer are collectively referred to as a charge injection layer.

  As the daylighting type of such an electroluminescent element, there are a bottom emission type for daylighting from the substrate side, a top emission type for daylighting from the opposite side of the substrate, and a double sided daylighting type.

  Further, by covering such an electroluminescent element with a sealing film or a sealing substrate, a light emitting device in which the electroluminescent element is shielded from the outside air can be formed.

  Hereinafter, a detailed configuration of the electroluminescent element of the present invention will be described.

  The layer configuration of the electroluminescent element of the present invention includes the following layer configuration (a). In this layer configuration (a), the hole injection layer or the electron injection layer is a layer containing the polymer compound. Moreover, as a layer structure of the electroluminescent element of this invention, if it has a hole injection layer or an electron injection layer containing the said high molecular compound, from this layer structure (a), a hole injection layer, a hole A layer configuration in which one or more of the transport layer, the interlayer, the hole blocking layer, the electron transport layer, and the electron injection layer is omitted is also included.

(A) Anode-hole injection layer- (hole transport layer and / or interlayer) -light emitting layer- (hole block layer and / or electron transport layer) -electron injection layer-cathode

  Here, the symbol “-” indicates that the layers are arranged adjacent to each other.

  “(Hole transport layer and / or interlayer)” means a layer consisting of only a hole transport layer, a layer consisting only of an interlayer, a layer configuration of a hole transport layer-interlayer, an interlayer-hole transport layer A layer configuration or any other layer configuration including one or more hole transport layers and interlayers is shown.

  “(Hole blocking layer and / or electron transporting layer)” means a layer consisting of only a hole blocking layer, a layer consisting only of an electron transporting layer, a layer configuration of a hole blocking layer-electron transporting layer, an electron transporting layer—positive The layer configuration of the hole blocking layer, or any other layer configuration including at least one hole blocking layer and one electron transporting layer is shown. The same applies to the following description of the layer configuration.

  Moreover, the electroluminescent element of this invention may be equipped with the two light emitting layers in one laminated structure. In this case, the layer configuration of the electroluminescent element includes the following layer configuration (b). In this layer structure (b), the hole injection layer adjacent to the anode or the electron injection layer adjacent to the cathode is a layer containing the polymer compound. Moreover, as a layer structure of the electroluminescent element of this invention, if it has a hole injection layer or an electron injection layer containing the said high molecular compound, from this layer structure (b), a hole injection layer, a hole A layer configuration in which one or more of a transport layer, an interlayer, a hole blocking layer, an electron transport layer, an electron injection layer, and an electrode are omitted is also included.

(B) Anode-hole injection layer- (hole transport layer and / or interlayer) -light emitting layer- (hole block layer and / or electron transport layer) -electron injection layer-electrode-hole injection layer- ( Hole transport layer and / or interlayer) -light emitting layer- (hole block layer and / or electron transport layer) -electron injection layer-cathode

  Furthermore, the electroluminescent element of the present invention may include three or more light emitting layers in one laminated structure. In this case, the following layer structure (c) is mentioned as a layer structure of the electroluminescent element. In this layer configuration (c), the hole injection layer adjacent to the anode or the electron injection layer adjacent to the cathode is a layer containing the polymer compound. Moreover, as a layer structure of the electroluminescent element of this invention, if a hole injection layer or electron injection layer containing the said high molecular compound is provided, from this layer structure (c), a hole injection layer, a hole A layer configuration in which one or more of a transport layer, an interlayer, a hole blocking layer, an electron transport layer, an electron injection layer, and an electrode are omitted is also included.

(C) Anode-hole injection layer- (hole transport layer and / or interlayer) -light emitting layer- (hole block layer and / or electron transport layer) -electron injection layer-repeating unit A-repeating unit A. Here, “Repeating unit A” is an electrode—a hole injection layer— (a hole transport layer and / or an interlayer) —a light emitting layer— (a hole block layer and / or an electron transport layer) —electrons The unit of the layer structure of the injection layer is shown.

Preferable examples of the layer structure of the electroluminescent element of the present invention include the following.
(D) Anode-charge injection layer-light emitting layer-cathode (e) Anode-light emitting layer-charge injection layer-cathode (f) Anode-charge injection layer-light emitting layer-charge injection layer-cathode (g) anode-charge injection Layer-hole transport layer-light emitting layer-cathode (h) anode-hole transport layer-light emitting layer-charge injection layer-cathode (i) anode-charge injection layer-hole transport layer-light emitting layer-charge injection layer- Cathode (j) Anode-charge injection layer-light-emitting layer-electron transport layer-cathode (k) anode-light-emitting layer-electron transport layer-charge injection layer-cathode (l) anode-charge injection layer-light-emitting layer-electron transport layer -Charge injection layer-Cathode (m) anode-Charge injection layer-Hole transport layer-Light emitting layer-Electron transport layer-Cathode (n) Anode-Hole transport layer-Light emitting layer-Electron transport layer-Charge injection layer-Cathode (O) 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 and the positive layer There is also a structure in which an interlayer is disposed adjacent to the light emitting layer between the electrodes. In this case, the interlayer may also serve as a hole injection layer and / or a hole transport layer.

  The electroluminescent device of the present invention may further be provided with an insulating layer adjacent to the electrode in order to improve the adhesion with the electrode and improve the injection of charges from the electrode (that is, holes or electrons), In addition, a thin buffer layer may be inserted at the interface of the charge transport layer (that is, the hole transport layer or the electron transport layer) or the light emitting layer in order to improve the adhesion at the interface or prevent mixing. The order and number of layers to be stacked, and the thickness of each layer can be appropriately set in consideration of the light emission efficiency and the element lifetime.

  Next, the material and forming method of each layer constituting the electroluminescent element of the present invention will be described.

<Board>
The substrate constituting the electroluminescent element of the present invention may be any substrate as long as it does not change when an electrode is formed and an organic layer is formed, for example, a glass substrate, a plastic substrate, a polymer film, a metal film, a silicon substrate. A laminate of these is used. A commercially available substrate is available as the substrate, or can be manufactured by a known method.

  When the electroluminescent element of the present invention constitutes a pixel of a display device, a circuit for driving a pixel may be provided on the substrate, or a planarization film may be provided on the drive circuit. Good. When a planarizing film is provided, it is preferable that the center line average roughness (Ra) of the planarizing film satisfies Ra <10 nm. Ra can be measured with reference to JIS-B0651 to JIS-B0656 and JIS-B0671-1 based on JIS-B0601-2001 of Japanese Industrial Standards JIS.

<Anode>
The anode constituting the electroluminescent device of the present invention has a work function of 4 on the surface of the anode on the side of the light emitting layer from the viewpoint of supplying holes to the hole injection layer, hole transport layer, interlayer, light emitting layer and the like. The thing of 0 eV or more is preferable.

  As the anode material, metals, alloys, metal oxides, electrically conductive compounds such as metal sulfides, and mixtures thereof can be used. Specifically, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), conductive metal oxides such as molybdenum oxide, metals such as gold, silver, chromium, nickel, and Examples thereof include a mixture of these conductive metal oxides and metals.

  The anode may have a single layer structure composed of one or more of these materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. In the case of a multilayer structure, it is more preferable to use a material having a work function of 4.0 eV or more for the outermost surface layer on the light emitting layer side.

  As a method for producing the anode, a known method can be used, and examples thereof include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. For the anode prepared by these methods, electrons such as UV ozone, silane coupling agent, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane are used as necessary. The surface treatment may be performed with a solution containing a receptive compound. The surface treatment can improve the electrical connection with the organic layer in contact with the anode.

  The film thickness of the anode is usually 10 nm to 10 μm, preferably 50 nm to 500 nm. Further, from the viewpoint of preventing poor electrical connection such as a short circuit, the center line average roughness (Ra) of the light emitting layer side surface of the anode preferably satisfies Ra <10 nm, and more preferably satisfies Ra <5 nm. .

  When the anode is used as a light reflecting electrode in the electroluminescent element of the present invention, the anode includes a light reflecting layer made of a highly light reflecting metal and a material having a work function of 4.0 eV or higher. It is preferable to have a multilayer structure in which

As a configuration example of such an anode,
(I) Ag-MoO ₃
(Ii) (Ag—Pd—Cu alloy) — (ITO and / or IZO)
(Iii) (Al—Nd alloy) — (ITO and / or IZO)
(Iv) (Mo—Cr alloy) — (ITO and / or IZO)
(V) (Ag—Pd—Cu alloy) — (ITO and / or IZO) —MoO ₃
Etc. In order to obtain sufficient light reflectance, the film thickness of the highly light-reflective metal layer such as Al, Ag, Al alloy, Ag alloy, Cr alloy is preferably 50 nm or more, and more preferably 80 nm or more. . The film thickness of the high work function material layer such as ITO, IZO, MoO ₃ is usually 5 nm to 500 nm.

<Hole injection layer>
Among the hole injection layers constituting the electroluminescent device of the present invention, the hole injection layer not containing the polymer compound according to the present invention, that is, the other hole injection layer forming material, carbazole derivative, Triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, starburst amines, phthalocyanine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly ( - vinylcarbazole) derivatives, organic silane derivatives, and polymers containing these structures. In addition, conductive metal oxides such as vanadium oxide, tantalum oxide, tungsten oxide, molybdenum oxide, ruthenium oxide, and aluminum oxide, conductive polymers and oligomers such as polyaniline, aniline-based copolymers, thiophene oligomers, and polythiophenes, poly ( 3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, organic conductive materials such as polypyrrole, polymers containing these, and amorphous carbon. Furthermore, tetracyanoquinodimethane derivatives (for example, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), 1,4-naphthoquinone derivatives, diphenoquinone derivatives, polynitro compounds, etc. An acceptor organic compound, a silane coupling agent such as octadecyltrimethoxysilane, and the like can also be suitably used.

  The material may be used as a single component or as a composition comprising a plurality of components. In addition, the other hole injection layer may have a single layer structure composed of one or more of the materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. Moreover, the material illustrated as a material which can be used with the positive hole transport layer and interlayer which are mentioned later can also be used with the said other hole injection layer.

  Various known methods can be used for forming the other hole injection layer. In the case of inorganic compound materials, examples include vacuum deposition, sputtering, and ion plating. In the case of low-molecular organic materials, vacuum deposition, transfer methods such as laser transfer and thermal transfer, and film formation from solution. And a method (a mixed solution with a polymer binder may be used). In the case of a polymer organic material, a method by film formation from a solution can be mentioned.

  When the hole injection material is a low molecular compound such as a pyrazoline derivative, an arylamine derivative, a stilbene derivative, or a triphenyldiamine derivative, another hole injection layer can be formed by a vacuum deposition method.

  In addition, the other hole injection layer may be formed using a mixed solution in which a polymer compound binder other than the polymer compound according to the present invention and the low molecular hole injection material are dispersed. As the polymer compound binder to be mixed, those that do not extremely inhibit charge transport are preferable, and those that do not strongly absorb visible light are suitably used. Examples of the polymer compound binder include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof. , Polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

  As a solvent used for film formation from a solution, any solvent that dissolves the hole injection material may be used. Examples of such solvents include water, chlorine-containing solvents such as chloroform, methylene chloride, and dichloroethane, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone and methyl ethyl ketone, ethyl acetate, and acetic acid. Examples include ester solvents such as butyl and ethyl cellosolve acetate.

  Examples of the film forming method from the solution include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, and capillary coating. Coating methods such as coating methods such as coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reverse printing, and ink jet printing can be used. From the viewpoint of easy pattern formation, a printing method such as a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, an ink jet printing method, or a nozzle coating method is preferable.

  The thickness of the other hole injection layer needs to be a thickness that does not cause pinholes, but the optimum value differs depending on the material used, so that the drive voltage and the light emission efficiency are appropriate. It is preferable to select. Such a film thickness is preferably 1 nm to 1 μm, more preferably 2 nm to 500 nm, and still more preferably 10 nm to 100 nm. When the film thickness of the other hole injection layer is less than the lower limit, pinholes tend to be generated. On the other hand, when the film thickness exceeds the upper limit, the driving voltage of the electroluminescent element tends to increase.

  In the electroluminescent device of the present invention, an organic layer such as a hole transport layer, an interlayer, or a light emitting layer is formed following the hole injection layer containing the polymer compound according to the present invention or the other hole injection layer. In particular, in the case where both layers are formed by a coating method, the previously applied layer may be dissolved in a solvent contained in the solution of the layer to be applied later, and a laminated structure may not be formed. In this case, it is preferable to use a method of insolubilizing the lower layer in the solvent. As a method for insolubilizing in a solvent, a crosslinking group is introduced into a polymer compound, and this is crosslinked to insolubilize, or a low molecular compound having a crosslinking group having an aromatic ring represented by aromatic bisazide is crosslinked. Mixing as an agent and cross-linking it to insolubilize, mixing a low-molecular compound with a cross-linking group that does not have an aromatic ring represented by an acrylate group as a cross-linking agent, cross-linking this to insolubilize, lower layer Are exposed to ultraviolet light to be crosslinked and insolubilized in a solvent used for forming an upper layer, and a method in which a lower layer is heated to be crosslinked and insolubilized in a solvent used for forming an upper layer. When heating the lower layer, the heating temperature is usually 100 ° C. to 300 ° C., and the time is usually 1 minute to 1 hour.

  Moreover, as a method of laminating | stacking without dissolving a lower layer by methods other than bridge | crosslinking, the method of using a different polar solution for formation of an adjacent layer is mentioned. For example, there is a method in which a water-soluble polymer compound is used for the lower layer and an oil-soluble polymer compound is used for the upper layer so that the lower layer does not dissolve even when the upper layer solution is applied.

<Hole transport layer and interlayer>
Materials for forming the hole transport layer and the interlayer constituting the electroluminescent device of the present invention include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives. , Phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrins Examples thereof include compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, organosilane derivatives, and polymers containing these structures. In addition, conductive polymers and oligomers such as aniline copolymers, thiophene oligomers, and polythiophenes, and organic conductive materials such as polypyrrole are also included.

  The material may be used as a single component or as a composition comprising a plurality of components. In addition, the hole transport layer and the interlayer may have a single layer structure composed of one or more of the materials, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. Good. Moreover, the material illustrated as a material which can be used with the said other hole injection layer can also be used with a hole transport layer.

  JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992. JP-A-3-152184, JP-A-5-263073, JP-A-6-1972, WO2005 / 52027 pamphlet, JP-A-2006-295203, etc. are correct. Can be used as material for pore transport layer and interlayer. Among these, a polymer containing a divalent aromatic amine residue as a repeating unit is preferable.

  Examples of the divalent aromatic amine residue include groups represented by the following formula (V).

In the formula (V), Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are each independently an arylene group which may have a substituent or a divalent heterocyclic ring which may have a substituent. Ar ⁶ , Ar ⁷ and Ar ⁸ represent an aryl group which may have a substituent or a monovalent heterocyclic group which may have a substituent, and m ¹ and n ³ are Each independently represents 0 or 1.

  Examples of the substituent that the arylene group, aryl group, divalent heterocyclic group and monovalent heterocyclic group may have include a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, and an aryloxy group. Group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substitution Amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, alkyloxycarbonyl group, aryloxycarbonyl Group, arylalkyloxycarbonyl group, Hetero aryloxycarbonyl group, and a carboxyl group. The substituent is vinyl group, acetylene group, butenyl group, acrylic group, acrylate group, acrylamide group, methacryl group, methacrylate group, methacrylamide group, vinyl ether group, vinylamino group, silanol group, small ring (cyclopropyl group) , A group having a cyclobutyl group, an epoxy group, an oxetane group, a diketene group, an episulfide group, etc.), a lactone group, a lactam group, or a group containing a structure of a siloxane derivative.

  The polymer containing a divalent aromatic amine residue as a repeating unit may further have another repeating unit. Other repeating units include arylene groups such as a phenylene group and a fluorenediyl group. Of these polymers, those containing a crosslinking group are more preferred.

  Examples of the method for forming the hole transport layer and the interlayer include the same methods as those for forming the other hole injection layer. Film formation methods from solution include spin coating, casting, bar coating, slit coating, spray coating, nozzle coating, and other coating methods, as well as gravure printing, screen printing, flexographic printing, and inkjet. Examples of the printing method include a printing method, and in the case of using a sublimable compound material, a vacuum deposition method, a transfer method, and the like. Examples of the solvent used for film formation from a solution include the solvents exemplified above for the other hole injection layer film formation method.

  When an organic layer such as a light-emitting layer is formed by a coating method following the hole transport layer and the interlayer, if the lower layer dissolves in the solvent contained in the solution of the layer to be applied later, the hole injection layer It is preferable to insolubilize the lower layer with respect to the solvent by the same method as exemplified in the film forming method.

  The film thickness of the hole transport layer and the interlayer should be such that pinholes do not occur, but the optimum values differ depending on the materials used, so that the drive voltage and luminous efficiency are appropriate. It is preferable to select. Such a film thickness is preferably 1 nm to 1 μm, more preferably 2 nm to 500 nm, and still more preferably 5 nm to 100 nm. When the thickness of the hole transport layer and the interlayer is less than the lower limit, pinholes tend to be generated, and when the upper limit is exceeded, the driving voltage of the electroluminescent element tends to increase.

<Light emitting layer>
In the electroluminescent device of the present invention, when the light emitting layer contains a polymer compound material, the polymer compound material includes a polyfluorene derivative, a polyparaphenylene vinylene derivative, a polyphenylene derivative, a polyparaphenylene derivative, a polythiophene derivative, and a polydialkyl. Conjugated polymer compounds such as fluorene, polyfluorene benzothiadiazole and polyalkylthiophene are preferred.

  In addition, the light emitting layer containing these polymer compound materials includes polymer dye compounds such as perylene dyes, coumarin dyes, rhodamine dyes, rubrene, perylene, 9,10-diphenylanthracene, tetraphenylbutadiene, and Nile. Low molecular dye compounds such as red, coumarin 6 and quinacridone may be contained. In addition, naphthalene derivatives, anthracene and derivatives thereof, perylene and derivatives thereof, polymethine, xanthene, coumarin, and cyanine dyes, metal complexes of 8-hydroxyquinoline and derivatives thereof, aromatic amines, tetraphenylcyclopentadiene And a derivative thereof, or a metal complex that emits phosphorescence, such as tetraphenylbutadiene and a derivative thereof, tris (2-phenylpyridine) iridium, and the like.

  The light emitting layer constituting the electroluminescent element of the present invention may be composed of a composition containing a light emitting organic compound such as the organic dye or the metal complex and a non-conjugated polymer compound. Examples of such non-conjugated polymer compounds include polyethylene, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, Examples include ketone resins, phenoxy resins, polyamides, ethyl cellulose, vinyl acetate, ABS resins, polyurethanes, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, and silicon resins.

  The non-conjugated polymer compound is a carbazole derivative, triazole derivative, oxazole derivative, oxadiazole derivative, imidazole derivative, polyarylalkane derivative, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, arylamine derivative, amino-substituted in the side chain. One selected from the group consisting of chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, and organosilane derivatives It may have a structure derived from the above derivatives or compounds.

  On the other hand, when the light emitting layer contains a low molecular weight compound material, examples of the low molecular weight compound material include low molecular weight compounds such as rubrene, perylene, 9,10-diphenylanthracene, tetraphenylbutadiene, nile red, coumarin 6, carbazole, and quinacridone. Dye compounds, naphthalene derivatives, anthracene and derivatives thereof, perylene and derivatives thereof, polymethine, xanthene, coumarin, cyanine, indigo and other dyes, metal complexes of 8-hydroxyquinoline and derivatives thereof, phthalocyanine and derivatives thereof Metal complexes, aromatic amines, tetraphenylcyclopentadiene and derivatives thereof, tetraphenylbutadiene and derivatives thereof, and the like.

  When the light-emitting layer includes a metal complex that emits phosphorescence, such metal complexes include tris (2-phenylpyridine) iridium, thienylpyridine ligand-containing iridium complex, phenylquinoline ligand-containing iridium complex, triaza Examples thereof include a cyclononane skeleton-containing terbium complex.

  Examples of the polymer compound material used in the light emitting layer include International Publication No. 97/09394, International Publication No. 98/27136, International Publication No. 99/54385, International Publication No. 00/22027, and International Publication. No. 01/19834, British Patent Application No. 2340304, British Patent No. 2348316, US Pat. No. 5,736,636, US Pat. No. 5,741,921, US Pat. No. 5,777,070, European Japanese Patent No. 0707020, Japanese Patent Application Laid-Open No. 9-111233, Japanese Patent Application Laid-Open No. 10-324870, Japanese Patent Application Laid-Open No. 2000-80167, Japanese Patent Application Laid-Open No. 2001-123156, Japanese Patent Application Laid-Open No. 2004-168999, Japanese Patent Application Laid-Open No. 2007. -162009, “Yes Polyfluorenes, derivatives and copolymers thereof, polyarylenes, derivatives and copolymers thereof, polyarylene vinylenes, derivatives thereof, and the like disclosed in “EL Element Development and Constituent Materials” (CMC Publishing, 2006) Examples thereof include (co) polymers of copolymers, aromatic amines and derivatives thereof.

  Further, as low molecular compound materials, JP-A-57-51781, “Organic thin film work function data collection [2nd edition]” (CMC Publishing, 2006), “Development of organic EL elements and constituent materials” (SMC Publishing Co., Ltd., published in 2006) and the like.

  The material may be used as a single component or as a composition comprising a plurality of components. In addition, the light emitting layer may have a single layer structure composed of one or more of the materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

  Examples of the method for forming the light emitting layer include the same methods as those for forming the other hole injection layer. Film formation methods from solution include spin coating, casting, bar coating, slit coating, spray coating, nozzle coating, and other coating methods, gravure printing, screen printing, flexographic printing, and inkjet printing. Examples of the printing method include a vacuum deposition method and a transfer method. Examples of the solvent used for film formation from a solution include the solvents exemplified above for the other hole injection layer film formation method.

  When an organic layer such as an electron transport layer is formed by a coating method following the light emitting layer, if the lower layer is dissolved in a solvent contained in a solution of a layer to be applied later, a method for forming a hole injection layer It is preferable that the lower layer is insolubilized with respect to the solvent by the same method as that exemplified in.

  The thickness of the light emitting layer needs to be such that pinholes do not occur. However, since the optimum value differs depending on the material used, it is preferable to select the driving voltage and the light emitting efficiency to be appropriate values. . Such a film thickness is preferably 5 nm to 1 μm, more preferably 10 nm to 500 nm, and further preferably 30 nm to 200 nm. When the film thickness of the light emitting layer is less than the lower limit, pinholes tend to occur, and when the film thickness exceeds the upper limit, the driving voltage of the electroluminescent element tends to increase.

<Electron transport layer and hole blocking layer>
As materials for forming the electron transport layer and the hole blocking layer constituting the electroluminescent device of the present invention, known materials can be used, and triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, benzoquinone and Its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, anthraquinodimethane derivatives, anthrone derivatives, thiopyran dioxide derivatives , Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives Various metal complexes represented by metal complexes of 8-quinolinol derivatives, metal phthalocyanines, metal complexes having benzoxazole and benzothiazole as ligands, organosilane derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its Derivatives, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, and the like. Among these, triazole derivatives, oxadiazole derivatives, benzoquinone and its derivatives, anthraquinone and its derivatives, or metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives Is preferred.

  The material may be used as a single component or as a composition comprising a plurality of components. Further, the electron transport layer and the hole blocking layer may have a single layer structure composed of one or more of the materials, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. Also good. Moreover, the material illustrated as a material which can be used with the other electron injection layer mentioned later can also be used with an electron carrying layer and a hole block layer.

  Examples of the method for forming the electron transport layer and the hole blocking layer include the same methods as those for forming the other hole injection layers. Film formation methods from solution include spin coating, casting, bar coating, slit coating, spray coating, nozzle coating, and other coating methods, gravure printing, screen printing, flexographic printing, and inkjet printing. Examples of the printing method include a vacuum deposition method and a transfer method. Examples of the solvent used for film formation from a solution include the solvents exemplified above for the other hole injection layer film formation method.

  When an organic layer such as an electron injection layer is formed by a coating method following the electron transport layer and the hole blocking layer, if the lower layer dissolves in the solvent contained in the solution of the layer to be applied later, It is preferable to insolubilize the lower layer in the solvent by the same method as exemplified in the method for forming the injection layer.

  The film thickness of the electron transport layer and the hole blocking layer must be such that pinholes do not occur, but the optimum values differ depending on the materials used, so that the drive voltage and light emission efficiency are appropriate. It is preferable to select. Such a film thickness is preferably 1 nm to 1 μm, more preferably 2 nm to 500 nm, and still more preferably 5 nm to 100 nm. When the film thickness of the electron transport layer and the hole blocking layer is less than the lower limit, pinholes tend to be generated. On the other hand, when the film thickness exceeds the upper limit, the driving voltage of the electroluminescent element tends to increase.

<Electron injection layer>
Among the electron injection layers constituting the electroluminescent device of the present invention, known materials can be used as the material for forming the electron injection layer not containing the polymer compound according to the present invention, that is, other electron injection layers. , Triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and Its derivatives, diphenoquinone derivatives, anthraquinodimethane derivatives, anthrone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthalene , Aromatic metal tetracarboxylic anhydrides such as perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, metal complexes represented by benzoxazole and benzothiazole ligands, organosilane derivatives Etc.

  The material may be used as a single component or as a composition comprising a plurality of components. In addition, the other electron injection layer may have a single layer structure composed of one or more of the materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. In addition, materials exemplified as materials that can be used in the electron transport layer and the hole blocking layer can also be used in the other electron injection layers.

  Examples of the method for forming the other electron injection layer include the same method as the method for forming the other hole injection layer. Film formation methods from solution include spin coating, casting, bar coating, slit coating, spray coating, nozzle coating, and other coating methods, gravure printing, screen printing, flexographic printing, and inkjet printing. Examples of the printing method include a vacuum deposition method and a transfer method. Examples of the solvent used for film formation from a solution include the solvents exemplified above for the other hole injection layer film formation method.

  The film thickness of the other electron injection layer must be such that pinholes do not occur, but the optimum value differs depending on the material used, so the drive voltage and light emission efficiency are selected to be appropriate values. It is preferable to do. Such a film thickness is preferably 1 nm to 1 μm, more preferably 2 nm to 500 nm, and still more preferably 5 nm to 100 nm. When the film thickness of the other electron injection layer is less than the lower limit, pinholes tend to be generated. On the other hand, when the film thickness exceeds the upper limit, the driving voltage of the electroluminescent element tends to increase.

<Cathode>
In the electroluminescent device of the present invention, the cathode has a function of supplying electrons to these layers adjacent to the light emitting layer, the electron transport layer, the hole blocking layer, the electron injection layer, and the like. The cathode may have a single layer structure made of a single material or a plurality of materials, or may have a multilayer structure made of a plurality of layers. In the case of a multilayer structure, a two-layer structure of a first cathode layer and a cover cathode layer or a three-layer structure of a first cathode layer, a second cathode layer and a cover cathode layer is preferable. Here, the first cathode layer refers to the layer closest to the light emitting layer in the cathode, and the cover cathode layer is the first cathode layer in the case of a two-layer structure, and the first cathode layer in the case of a three-layer structure. A layer covering the second cathode layer.

  Among the cathodes, the material of the first cathode layer preferably has a work function of 3.5 eV or less from the viewpoint of electron supply capability. As the material for the first cathode layer, metal oxides, fluorides, carbonates, composite oxides, and the like having a work function of 3.5 eV or less are preferably used. As the material for the cover cathode layer, a metal, metal oxide, or the like having a low resistivity and high corrosion resistance to moisture is preferably used.

  Examples of the material for the first cathode layer include alkali metals and alkaline earth metals, alloys containing one or more of the metals, oxides of the metals, halides, carbonates, composite oxides, and mixtures thereof. . Examples of the alkali metal or its oxide, halide, carbonate and composite oxide include lithium, sodium, potassium, rubidium, cesium, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium fluoride, fluorine. Examples thereof include sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, potassium molybdate, potassium titanate, potassium tungstate, and cesium molybdate. Examples of the alkaline earth metal or its oxide, halide, carbonate and composite oxide include magnesium, calcium, strontium, barium, magnesium oxide, calcium oxide, strontium oxide, barium oxide, magnesium fluoride, calcium fluoride, Examples include strontium fluoride, barium fluoride, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, barium molybdate, and barium tungstate. Examples of the alloy containing at least one alkali metal or alkaline earth metal include Li—Al alloy, Mg—Ag alloy, Al—Ba alloy, Mg—Ba alloy, Ba—Ag alloy, and Ca—Bi—Pb—Sn. An alloy etc. are mentioned. Moreover, the composition containing the material illustrated as a material of a 1st cathode layer and the material illustrated as a material which comprises an electron injection layer can also be used for a 1st cathode layer. Examples of the material for the second cathode layer include the same materials as the material for the first cathode layer.

  Cover cathode layer materials include low resistance metals such as gold, silver, copper, aluminum, chromium, tin, lead, nickel, titanium and alloys containing these metals, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO) And conductive metal oxides such as indium zinc oxide (IZO) and molybdenum oxide, and a mixture of these conductive metal oxides and metals.

Examples of when the cathode is a multilayer structure, Mg / Al, Ca / Al , Ba / Al, NaF / Al, KF / Al, RbF / Al, CsF / Al, Na 2 CO 3 / Al, K 2 CO ₃ / Al, Cs ₂ CO ₃ / Al, etc., the first cathode layer / cover cathode layer two-layer structure, LiF / Ca / Al, NaF / Ca / Al, KF / Ca / Al, RbF / Ca / Al, CsF / Ca / Al, Ba / Al / Ag, KF / Al / Ag, KF / Ca / Ag, K ₂ CO ₃ / Ca / Ag, etc., three-layer structure of first cathode layer / second cathode layer / cover cathode layer (Here, the symbol “/” indicates that the layers are adjacent to each other). The material of the second cathode layer preferably has a reducing action on the material of the first cathode layer. Here, the presence / absence / degree of the reducing action between materials can be estimated from, for example, bond dissociation energy (ΔrH °) between compounds. That is, in a reduction reaction of the material constituting the second cathode layer to the material constituting the first cathode layer, when the combination is such that the bond dissociation energy is positive, the material of the second cathode layer is the first cathode layer It can be said that this material has a reducing action. The bond dissociation energy can be referred to, for example, in “Electrochemical Handbook 5th Edition” (Maruzen, published in 2000), “Thermodynamic Database MALT” (Science and Technology, published in 1992), and the like.

  Various known methods can be used for producing the cathode, and examples thereof include vacuum deposition, sputtering, and ion plating. When using metals, metal oxides, fluorides, and carbonates, vacuum evaporation is often used, and high-boiling metal oxides, metal composite oxides, and conductive metal oxides such as indium tin oxide (ITO) are used. In this case, sputtering and ion plating are frequently used. In the case of forming a composition with a different material, a co-evaporation method, a sputtering method, an ion plating method, or the like is used. In particular, a co-evaporation method is suitable for forming a film containing a low molecular organic substance and a metal or metal oxide, fluoride, or carbonate.

  The film thickness of the cathode varies depending on the material used and the layer structure, and may be selected so that the driving voltage, the light emission efficiency, and the element lifetime are appropriate. Usually, the film thickness of the first cathode layer is 0.5 nm to 20 nm, and the film thickness of the cover cathode layer is 10 nm to 1 μm. When Ba or Ca is used for the first cathode layer and Al is used for the cover cathode layer, the film thickness of Ba or Ca is preferably 2 nm to 10 nm, and the film thickness of Al is preferably 10 nm to 500 nm. When Al is used for KF and the cover cathode layer, the film thickness of NaF or KF is preferably 1 nm to 8 nm, and the film thickness of Al is preferably 10 nm to 500 nm.

  When the cathode is used as the light transmissive electrode in the electroluminescent element of the present invention, the visible light transmittance of the cover cathode layer is preferably 40% or more, and preferably 50% or more. This visible light transmittance is obtained by using a transparent conductive metal oxide such as indium tin oxide (ITO), indium zinc oxide (IZO), and molybdenum oxide as a cover cathode layer material, or gold, silver, copper, aluminum, This can be achieved by setting the film thickness of the cover cathode layer using a low-resistance metal such as chromium, tin, or lead and an alloy containing these metals to 30 nm or less. In the case of a cathode structure in which 5 nm of Ba is laminated on the first cathode layer, 1 nm of Al is laminated on the second cathode layer, and 15 nm of Ag is laminated on the cover cathode layer, the visible light transmittance of the cathode is 50%.

Further, in order to improve the light transmittance from the cathode side, an antireflection layer may be provided on the cover cathode layer of the cathode. Examples of the material used for the antireflection layer, the refractive index is preferably the material is 1.8 to 3.0, ZnS, ZnSe, etc. WO ₃ and the like. The film thickness of the antireflection layer varies depending on the combination of materials, but is usually 10 nm to 150 nm. When 5 nm of Ba is laminated as the first cathode layer, 1 nm of Al is laminated as the second cathode layer, and 15 nm of Ag is laminated as the cover cathode layer, 21 nm of WO ₃ is laminated as the antireflection layer in contact with the cover cathode layer. The light transmittance from the side is improved by about 10%.

<Insulating layer>
The electroluminescent element of the present invention may include an insulating layer. The thickness of the insulating layer is 5 nm or less, and such an insulating layer has functions such as improving adhesion with the electrode, improving charge injection from the electrode (ie, holes or electrons), and preventing mixing with adjacent layers. Is. Examples of the material for the insulating layer include metal fluorides, metal oxides, organic insulating materials (such as polymethyl methacrylate), and the like. As an electroluminescent element provided with an insulating layer having a thickness of 5 nm or less, an element having an insulating layer having a thickness of 5 nm or less adjacent to the cathode and an insulating layer having a thickness of 5 nm or less adjacent to the anode are provided. Can be mentioned.

  The electroluminescent element of the present invention can be produced, for example, by sequentially laminating each layer on a substrate. Specifically, an anode is formed on a substrate, a hole injection layer is formed thereon, a layer such as a hole transport layer or an interlayer is formed thereon as necessary, and a light emitting layer is formed thereon. Can be manufactured by forming a layer such as an electron transport layer and a hole blocking layer thereon, forming an electron injection layer thereon, and further forming a cathode thereon. it can.

  In addition, by using the electroluminescent element of the present invention, a display device with high luminance can be manufactured. This display device is provided with the electroluminescent element of the present invention as a pixel unit. The arrangement form of the pixel unit can be an arrangement usually adopted in a display device such as a television, and can be an arrangement in which a large number of pixels are arranged on a common substrate. In such a display device, the pixels arranged on the substrate can be formed in a pixel region defined by the bank.

  The display device may include a sealing member on the side opposite to the substrate with the light emitting layer or the like interposed therebetween. In addition, any member for constituting the display device such as a filter such as a color filter or a fluorescence conversion filter, a circuit and a wiring necessary for driving the pixel, and the like can be provided.

<Photoelectric conversion element>
Next, the case where the electronic device of the present invention is a photoelectric conversion device (hereinafter referred to as “the photoelectric conversion device of the present invention”) will be described. The photoelectric conversion element of the present invention includes a cathode, an anode, a charge separation layer disposed between the cathode and the anode, and between the cathode and the charge separation layer or between the anode and the charge separation layer. And a charge injection layer containing the polymer compound according to the present invention disposed between the two.

  The charge separation layer of the photoelectric conversion element of the present invention contains an electron donating compound and an electron accepting compound. Examples of the electron donating compound include a conjugated polymer compound, and a polymer compound containing a thiophenediyl group, a polymer compound containing a fluorenediyl group, and the like are preferable. Examples of the electron accepting compound include fullerene and fullerene derivatives.

  The photoelectric conversion element of the present invention is usually formed on a support substrate. Such a support substrate may be any substrate that does not impair the characteristics of the organic photoelectric conversion element, and a glass substrate, a flexible film substrate, or a plastic substrate can be used.

  The photoelectric conversion element of the present invention can be produced by a known method, for example, Synth. Met. , 102, 982 (1999) and Science, 270, 1789 (1995).

  Hereinafter, the present invention will be described based on examples and comparative examples. The structural analysis and molecular weight measurement of the polymer were carried out by the following methods.

<Structural analysis of polymer>
The polymer was dissolved in deuterated methanol to a concentration of 20 mg / mL, and an NMR spectrometer (Example 1: “EX-270” manufactured by JEOL Ltd., Preparation Example 1: “300 MHz NMR” manufactured by Varian Inc. ¹ H-NMR measurement was performed using a spectrometer ”).

<Measurement of molecular weight of polymer>
In Example 1, the calculating the integral ratio from the NMR chart obtained in ^{the 1 H-NMR} measurement, molecular weight was determined from the obtained integral ratio polymer. In Preparation Example 1, tetrahydrofuran was added to a solution containing the polymer so that the concentration of the polymer was about 0.5% by mass to dissolve the polymer, and gel permeation chromatography (GPC) (Tosoh Corporation) The number average molecular weight and weight average molecular weight in terms of standard polystyrene were determined using “HLC-8220GPC” manufactured by HLC-8220 GPC, column: TSKgel SuperMultipore HZ-M, TSKgel guard column super MPHZ-M). The sample injection volume in GPC was 50 μl, and tetrahydrofuran (flow rate: 0.5 ml / min) was used as the mobile phase of GPC.

Example 1
Synthesis of polyviologen (polymer compound 1) Diethylene glycol (3.4 g, 32 mmol) and triethylamine (1.62 g, 16 mmol) were placed in a 100 mL eggplant flask, dissolved in dichloromethane (40 ml), and then p-toluenesulfonyl chloride ( 1.53 g, 8 mmol) in dichloromethane (20 ml) was added dropwise to the eggplant flask. After stirring the obtained solution at room temperature for 20 hours, the reaction solution was subjected to liquid separation extraction with a 1 mol / L potassium hydrogen sulfate aqueous solution and a 5 mass% sodium hydrogen carbonate aqueous solution, and the organic layer was dried over sodium sulfate. The resulting solution was concentrated under reduced pressure, purified by silica gel column chromatography (using a mixed solution of ethyl acetate: hexane = 9: 1 as an eluent), and the column treatment liquid was concentrated under reduced pressure to obtain a clear oil (1 .31 g) was obtained.

  Next, this oil (1.31 g), anthralphine (0.41 g, 1.7 mmol) and triphenylphosphine (1.31 g, 5.0 mmol) were put into a 50 mL Schlenk flask, and the inside of the flask was replaced with argon. And cooled to 0 ° C. After adding tetrahydrofuran (10 ml) to the Schlenk flask, a toluene solution of diethyl azodicarboxylate (2.2 mol / l, 2.3 ml) diluted with 5 ml of tetrahydrofuran was added dropwise and stirred for 1 day. The reaction solution was concentrated, dichloromethane was added, and the mixture was extracted with water. After extracting the organic layer, the extract is concentrated under reduced pressure and purified by silica gel column chromatography (using a mixture of ethyl acetate: hexane = 5: 1 as the eluent), and the column treatment solution is concentrated under reduced pressure to give a yellow powder. (0.53 g) was obtained.

Next, this yellow powder (0.53 g, 0.7 mmol) and 4,4′-bipyridyl (0.11 g, 0.7 mmol) were placed in a 20 mL eggplant flask, and the inside of the flask was replaced with argon. N, N′-dimethylformamide (5 ml) was added to the eggplant flask and stirred at 80 ° C. for 5 days. After the reaction solution was concentrated, the concentrated solution was added to ethyl acetate. The resulting precipitate was collected by filtration and dried under reduced pressure to obtain polymer compound 1 (426 mg). The obtained polymer compound 1 was identified by ¹ H-NMR measurement, and the following formula (P1):

It was confirmed to have a repeating unit represented by The results are shown below.
¹ H-NMR (270 MHz, solvent: deuterated methanol): 2.34, 2.66, 2.69, 2.89, 3.33, 3.36, 3.76, 3.78, 3.9-4 0.0 (br), 4.1-4.4 (br), 4.78, 7.18, 7.21, 7.32, 7.35, 7.38-7.42 (br), 7. 68, 7.71, 7.75 to 7.82 (br), 7.88, 7.90, 8.2 to 8.3 (br), 8.3 to 8.5 (br), 8.99 9.02, 9.08 to 9.13 (br), 9.17 to 9.26 (br)

  Moreover, it was 1643 when the molecular weight of the high molecular compound 1 was computed from the obtained NMR chart.

(Preparation Example 1)
Synthesis of polyurethane sodium salt (polymer compound 2) 1,3-butanediol (1.0 g), dibutyltin dilaurate (7.5 mg) and dimethylolpropionic acid (0.5 g) were placed in a 100 mL flask, and dimethylformamide ( 50 mL) was added and stirred at 90 ° C. for 30 minutes. Isophorone diisocyanate (3.3 g) was added to the resulting solution and heated at 90 ° C. for 3 hours. At this stage, the obtained polymer-containing solution was subjected to GPC measurement according to the method described above, and the molecular weight of the polymer was calculated. The number average molecular weight was 1900 and the weight average molecular weight was 3000. Thereafter, the temperature was lowered to 60 ° C., and a 1 mol / L sodium hydroxide aqueous solution was added for neutralization. After further stirring at 60 ° C. for 1 hour, the solvent was distilled off to obtain a white solid polyurethane sodium salt (2.0 g) (hereinafter referred to as “polymer compound 2”). The obtained polymer compound 2 was identified by ¹ H-NMR measurement, and the following formula (P2):

で表される繰り返し単位を有することを確認した。その結果を以下に示す。
^１Ｈ−ＮＭＲ（３００ＭＨｚ、溶媒：重メタノール）：０．９４、０．９９、１．０４、１．０７、１．１３、１．１８、１．２０、１．２３、１．２５、１．５〜１．７（ｂｒ）、１．７〜１．８（ｂｒ）、１．８４、２．８４、２．８６、２．８８、２．９１、３．６〜３．８（ｂｒ）、３．８〜３．９（ｂｒ）、４．０〜４．２（ｂｒ）、７．９８、８．５５

It was confirmed to have a repeating unit represented by The results are shown below.
¹ H-NMR (300MHz, solvent: methanol): 0.94,0.99,1.04,1.07,1.13,1.18,1.20,1.23,1.25,1 .5 to 1.7 (br), 1.7 to 1.8 (br), 1.84, 2.84, 2.86, 2.88, 2.91, 3.6 to 3.8 (br ), 3.8-3.9 (br), 4.0-4.2 (br), 7.98, 8.55

(Example 2)
Fabrication of electroluminescent device Poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid solution (Stark Vitec Co., Ltd.) as the hole injection material solution on the ITO anode of the glass substrate on which ITO was formed and patterned as the anode ) “Baytron”) was applied by spin coating so as to have a film thickness of 60 nm to form a coating film. The substrate on which the coating film was formed was heated in air at 200 ° C. for 10 minutes to insolubilize the coating film. Thereafter, the substrate was naturally cooled to room temperature to form a hole injection layer on the ITO anode.

  Next, a polymer containing a divalent aromatic amine residue and a crosslinking group as a repeating unit, which is a hole transporting polymer material (a polymer synthesized according to Examples 1 and 2 of WO 2005/052027 pamphlet). The combination (P1)) and xylene were mixed to obtain a hole transport layer forming composition containing 0.7% by mass of the hole transporting polymer material.

  On the hole injection layer of the substrate on which the hole injection layer was formed, this composition for forming a hole transport layer was applied by spin coating to form a coating film having a thickness of 20 nm. The substrate on which this coating film was formed was heated at 190 ° C. for 20 minutes in an inert (nitrogen) gas atmosphere to insolubilize the coating film. Thereafter, the substrate was naturally cooled to room temperature to form a hole transport layer on the hole injection layer.

  Next, a light emitting polymer material (“BP361” manufactured by Summation Co., Ltd.) and xylene were mixed to obtain a composition for forming a light emitting layer containing 1.4% by mass of the light emitting polymer material.

  On the hole transport layer of the substrate on which the hole transport layer had been formed, this light emitting layer forming composition was applied by spin coating to form a coating film having a thickness of 80 nm. The substrate on which this coating film was formed was heated at 130 ° C. for 20 minutes in an inert (nitrogen) gas atmosphere to evaporate the solvent, and then the substrate was naturally cooled to room temperature to form a light emitting layer on the hole transport layer. did.

  Next, the polymer compound 1 as a charge injection material and methanol were mixed to obtain a composition for forming a charge injection layer containing 0.2% by mass of the polymer compound 1.

  On the light emitting layer of the substrate on which the light emitting layer was formed, this charge injection layer forming composition was applied by spin coating to form a coating film having a thickness of 10 nm. The substrate on which this coating film was formed was heated at 100 ° C. for 10 minutes in an inert (nitrogen) gas atmosphere to evaporate the solvent, and then the substrate was naturally cooled to room temperature to contain the polymer compound 1 on the light emitting layer. A charge injection layer was formed.

  The substrate on which the charge injection layer containing the polymer compound 1 is formed is placed in a vacuum apparatus, an aluminum film having a thickness of 80 nm is formed by a vacuum deposition method, and a cathode is formed on the charge injection layer. 1 was obtained.

  The obtained electroluminescent element 1 was taken out from the vacuum apparatus and sealed with sealing glass and a two-component mixed epoxy resin in an inert (nitrogen) gas atmosphere to obtain the light emitting apparatus 1.

(Comparative Example 1)
An electroluminescent element 2 was produced in the same manner as in Example 2 except that the polymer compound 2 was used instead of the polymer compound 1, and this was sealed to obtain a light emitting device 2.

(Comparative Example 2)
An electroluminescent element 3 was produced in the same manner as in Example 2 except that the charge injection layer containing the polymer compound 1 was not formed, and this was sealed to obtain a light emitting device 3.

(Comparative Example 3)
The same procedure as in Example 2 was conducted except that 1,1′-di-n-octyl-4,4′-bipyridinium dibromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the low molecular compound 1 instead of the polymer compound 1. Thus, an electroluminescent element 4 was produced and sealed to obtain a light emitting device 4.

<Performance evaluation>
A forward voltage of 10 V was applied to each of the light emitting devices 1 to 4 obtained in Example 2 and Comparative Examples 1 to 3, and the light emission luminance and the light emission efficiency were measured. The results are shown in Table 1.

  As is clear from the results shown in Table 1, an electronic device (electroluminescent device) (Example 2) provided with a layer containing the polymer compound according to the present invention is an electron provided with a layer containing a conventional polymer compound. Compared with the device (Comparative Example 1) and the electronic device (Comparative Example 2) in which the layer containing the polymer compound according to the present invention was not formed, both the light emission luminance and the light emission efficiency were remarkably excellent. Thus, since the electronic device of this invention was excellent in luminous efficiency, it was confirmed that it is excellent in conversion efficiency.

  As described above, according to the present invention, a polymer compound excellent in charge injection property can be obtained, and an electronic device excellent in conversion efficiency can be obtained.

  Therefore, since the electroluminescent element which is the electronic element of the present invention has high emission luminance and excellent luminous efficiency, various light sources such as a planar light source, various display devices such as a segment display device and a dot matrix display device, and a liquid crystal display It is useful as a backlight for devices and various illuminations.

  Moreover, since the photoelectric conversion element which is an electronic element of this invention is excellent in photoelectric conversion efficiency, it is useful as a solar cell etc.

Claims (7)

A first electrode; a second electrode; a light-emitting layer or charge separation layer disposed between the first electrode and the second electrode; the light-emitting layer or charge separation layer; and the first electrode Or the second electrode, and the following formula (I):

(In the formula (I), X ¹ and X ² are each independently F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^a SO ₃ ⁻ , R ^a COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , One selected from the group consisting of ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ , BR ^a ₄ ⁻ and PF ₆ ⁻ R ^a represents one group selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 50 carbon atoms, and a monovalent heterocyclic group having 2 to 50 carbon atoms. And the alkyl group, aryl group and monovalent heterocyclic group may have a substituent, and * represents a bonding site with another structure.)
And an electric charge injection layer containing a polymer compound having a structure represented by:   The polymer compound has a divalent aromatic group which may have a substituent, an alkylene group which may have a substituent, an oxyalkylene group which may have a substituent, and a substituent. The electronic device according to claim 1, wherein the electronic device further comprises at least one group selected from the group consisting of dioxyalkylene groups which may be present. The polymer compound has the following formula (II):

(In the formula (II), X ³ and X ⁴ each independently represent F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^b SO ₃ ⁻ , R ^b COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , One selected from the group consisting of ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ , BR ^b ₄ ⁻ and PF ₆ ^{− Rb} represents one group selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 50 carbon atoms, and a monovalent heterocyclic group having 2 to 50 carbon atoms. The alkyl group, aryl group and monovalent heterocyclic group each may have a substituent, Ar ¹ represents a divalent aromatic group which may have a substituent, R ¹ and R ² each independently represents an alkylene group having 1 to 20 carbon atoms, * represents other And n ¹ and n ² are each independently an integer of 1 to 20.)
The electronic device according to claim 2, wherein the electronic device is a compound having a structure represented by: Electronic device according to any one of claims 1 to 3, wherein the molecular weight of the polymer compound is 1 × 10 ⁸ or less 1 × 10 ³ or more.   An electroluminescent device comprising the electronic device according to claim 1, wherein a light emitting layer is disposed between the first electrode and the second electrode. .   A photoelectric conversion comprising the electronic device according to any one of claims 1 to 3, wherein a charge separation layer is disposed between the first electrode and the second electrode. element. Formula (II) below:

(In the formula (II), X ³ and X ⁴ each independently represent F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OH ⁻ , R ^b SO ₃ ⁻ , R ^b COO ⁻ , ClO ⁻ , ClO ₂ ⁻ , One selected from the group consisting of ClO ₃ ⁻ , ClO ₄ ⁻ , SCN ⁻ , CN ⁻ , NO ₃ ⁻ , HSO ₄ ⁻ , H ₂ PO ₄ ⁻ , BF ₄ ⁻ , BR ^b ₄ ⁻ and PF ₆ ⁻ represents an ion, the R ^b is one group selected from the group consisting of an alkyl group, a monovalent heterocyclic group of aryl and 2 to 50 carbon atoms having 6 to 50 carbon atoms having 1 to 30 carbon atoms The alkyl group, aryl group and monovalent heterocyclic group each may have a substituent, Ar ¹ represents a divalent aromatic group which may have a substituent, R ¹ and R ² each independently represents an alkylene group having 1 to 20 carbon atoms, * represents other And n ¹ and n ² are each independently an integer of 1 to 20.)
A polymer compound having a structure represented by: