JP5703680B2 - Organic electroluminescence device - Google Patents

Description

  The present invention relates to an organic electroluminescence element.

  In recent years, organic electroluminescence devices having a hole transport layer using a polymer compound have been developed. Examples of the organic electroluminescence element include an organic electroluminescence element having a hole transport layer composed of a polymer compound having a substituted triphenylamine residue as a repeating unit and a polymer compound having a fluorenediyl group as a repeating unit. An organic electroluminescence device having a hole transport layer is known (Patent Documents 1 and 2).

JP-A-10-92582 International Publication No. 2005/49548 Pamphlet

  However, these organic electroluminescence elements have a problem that when driven at a constant current value, the driving voltage rises when the luminance is halved.

  Accordingly, an object of the present invention is to provide an organic electroluminescence device that suppresses an increase in driving voltage when the luminance is reduced by half when driven at a constant current value.

The present invention is an organic electroluminescence device comprising an anode and a cathode, and a hole transport layer and a light emitting layer provided between the anode and the cathode,
The hole transport layer is
1) A mixture of a 2,2′-bipyridine and / or a 2,2′-bipyridine derivative and a 2,2′-bipyridinediyl group-free hole transporting polymer compound,
2) Selected from the group consisting of a structural unit composed of an unsubstituted or substituted 2,2′-bipyridinediyl group, a structural unit composed of a divalent aromatic amine residue, and a structural unit composed of an unsubstituted or substituted arylene group. 2,2′-bipyridinediyl group-containing polymer compound having at least one kind of structural unit,
Or a combination of these [ie, a combination of 1) and 2)]
The organic electroluminescent element containing this is provided.

  The organic electroluminescent element of the present invention is an organic electroluminescent element in which an increase in driving voltage is suppressed when the luminance is reduced by half when driven at a constant current value.

  First, terms commonly used in this specification will be described. In this specification, unless otherwise specified, it is as described below.

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

  The alkyl group may be linear or branched, and may be a cycloalkyl group. The alkyl group may have a substituent. When the alkyl group has a substituent, the number of substituents may be one or plural, and when there are a plurality of substituents, they may be the same or different. Carbon number of the alkyl group except a substituent is 1-20 normally.

  Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2- Examples include ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, and dodecyl group.

  As the substituent that the alkyl group may have, an alkoxy group, an aryl group, an aryloxy group, and a cyano group are preferable from the viewpoint of light emitting characteristics of the device.

  The alkenyl group may be linear or branched, and may be a cycloalkenyl group. The alkenyl group may have a substituent. When the alkenyl group has a substituent, the number of substituents may be one or more, and when there are a plurality of substituents, they may be the same or different. The carbon number of the alkenyl group excluding the substituent is usually 2-20.

  Examples of the alkenyl group include vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4- Pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-heptenyl group, 2-heptenyl group, 3-heptenyl group, 4- Heptenyl group, 5-heptenyl group, 6-heptenyl group, 1-octenyl group, 2-octenyl group, 3-octenyl group, 4-octenyl group, 5-octenyl group, 6-octenyl group, 7-octenyl group, 1- Examples include a cyclohexenyl group, a 2-cyclohexenyl group, and a 3-cyclohexenyl group. The alkenyl group also includes alkadienyl groups such as 1,3-butadienyl group.

  As the substituent that the alkenyl group may have, an alkoxy group, an aryl group, an aryloxy group, and a cyano group are preferable from the viewpoint of light emitting characteristics of the device.

  The alkynyl group may be linear or branched, and may be a cycloalkynyl group. The alkynyl group may have a substituent. When the alkynyl group has a substituent, there may be one or a plurality of substituents, and when there are a plurality of substituents, they may be the same or different. The carbon number of the alkynyl group excluding the substituent is usually 2-20.

  Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4- Pentynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, 1-heptynyl group, 2-heptynyl group, 3-heptynyl group, 4-heptynyl group, 5- Heptynyl group, 6-heptynyl group, 1-octynyl group, 2-octynyl group, 3-octynyl group, 4-octynyl group, 5-octynyl group, 6-octynyl group, 7-octynyl group, 2-cyclohexynyl group, 3 -A cyclohexylinyl group and a cyclohexylethynyl group are illustrated. The alkynyl group also includes a group having both a double bond and a triple bond such as an alkidienyl group such as a 1,3-butadiynyl group and a 2-pentene-4-ynyl group.

  As the substituent that the alkynyl group may have, an alkoxy group, an aryl group, an aryloxy group, and a cyano group are preferable from the viewpoint of light emitting characteristics of the device.

  The alkoxy group may be linear or branched, and may be a cycloalkyloxy group. The alkoxy group may have a substituent. When the alkoxy group has a substituent, there may be one or a plurality of substituents, and when there are a plurality of substituents, they may be the same or different. Carbon number of the alkoxy group except a substituent is 1-20 normally.

  As the alkoxy group, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group Octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, dodecyloxy group, methoxymethyloxy group, 2-methoxyethyloxy group.

  As the substituent that the alkoxy group may have, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an aryloxy group, and a cyano group are preferable from the viewpoint of light emitting characteristics of the device.

  The alkylthio group may be linear or branched, and may be a cycloalkylthio group. The alkylthio group may have a substituent. When the alkylthio group has a substituent, the number of substituents may be one or plural, and when there are a plurality of substituents, they may be the same or different. Carbon number of the alkylthio group except a substituent is 1-20 normally.

  As the alkylthio group, methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group , 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, dodecylthio group.

  As the substituent that the alkylthio group may have, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an aryloxy group, and a cyano group are preferable from the viewpoint of light emitting characteristics of the device.

  The alkylsilyl group may be linear or branched, and may be a cycloalkylsilyl group. The alkylsilyl group may have a substituent. When the alkylsilyl group has a substituent, there may be one or more substituents, and when there are a plurality of substituents, they may be the same or different. Carbon number of the alkylsilyl group except a substituent is 1-20 normally.

  Examples of the alkylsilyl group include methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, butylsilyl group, isobutylsilyl group, sec-butylsilyl group, tert-butylsilyl group, dibutylsilyl group, tributylsilyl group Group, tert-butyldimethylsilyl group, dimethyloctylsilyl group, cyclohexyldimethylsilyl group, and tricyclohexylsilyl group. The alkylsilyl group also includes silacycloalkane-1-yl groups such as silacyclobutan-1-yl group and 1-methylsilacyclohexane-1-yl group.

  As the substituent that the alkylsilyl group may have, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an aryloxy group, and a cyano group are preferable from the viewpoint of light emitting characteristics of the device.

  An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and two or more of either or both of a group having a condensed ring, an independent benzene ring or a condensed ring are directly or vinylene group, etc. Also included are groups bonded through each other. The aryl group may have a substituent. When the aryl group has a substituent, there may be one or a plurality of substituents, and when there are a plurality of substituents, they may be the same or different. Carbon number of the part except the substituent of the aryl group is 6-60 normally.

  As the aryl group, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 1- Phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-azurenyl group, 2-azurenyl group, 3-azurenyl group, 4-azurenyl group, 5-azurenyl group, 6- Azulenyl group, 7-azurenyl group, 8-azurenyl group, 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 9-fluorenyl group, 1-biphenylenyl group, 2-biphenylenyl group, 2- Perylenyl group, 3-perylenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 7- ( - anthryl) -2-naphthyl groups.

  As the substituent that the aryl group may have, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, and a cyano group are preferable from the viewpoint of light emitting characteristics of the device.

  The aryloxy group is a group represented by —OAr (wherein Ar represents an aryl group, the same shall apply hereinafter). The aryl group is the same as described above. The aryloxy group may have a substituent. When the aryloxy group has a substituent, there may be one or a plurality of substituents, and when there are a plurality of substituents, they may be the same or different. Carbon number of the part except the substituent of the aryl group is 6-60 normally.

  As the aryloxy group, phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthryloxy group, 2-anthryloxy group, 9-anthryloxy group, 1-pyrenyloxy group, 2- Pyrenyloxy group, 4-pyrenyloxy group, 1-phenanthryloxy group, 2-phenanthryloxy group, 3-phenanthryloxy group, 4-phenanthryloxy group, 9-phenanthryloxy group, 1- Azulenyloxy group, 2-azurenyloxy group, 3-azurenyloxy group, 4-azurenyloxy group, 5-azurenyloxy group, 6-azurenyloxy group, 7-azurenyloxy group, 8-azurenyloxy group, 1-fluorenyloxy group, 2-fluorenyloxy group Nyloxy, 3-fluorenyloxy, 4-fluorenyloxy, 9-fluoro Luenyloxy group, 1-biphenylenyloxy group, 2-biphenylenyloxy group, 2-perylenyloxy group, 3-perylenyloxy group, 2-biphenylyloxy group, 3-biphenylyloxy group, 4-biphenylyloxy group, A 7- (2-anthryl) -2-naphthyloxy group is exemplified.

  As the substituent that the aryloxy group may have, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, and a cyano group are preferable from the viewpoint of light emitting characteristics of the device.

Aryl silyl group, a group represented by -SiH ₂ Ar, -SiHAr ₂ or -SiAr _3. When there are a plurality of Ar, they may be the same or different. The arylsilyl group may have a substituent. When the arylsilyl group has a substituent, the number of substituents may be one or plural, and when there are a plurality of substituents, they may be the same or different. Carbon number of the part except the substituent of the aryl silyl group is 6-60 normally.

  The arylsilyl group includes phenylsilyl group, diphenylsilyl group, triphenylsilyl group, 1-naphthylsilyl group, di (1-naphthyl) silyl group, tris (1-naphthyl) silyl group, and di (1-naphthyl) phenyl. Silyl group, 1-anthrylsilyl group, 9-anthrylsilyl group, 1-pyrenylsilyl group, 2-pyrenylsilyl group, 1-fluorenylsilyl group, 1-biphenylenylsilyl group, di (1-biphenylenyl) silyl Group, di (4-biphenylyl) silyl group, 7- (2-anthryl) -2-naphthylsilyl group.

  As the substituent that the arylsilyl group may have, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, and a cyano group are preferable from the viewpoint of light emitting characteristics of the device.

  The organic electroluminescence device of the present invention includes an anode and a cathode, and a hole transport layer and a light emitting layer provided between the anode and the cathode. A hole injection layer may be provided between the anode and the hole transport layer, and an electron transport layer and an electron injection layer may be provided between the light emitting layer and the cathode. In addition, the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer may be independently two or more layers. Hereinafter, the hole injection layer and the electron injection layer are collectively referred to as a “charge injection layer”.

In the organic electroluminescence device of the present invention, when there are two or more hole transport layers, at least one layer is
1) A mixture of a 2,2′-bipyridine and / or a 2,2′-bipyridine derivative and a 2,2′-bipyridinediyl group-free hole transporting polymer compound,
2) Selected from the group consisting of a structural unit composed of an unsubstituted or substituted 2,2′-bipyridinediyl group, a structural unit composed of a divalent aromatic amine residue, and a structural unit composed of an unsubstituted or substituted arylene group. 2,2′-bipyridinediyl group-containing polymer compound having at least one kind of structural unit,
Or what is necessary is just to contain these combination.

  In the organic electroluminescence device of the present invention, the hole transport layer and the light emitting layer are in contact with each other, and a driving hole injection layer is provided between the hole transport layer and the anode. From the viewpoint of voltage and device life, it is preferable.

The light emitting layer means a layer mainly responsible for light emission as an element.
The hole transport layer means a layer mainly having a function of transporting holes and substantially not emitting light. The emission energy emitted from the hole transport layer is preferably 5% or less of the entire emission energy emitted from the organic electroluminescence element.

  The electron transport layer means a layer mainly having a function of transporting electrons and substantially not emitting light. The emission energy emitted from the electron transport layer is preferably 5% or less of the entire emission energy emitted from the organic electroluminescence element.

  These electron transport layer and hole transport layer are collectively referred to as a charge transport layer.

  The charge injection layer means a layer having a function of improving charge injection efficiency from the electrode.

Examples of the structure of the organic electroluminescence device of the present invention include the following structures a) to g).
a) Anode / hole transport layer / light emitting layer / cathode b) Anode / hole transport layer / hole transport layer / light emitting layer / cathode c) Anode / hole transport layer / hole transport layer / hole transport layer / Emissive layer / cathode d) anode / hole transport layer / emission layer / emission layer / cathode e) anode / hole transport layer / hole transport layer / emission layer / emission layer / cathode f) anode / hole transport layer / Light emitting layer / electron transporting layer / cathode g) Anode / hole transporting layer / light emitting layer / electron transporting layer / electron transporting layer / cathode (where / indicates that each layer is laminated adjacently. .)

  The order and number of layers to be stacked, and the thickness of each layer can be used in consideration of light emission efficiency and element lifetime.

  In addition, in order to improve the charge injection property from the electrode, the charge injection layer or the insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode, and the adhesion at the interface is improved or mixing is prevented. For this purpose, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.

  Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials.

  The organic electroluminescence element provided with an insulating layer having a thickness of 2 nm or less includes an organic electroluminescence element provided with an insulating layer having a thickness of 2 nm or less adjacent to the cathode, or an insulating layer having a thickness of 2 nm or less adjacent to the anode. And an organic electroluminescence element provided with the above.

In the organic electroluminescence device of the present invention, from the viewpoint of light emission characteristics,
1) A mixture of a 2,2′-bipyridine and / or a 2,2′-bipyridine derivative and a 2,2′-bipyridinediyl group-free hole transporting polymer (hereinafter also referred to as “Material 1”). ),
2) Selected from the group consisting of a structural unit composed of an unsubstituted or substituted 2,2′-bipyridinediyl group, a structural unit composed of a divalent aromatic amine residue, and a structural unit composed of an unsubstituted or substituted arylene group. 2,2′-bipyridinediyl group-containing polymer compound (hereinafter also referred to as “Material 2”) having at least one kind of structural unit.
Alternatively, the hole transport layer containing a combination of these is preferably adjacent to the light-emitting layer, is present adjacent to the light-emitting layer, and hole injection is performed between the hole transport layer and the anode. More preferably, the layer is present, more preferably adjacent to the light emitting layer and the hole injection layer.

<Hole transport layer>
Next, the hole transport layer will be described.

(Material 1: mixture of 2,2'-bipyridine and / or 2,2'-bipyridine derivative and 2,2'-bipyridinediyl group-free hole transporting polymer compound)
The 2,2′-bipyridinediyl group-free hole transporting polymer compound is preferably a polymer compound represented by the following formula (2).

（２）
〔式（２）中、Ａｍ^2pは２価の芳香族アミン残基を表し、Ａｒ^2pは非置換又は置換のアリーレン基を表す。ｎ^22p及びｎ^23pは、それぞれ独立に、該高分子化合物中のＡｍ^2pで表される２価の芳香族アミン残基とＡｒ^2pで表される非置換又は置換のアリーレン基とのモル比を表す数であるが、ｎ^22p＋ｎ^23p＝１、０．００１≦ｎ^22p≦１、及び、０≦ｎ^23p≦０．９９９を満たす数である。Ａｍ^2pが複数ある場合、それらは同一であっても異なっていてもよい。Ａｒ^2pが複数ある場合、それらは同一であっても異なっていてもよい。〕

(2)
[In formula (2), Am ^2p represents a divalent aromatic amine residue, and Ar ^2p represents an unsubstituted or substituted arylene group. n ^22p and n ^23p each independently represent the molar ratio of the divalent aromatic amine residue represented by Am ^2p and the unsubstituted or substituted arylene group represented by Ar ^2p in the polymer compound. is a number that represents ^{but, n 22p + n 23p = 1,0.001} ≦ n 22p ≦ 1, and a number satisfying 0 ≦ n ^23p ≦ 0.999. When there are a plurality of Am ^{2p s} , they may be the same or different. When there are a plurality of Ar ^{2p s} , they may be the same or different. ]

In the formula (2), a plurality of Am ^2p may be present, and from the viewpoint of synthesis of the polymer compound, it is preferable that all Am ^2p are the same, and from the viewpoint of light emission characteristics, a plurality of Am ^{2p is present. Are} preferably different (that is, a plurality of types of Am ^2p are present in the formula (2)).

The divalent aromatic amine residue represented by Am ^2p means an atomic group obtained by removing two hydrogen atoms from an aromatic amine. The divalent aromatic amine residue may have a substituent, and the carbon number of the portion excluding the substituent is usually 12 to 100, preferably 18 to 60.

  The substituent of the divalent aromatic amine residue includes an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group from the viewpoint of the synthesis of a 2,2′-bipyridinediyl group-free polymer compound. Group, a halogen atom, and a cyano group are preferable, and an alkyl group, an alkenyl group, and an alkynyl group are more preferable.

  Examples of the divalent aromatic amine residue include groups represented by the following formulas Am1 to Am31. From the viewpoint of the hole transportability and light emission characteristics of the device when used in the production of the device, the formula Am1 to Am5, Formulas Am10 to Am16, Formula Am19, Formula Am21, Formula Am23, Formula Am25, Formula Am27, and Formula Am30 are preferred, and Formulas Am12 to Am16, Formula Am19, Formula Am21, Formula Am23, and Formula Am25 are preferred. And groups represented by Formula Am27 and Formula Am30 are more preferable, and from the viewpoint of the synthesis of the 2,2′-bipyridinediyl group-free polymer compound, Formula Am1 to Am5, Formula Am10 to Am12, Formula Am14, Formula Am15 , Groups represented by formula Am21 and formula Am27 are preferable, and groups represented by formulas Am1 to Am5, formulas Am10 to Am12, formula Am14, and formula Am15 are more preferable. The divalent aromatic amine residue may have a substituent.

In the formula (2), a plurality of Ar ^2p may be present, and from the viewpoint of the synthesis of the polymer compound, it is preferable that all Ar ^2p are the same. ^2p is preferably different (that is, a plurality of Ar ^2p are present in the formula (2)). Further, from the viewpoint of device lifetime characteristics and charge transport characteristics, the unsubstituted or substituted arylene group represented by Ar ^2p is an unsubstituted or substituted fluorenediyl group and an unsubstituted or substituted phenylenediyl group. It is particularly preferable to include at least one selected from the group consisting of:

The unsubstituted or substituted arylene group represented by Ar ^2p is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and is either a group having a condensed ring, an independent benzene ring or a condensed ring, or both A group in which two or more of these are bonded directly or via a vinylene group or the like. The arylene group may have a substituent.

  The arylene group may have one or more substituents, and when there are a plurality of substituents, they may be the same or different.

  Carbon number of the part except the substituent of the said arylene group is 6-60 normally, and carbon number including a substituent is 6-100 normally.

  As the substituent of the arylene group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an aryloxy group, a halogen atom, and the like from the viewpoint of the synthesis of a 2,2′-bipyridinediyl group-free polymer compound. An atom and a cyano group are preferable, and an alkyl group, an alkenyl group, an alkynyl group, and an aryl group are more preferable.

  Examples of the arylene group include a phenylene group (formula Ar1 to Ar3), a naphthalenediyl group (formula Ar4 to Ar13), an anthracenediyl group (formula Ar14 to Ar19), a biphenyldiyl group (formula Ar20 to Ar25), and a terphenyldiyl group ( Formula Ar26 to Ar28), condensed ring group (formula Ar29 to Ar35), fluorenediyl group (formula Ar36 to Ar48), and benzofluorenediyl group (formula Ar49 to Ar67). From the viewpoint of the light emitting characteristics of the device, a phenylene group, a biphenyldiyl group, a terphenyldiyl group and a fluorenediyl group are preferable, a phenylene group and a fluorenediyl group are more preferable, and no 2,2′-bipyridinediyl group is contained. From the viewpoint of the synthesis of the polymer compound, formula Ar1, formula Ar4, formula Ar7, formula Ar1 To Ar14, Formula Ar16, Formula Ar17, Formula Ar19 to Ar21, Formula Ar23, Formula Ar26, Formula Ar27, Formula Ar29 to Ar33, Formula Ar35 to Ar37, Formula Ar40, Formula Ar41, Formula Ar43 to Ar46, Formula Ar49 to Ar67 Preferred are the groups In addition, these groups may have a substituent.

In the formula (2), n ^22p is preferably a number satisfying 0.001 ≦ n ^22p ≦ 0.5, and a number satisfying 0.001 ≦ n ^22p ≦ 0.4 from the viewpoint of the synthesis of the polymer compound. More preferably, a number satisfying 0.001 ≦ n ^22p ≦ 0.3 is still more preferable, but from the viewpoint of light emission characteristics and hole transportability, a number satisfying 0.1 ≦ n ^22p ≦ 0.999 is preferable, A number satisfying 0.2 ≦ n ^22p ≦ 0.999 is more preferable, and a number satisfying 0.4 ≦ n ^22p ≦ 0.999 is still more preferable.

The polymer compound represented by the formula (2) preferably has a polystyrene-equivalent number average molecular weight of 1 × 10 ³ to 1 × 10 ⁸ from the viewpoint of lifetime characteristics of the organic electroluminescence device. ³ to 1 × 10 ⁷ is more preferable, and the weight average molecular weight in terms of polystyrene is preferably 1 × 10 ³ to 1 × 10 ⁸ , and more preferably 1 × 10 ³ to 1 × 10 ^7. preferable. The number average molecular weight and the weight average molecular weight can be measured using, for example, size exclusion chromatography (SEC).

  The polymer compound represented by the formula (2) may be any of an alternating copolymer, a random copolymer, a block copolymer, and a graft copolymer, and has an intermediate structure therebetween. It may be a high molecular compound, for example, a random copolymer having a block property.

  Examples of the polymer compound represented by the formula (2) include polymer compounds represented by the following formulas (EX2-1P) to (EX2-3P).

（ＥＸ２−１Ｐ）
〔式（ＥＸ２−１Ｐ）中、Ｘ^exは、水素原子、アルキル基又はアリール基を表す。ｎ^ex12及びｎ^ex13は、ｎ^ex12＋ｎ^ex13＝１、０．０１≦ｎ^ex12≦０．９、及び、０．１≦ｎ^ex13≦０．９９を満たす数である。複数あるＸ^exは、同一であっても異なっていてもよい。〕

(EX2-1P)
Wherein (EX2-1P), X ^ex represents a hydrogen atom, an alkyl group or an aryl group. n ^EX12 and n ^{Ex13 is, n ex12 + n ex13 = 1,0.01} ≦ n ex12 ≦ 0.9, and a number satisfying a 0.1 ≦ ⁿ ex13 ≦ 0.99. A plurality of X ^ex may be the same or different. ]

（ＥＸ２−２Ｐ）
〔式（ＥＸ２−２Ｐ）中、Ｘ^exは前記と同様である。Ｒ^exは、アルキル基又はアルケニル基を表す。ｎ^ex14、ｎ^ex15及びｎ^ex16は、ｎ^ex14＋ｎ^ex15＋ｎ^ex16＝１、０．０１≦ｎ^ex14≦０．４、０．０１≦ｎ^ex15≦０．６、及び、０≦ｎ^ex16≦０．９８を満たす数である。複数あるＸ^exは、同一であっても異なっていてもよい。Ｒ^exが複数ある場合、それらは同一であっても異なっていてもよい。〕

(EX2-2P)
Wherein (EX2-2P), the X ^ex is the same as above. R ^ex represents an alkyl group or an alkenyl group. n ^ex14 , n ^ex15 and n ^ex16 are n ^ex14 + n ^ex15 + n ^ex16 = 1, ^0.01 ≦ n ^ex14 ≦ 0.4, 0.01 ≦ n ^ex15 ≦ 0.6, and 0 ≦ n ^ex16 ≦ 0. It is a number satisfying 98. A plurality of X ^ex may be the same or different. When there are a plurality of R ^ex , they may be the same or different. ]

（ＥＸ２−３Ｐ）
〔式（ＥＸ２−３Ｐ）中、Ｘ^exは前記と同様である。Ｒ^exは、アルキル基又はアルケニル基を表す。ｎ^ex17、ｎ^ex18及びｎ^ex19は、ｎ^ex17＋ｎ^ex18＋ｎ^ex19＝１、０．０１≦ｎ^ex17≦０．４、０．０１≦ｎ^ex18≦０．６、及び、０≦ｎ^ex19≦０．９８を満たす数である。複数あるＸ^exは、同一であっても異なっていてもよい。複数あるＲ^exは、同一であっても異なっていてもよい。〕

(EX2-3P)
[In the formula (EX2-3P), X ^ex is the same as described above. R ^ex represents an alkyl group or an alkenyl group. ⁿ ex17, n ex18 and n ^{EX19 is, n ex17 + n ex18 + n} ex19 = 1,0.01 ≦ n ex17 ≦ 0.4,0.01 ≦ n ex18 ≦ 0.6 ^{and,, 0 ≦ n ex19 ≦ 0} . It is a number satisfying 98. A plurality of X ^ex may be the same or different. A plurality of R ^ex may be the same or different. ]

  The 2,2′-bipyridinediyl group-free hole-transporting polymer compound includes a 2,2′-bipyridinediyl group-free positive compound such as the polymer compound represented by the formula (2) described above. Also included are polymer compounds obtained by crosslinking pore-transporting polymer compounds between molecules or within molecules.

  The molecular weights of 2,2′-bipyridine and 2,2′-bipyridine derivatives are usually 156 to 1500, preferably 184 to 800.

In the above formula, the alkyl group and aryl group represented by X ^ex are the same as described above. In the above formula, the alkyl group and alkenyl group represented by R ^ex are the same as described above.

  As the 2,2′-bipyridine or the 2,2′-bipyridine derivative, a compound represented by the following formula (3) is preferable.

（３）
〔式（３）中、Ｅ^3m及びＲ^3mは、それぞれ独立に、水素原子、ハロゲン原子、水酸基、非置換若しくは置換のアルキル基、非置換若しくは置換のアルケニル基、非置換若しくは置換のアルキニル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアルキルチオ基、非置換若しくは置換のアルキルシリル基、非置換若しくは置換のアリール基、非置換若しくは置換のアリールオキシ基、又は非置換若しくは置換のアリールシリル基を表す。Ｘ^3mは、非置換若しくは置換のアリーレン基、非置換若しくは置換のアルカンジイル基、非置換若しくは置換のアルケンジイル基、又は非置換若しくは置換のアルキンジイル基を表す。複数あるＥ^3mは、同一であっても異なっていてもよい。複数あるＲ^3mは、同一であっても異なっていてもよい。ｍ^31mは、０〜３の整数を表す。ｍ^32mは、１〜３の整数を表す。ｍ^31mが複数ある場合、それらは同一であっても異なっていてもよい。Ｘ^3mが複数ある場合、それらは同一であっても異なっていてもよい。〕

(3)
[In formula (3), E ^3m and R ^3m each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, Unsubstituted or substituted alkoxy group, unsubstituted or substituted alkylthio group, unsubstituted or substituted alkylsilyl group, unsubstituted or substituted aryl group, unsubstituted or substituted aryloxy group, or unsubstituted or substituted arylsilyl Represents a group. X ^3m represents an unsubstituted or substituted arylene group, an unsubstituted or substituted alkanediyl group, an unsubstituted or substituted alkenediyl group, or an unsubstituted or substituted alkynediyl group. The plurality of E ^3m may be the same or different. A plurality of R ^3m may be the same or different. m ^31m represents an integer of 0 to 3. m ^32m represents an integer of 1 to 3. When there are a plurality of m ^31m , they may be the same or different. When there are a plurality of X ^{3m s} , they may be the same or different. ]

In formula (3), E ^3m represents a hydrogen atom, a halogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, from the viewpoint of the synthesis of the compound represented by formula (3), It is preferably an unsubstituted or substituted alkynyl group, an unsubstituted or substituted aryl group, more preferably a hydrogen atom, a halogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted aryl group. From the viewpoint of solubility of the compound represented by formula (3) in an organic solvent, a halogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group An unsubstituted or substituted aryl group, preferably a hydroxyl group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, or an unsubstituted or substituted alkynyl group. More preferably, from the viewpoint of luminescent properties, a hydrogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, an unsubstituted or substituted alkoxy group, unsubstituted or A substituted aryl group, an unsubstituted or substituted aryloxy group is preferred, and a hydrogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, and an unsubstituted or substituted aryl group are more preferred. In addition, from the viewpoint of the synthesis of the compound represented by the formula (3), it is preferable that all E ^3m are the same.

In formula (3), R ^3m represents a hydrogen atom, a halogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, from the viewpoint of the synthesis of the compound represented by formula (3), It is preferably an unsubstituted or substituted alkynyl group, an unsubstituted or substituted aryl group, more preferably a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, and a hydrogen atom In view of solubility of the compound represented by formula (3) in an organic solvent, a halogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, unsubstituted or It is preferably a substituted alkynyl group, an unsubstituted or substituted aryl group, a hydroxyl group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group More preferably, from the viewpoint of luminescent properties, a hydrogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, an unsubstituted or substituted alkoxy group, An unsubstituted or substituted aryl group and an unsubstituted or substituted aryloxy group are preferred, and a hydrogen atom is more preferred.

In formula (3), X ^3m is preferably an unsubstituted or substituted arylene group or an unsubstituted or substituted alkanediyl group. When there are a plurality of X ^{3m s} , they may be the same or different. X ^3m is the same as defined above for the unsubstituted or substituted arylene group.

Examples of the alkanediyl group represented by X ^3m include a methylene group, an ethylene group, a propylene group, a tetramethylene group, a pentaethylene group, a hexaethylene group, and a heptaethylene group. This alkanediyl group may have a substituent.

Examples of the alkenediyl group represented by X ^3m include vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, 1,2-butadienylene group, 1,3-butadienylene group, 1-pentenylene group, 2- Pentenylene group, 1,2-pentadienylene group, 1,3-pentadienylene group, 1,4-pentadienylene group, 2,3-pentadienylene group, 2,4-pentadienylene group, 1-hexenylene group, 2-hexenylene group, 3- A hexenylene group. This alkenediyl group may have a substituent.

Examples of the alkynediyl group represented by X ^3m include an ethynylene group, a propynylene group, a 1-butynylene group, a 2-butynylene group, and a 1,3-butyninylene group. This alkynediyl group may have a substituent.

In the formula (3), m ^32m is preferably 1 from the viewpoint of life characteristics.

  As a compound represented by Formula (3), the compound represented by following formula (4) or (5) is preferable.

（４）
〔式（４）中、Ｅ^4mは、水素原子、水酸基、非置換若しくは置換のアルキル基、又は非置換若しくは置換のアルコキシ基を表す。複数あるＥ^4mは、同一であっても異なっていてもよいが、少なくとも１個は、水酸基、非置換若しくは置換のアルキル基、又は非置換若しくは置換のアルコキシ基を表す。〕

(4)
[In formula (4), E ^4m represents a hydrogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted alkoxy group. Plural E ^4m may be the same or different, but at least one E ^4m represents a hydroxyl group, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted alkoxy group. ]

（５）
〔式（５）中、Ｅ^5mは、水素原子、水酸基、非置換若しくは置換のアルキル基、又は非置換若しくは置換のアルコキシ基を表す。複数あるＥ^5mは、同一であっても異なっていてもよい。Ｘ^5mは、非置換若しくは置換のアリーレン基、又は非置換若しくは置換のアルカンジイル基を表す。ｍ^5mは１〜３の整数を表す。Ｘ^5mが複数ある場合、それらは同一であっても異なっていてもよい。〕

(5)
[In formula (5), E ^5m represents a hydrogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted alkoxy group. The plurality of E ^5m may be the same or different. X ^5m represents an unsubstituted or substituted arylene group or an unsubstituted or substituted alkanediyl group. m ^5m represents an integer of 1 to 3. When there are a plurality of X ^5m , they may be the same or different. ]

In formula (4), E ^4m is preferably a hydroxyl group, an unsubstituted or substituted alkyl group, from the viewpoint of light emission characteristics. When E ^4m is a hydroxyl group, an unsubstituted or substituted alkyl group, the compound represented by the formula (4) is a compound represented by the following formulas (4-1) to (4-10). From the viewpoint, the compounds represented by formula (4-1), formula (4-5), formula (4-8), and formula (4-10) are preferable. Moreover, it is preferable that all ^E4m is the same.

〔式（４−１）〜（４−１０）中、Ｅ^41mは、水酸基、又は非置換若しくは置換のアルキル基を表す。複数あるＥ^41mは、同一であっても異なっていてもよい。〕

[In formulas (4-1) to (4-10), E ^41m represents a hydroxyl group or an unsubstituted or substituted alkyl group. The plurality of E ^41m may be the same or different. ]

In formula (5), E ^5m is preferably a hydroxyl group, an unsubstituted or substituted alkyl group, from the viewpoint of light emission characteristics. Moreover, it is preferable that all ^E5m is the same from a viewpoint of the synthesis | combination of the compound represented by Formula (5).

In formula (5), m ^5m is preferably 1 or 3 from the viewpoint of the synthesis of the compound represented by formula (5).

In the formula (5), when m ^5m is 1, from the viewpoint of luminescent properties, X ^5m is preferably an unsubstituted or substituted alkanediyl group, and from the viewpoint of synthesis of the compound represented by (5) Therefore, X ^5m is preferably an unsubstituted or substituted arylene group. The alkanediyl group and arylene group represented by X ^5m are the same as described above.

In the formula (5), when m ^5m is 3, the compound represented by the formula (5) is preferably a compound represented by the following formulas (5-1) to (5-8). It is more preferable that it is a compound represented by Formula (5-3) or (5-7).

〔式（５−１）〜（５−８）中、Ｅ^5mは、前記と同様である。Ｒ^51mは、非置換又は置換のアルカンジイル基（このアルカンジイル基は、前記と同様である。）を表す。Ａｒ^51mは、非置換又は置換のアリーレン基（このアリーレン基は、前記と同様である。）を表す。Ｒ^51mが複数ある場合、それらは同一であっても異なっていてもよい。Ａｒ^51mが複数ある場合、それらは同一であっても異なっていてもよい。〕

[In formulas (5-1) to (5-8), E ^5m is the same as described above. R ^51m represents an unsubstituted or substituted alkanediyl group (this alkanediyl group is the same as described above). Ar ^51m represents an unsubstituted or substituted arylene group (the arylene group is the same as described above). When there are a plurality of R ^51m , they may be the same or different. When there are a plurality of Ar ^{51m s} , they may be the same or different. ]

  The melting points of the compounds represented by formulas (3) to (5), formulas (4-1) to (4-10), and formulas (5-1) to (5-8) are as follows: 10-500 degreeC is preferable, 30-400 degreeC is more preferable, and 40-300 degreeC is still more preferable.

The saturated vapor pressure at 25 ° C. of the compounds represented by formulas (3) to (5), formulas (4-1) to (4-10), and formulas (5-1) to (5-8) In view of the above, 1 × 10 ⁻³ Torr or less is preferable, 1 × 10 ⁻⁴ Torr or less is more preferable, and 1 × 10 ⁻⁵ Torr or less is even more preferable.

  Compounds represented by formulas (3) to (5), formulas (4-1) to (4-10), and formulas (5-1) to (5-8) are chloroform, methylene chloride, 1,2- Chlorine solvents such as dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene; ether solvents such as tetrahydrofuran, dioxane and anisole; aromatic hydrocarbon solvents such as toluene and xylene; cyclohexane, methylcyclohexane, Aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, benzophenone and acetophenone; ethyl acetate , Ester solvents such as butyl acetate, ethyl cellosolve acetate, methyl benzoate and phenyl acetate Ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, 1,2-propanediol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, etc. Polyhydric alcohols and derivatives thereof; alcohol solvents such as methanol, ethanol, propanol, isopropanol and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide Preferably, it is a compound that can be dissolved in one or a plurality of solvents at 25 ° C. so as to have a concentration of 0.5% by weight or more. More preferably, it is a compound that can be dissolved at a concentration of 5% by weight or more, more preferably a compound that can be dissolved at a concentration of 5% by weight or more, and a compound that can be dissolved at a concentration of 10% by weight or more. It is particularly preferred.

  The ratio (total ratio) of 2,2′-bipyridine and 2,2′-bipyridine derivative contained in the hole transport layer is 0.01 to 50% by weight from the viewpoints of driving voltage and device lifetime. It is preferably 0.01 to 40% by weight.

(Material 2: a group consisting of a structural unit composed of an unsubstituted or substituted 2,2′-bipyridinediyl group, a structural unit composed of a divalent aromatic amine residue, and a structural unit composed of an unsubstituted or substituted arylene group 2,2′-bipyridinediyl group-containing polymer compound having at least one structural unit selected from
The carbon number including a substituent of a repeating unit composed of an unsubstituted or substituted 2,2′-bipyridinediyl group of the 2,2′-bipyridinediyl group-containing polymer compound is usually 10 to 100.

  The divalent aromatic amine residue and the unsubstituted or substituted arylene group in the material 2 are the same as those in the polymer compound containing no 2,2′-bipyridinediyl group.

  Examples of the substituent of the repeating unit composed of the 2,2′-bipyridinediyl group include a halogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an aryl group, and an aryloxy group. And an arylsilyl group.

  Examples of the 2,2′-bipyridinediyl group include groups represented by the following formulas Bpy1 to Bpy16. Some or all of the hydrogen atoms contained in these groups may be substituted with a substituent.

  The 2,2′-bipyridinediyl group-containing polymer compound is preferably a polymer compound represented by the following formula (1).

（１）
〔式（１）中、Ｂｐｙ^1pは、非置換又は置換の２,２'−ビピリジンジイル基を表す。Ａｍ^1pは、２価の芳香族アミン残基を表す。Ａｒ^1pは、非置換又は置換のアリーレン基を表す。ｎ^11p、ｎ^12p及びｎ^13pは、それぞれ独立に、該高分子化合物中のＢｐｙ^1pで表される非置換又は置換の２,２'−ビピリジンジイル基とＡｍ^1pで表される２価の芳香族アミン残基とＡｒ^1pで表される非置換又は置換のアリーレン基とのモル比を表す数であるが、ｎ^11p＋ｎ^12p＋ｎ^13p＝１、０．００１≦ｎ^11p≦０．９９９、０．００１≦ｎ^12p≦０．９９９、及び、０≦ｎ^13p≦０．９９８を満たす数である。Ｂｐｙ^1pが複数ある場合、それらは同一であっても異なっていてもよい。Ａｍ^1pが複数ある場合、それらは同一であっても異なっていてもよい。Ａｒ^1pが複数ある場合、それらは同一であっても異なっていてもよい。〕

(1)
[In Formula (1), Bpy ^1p represents an unsubstituted or substituted 2,2′-bipyridinediyl group. Am ^1p represents a divalent aromatic amine residue. Ar ^1p represents an unsubstituted or substituted arylene group. n ^11p , n ^12p and n ^13p are each independently an unsubstituted or substituted 2,2′-bipyridinediyl group represented by Bpy ^1p and a divalent fragrance represented by Am ^1p in the polymer compound. N ^11p + n ^12p + n ^13p = 1, 0.001 ≦ n ^11p ≦ 0.999, 0, which represents the molar ratio between the group amine residue and the unsubstituted or substituted arylene group represented by Ar ^1p .001 ≦ n ^12p ≦ 0.999 and 0 ≦ n ^13p ≦ 0.998. When there are a plurality of Bpy ^1p , they may be the same or different. When there are a plurality of Am ^1p , they may be the same or different. When there are a plurality of Ar ^{1p s} , they may be the same or different. ]

In the formula (1), the unsubstituted or substituted 2,2′-bipyridinediyl group represented by Bpy ^1p is preferably a group represented by the formula Bpy1 to Bpy16, but the 2,2′-bipyridinediyl group. The group is classified into a group represented by the following formula (1-2) or the following formula (1-3) depending on the position of the bonding group. In the formula (1), Bpy ^1p is preferably a group represented by the following formula (1-2) from the viewpoint of further suppressing a voltage increase during driving of the element, and was used for manufacturing the element. From the viewpoint of the emission lifetime in the case, the group represented by the formula (1-3) is preferable.

（１−２）
〔式（１−２）中、Ｒ^1pは、水素原子、ハロゲン原子、水酸基、非置換若しくは置換のアルキル基、非置換若しくは置換のアルケニル基、非置換若しくは置換のアルキニル基、非置換若しくは置換のアルコキシ基、非置換若しくは置換のアルキルチオ基、非置換若しくは置換のアルキルシリル基、非置換若しくは置換のアリール基、非置換若しくは置換のアリールオキシ基、又は非置換若しくは置換のアリールシリル基を表す。複数あるＲ^1pは、同一であっても異なっていてもよい。〕

(1-2)
[In the formula (1-2), R ^1p represents a hydrogen atom, a halogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, an unsubstituted or substituted It represents an alkoxy group, an unsubstituted or substituted alkylthio group, an unsubstituted or substituted alkylsilyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, or an unsubstituted or substituted arylsilyl group. A plurality of R ^1p may be the same or different. ]

（１−３）
〔式（１−３）中、Ｒ^1pは、前記と同様である。複数あるＲ^1pは、同一であっても異なっていてもよい。〕

(1-3)
[In formula (1-3), R ^1p is the same as described above. A plurality of R ^1p may be the same or different. ]

In the above formulas (1-2) and (1-3), R ^1p represents a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted group from the viewpoint of the light emitting characteristics of the device when used in the production of the device. Or a substituted alkenyl group, an unsubstituted or substituted alkynyl group, an unsubstituted or substituted aryl group, and a hydroxyl group are preferred, a hydrogen atom, an unsubstituted or substituted alkyl group is more preferred, a hydrogen atom is further preferred, and 2,2 ′ -From the viewpoint of the synthesis of a polymer compound containing a bipyridinediyl group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or A substituted aryl group, an unsubstituted or substituted aryloxy group, a halogen atom, and a cyano group are preferable. From the viewpoint of driving voltage or emission lifetime in the case of a device, a hydrogen atom, unsubstituted or substituted Alkyl group, unsubstituted or substituted alkenyl group, unsubstituted or substituted alkynyl group are preferred, more preferably a hydrogen atom.

Examples of the group represented by the formula (1-2) include groups represented by the following formulas (1-2-1) to (1-2-10), and includes a 2,2′-bipyridinediyl group. From the viewpoint of the synthesis of the polymer compound, groups represented by formulas (1-2-1) to (1-2-4) are preferable. R ¹ in the formula has the same meaning as R ^1p . A plurality of R ¹ may be the same or different.

Examples of the group represented by the formula (1-3) include groups represented by the following formulas (1-3-1) to (1-3-6), and a 2,2′-bipyridinediyl group is contained. From the viewpoint of the synthesis of the polymer compound, groups represented by formula (1-3-2), formula (1-3-3), and formula (1-3-5) are preferable. R ¹ in the formula has the same meaning as R ¹ . A plurality of R ¹ may be the same or different.

In the formula (1), examples of the divalent aromatic amine residue represented by Am ^1p include the same groups as the divalent aromatic amine residue. When there are a plurality of Am ^{1p s,} they may be the same or different, but are preferably the same from the viewpoint of the synthesis of the 2,2′-bipyridinediyl group-containing polymer compound, and are used for device fabrication. From the viewpoint of the light emitting characteristics of the device, it is preferable that they are different (that is, a plurality of types of Am ^1p are present in the formula (1)).

In the formula (1), examples of the unsubstituted or substituted arylene group represented by Ar ^1p include the same groups as the arylene group. When there are a plurality of Ar ^{1p s,} they may be the same or different, but are preferably the same from the viewpoint of the synthesis of the 2,2′-bipyridinediyl group-containing polymer compound. From the viewpoint of the light emission lifetime, it is preferable that they are different (that is, a plurality of types of Ar ^1p are present in the formula (1)).

In the formula (1), n ^11p is preferably a number satisfying 0.001 ≦ n ^11p ≦ 0.5, from the viewpoint of synthesis of the 2,2′-bipyridinediyl group-containing polymer compound, and 0.001 ≦ The number satisfying n ^11p ≦ 0.2 is more preferable, the number satisfying 0.001 ≦ n ^11p ≦ 0.1 is particularly preferable. From the viewpoint of the light emission characteristics of the device when used for manufacturing the device, the number A number satisfying 001 ≦ n ^11p ≦ 0.3 is preferable, a number satisfying 0.005 ≦ n ^11p ≦ 0.2 is more preferable, and a number satisfying 0.01 ≦ n ^11p ≦ 0.1 is particularly preferable.

In the formula (1), n ^12p is preferably a number satisfying 0.001 ≦ n ^12p ≦ 0.5, from the viewpoint of synthesis of the 2,2′-bipyridinediyl group-containing polymer compound, and 0.001 ≦ The number satisfying n ^12p ≦ 0.4 is more preferable, the number satisfying 0.001 ≦ n ^12p ≦ 0.3 is particularly preferable, and the device has a light emitting characteristic and a hole transport property when used for manufacturing the device. Is preferably a number satisfying 0.1 ≦ n ^12p ≦ 0.999, more preferably a number satisfying 0.2 ≦ n ^12p ≦ 0.999, and a number satisfying 0.4 ≦ n ^12p ≦ 0.999. Particularly preferred.

The 2,2′-bipyridinediyl group-containing polymer compound represented by the formula (1) has a polystyrene-equivalent number average molecular weight of 1 × from the viewpoint of the lifetime characteristics of the device when used in the production of the device. It is preferably 10 ³ to 1 × 10 ⁸ , more preferably 1 × 10 ³ to 1 × 10 ⁷ , and a weight average molecular weight in terms of polystyrene of 1 × 10 ³ to 1 × 10 ^8. Preferably, it is 1 × 10 ³ to 1 × 10 ⁷ . The number average molecular weight and the weight average molecular weight can be measured using, for example, size exclusion chromatography.

  The 2,2′-bipyridinediyl group-containing polymer represented by the formula (1) may be any one of an alternating copolymer, a random copolymer, a block copolymer, and a graft copolymer. .

    Examples of the 2,2′-bipyridinediyl group-containing polymer compound represented by the formula (1) include polymer compounds represented by the following formulas (EX1-1P) to (EX1-3P).

（ＥＸ１−１Ｐ）
〔式（ＥＸ１−１Ｐ）中、Ｘ^exは、前記と同様である。複数あるＸ^exは、同一であっても異なっていてもよい。ｎ^ex1、ｎ^ex2及びｎ^ex3は、それぞれ独立に、０．０１≦ｎ^ex1≦０．３を満たす数、０．０１≦ｎ^ex2≦０．８９を満たす数、及び、０．１≦ｎ^ex3≦０．９８を満たす数であり、かつ、ｎ^ex1＋ｎ^ex2＋ｎ^ex3＝１を満たす数である。〕

(EX1-1P)
[In the formula (EX1-1P), X ^ex is the same as described above. A plurality of X ^ex may be the same or different. n ^ex1 , n ^ex2 and n ^ex3 are each independently a number satisfying 0.01 ≦ n ^ex1 ≦ 0.3, a number satisfying 0.01 ≦ n ^ex2 ≦ 0.89, and 0.1 ≦ n ^ex3 It is a number satisfying ≦ 0.98 and satisfying n ^ex1 + n ^ex2 + n ^ex3 = 1. ]

（ＥＸ１−２Ｐ）
〔式（ＥＸ１−２Ｐ）中、Ｘ^ex及びＲ^exは、前記と同様である。ｎ^ex4、ｎ^ex5、ｎ^ex6及びｎ^ex7は、それぞれ独立に、０．０１≦ｎ^ex4≦０．３を満たす数、０．０１≦ｎ^ex5≦０．４を満たす数、０．０１≦ｎ^ex6≦０．６を満たす数、及び、０≦ｎ^ex7≦０．９７を満たす数であり、かつ、ｎ^ex4＋ｎ^ex5＋ｎ^ex6＋ｎ^ex7＝１を満たす数である。〕

(EX1-2P)
[In the formula (EX1-2P), X ^ex and R ^ex are the same as described above. n ^ex4 , n ^ex5 , n ^ex6 and n ^ex7 are each independently a number satisfying 0.01 ≦ n ^ex4 ≦ 0.3, a number satisfying 0.01 ≦ n ^ex5 ≦ 0.4, 0.01 ≦ n ^A number satisfying ^ex6 ≦ 0.6, a number satisfying 0 ≦ n ^ex7 ≦ 0.97, and a number satisfying n ^ex4 + n ^ex5 + n ^ex6 + n ^ex7 = 1. ]

（ＥＸ１−３Ｐ）
〔式（ＥＸ１−３Ｐ）中、Ｘ^ex及びＲ^exは、前記と同様である。ｎ^ex8、ｎ^ex9、ｎ^ex10及びｎ^ex11は、それぞれ独立に、０．０１≦ｎ^ex8≦０．３を満たす数、０．０１≦ｎ^ex9≦０．４を満たす数、０．０１≦ｎ^ex10≦０．６を満たす数、及び、０≦ｎ^ex11≦０．９７を満たす数であり、かつ、ｎ^ex8＋ｎ^ex9＋ｎ^ex10＋ｎ^ex11＝１を満たす数である。〕

(EX1-3P)
[In the formula (EX1-3P), X ^ex and R ^ex are the same as described above. ^{n ex8,} n ex9, n ex10 and n ^ex11 are each independently a number satisfying 0.01 ≦ n ^ex8 ≦ 0.3, number satisfying ^{0.01 ≦ n ex9 ≦ 0.4, 0.01} ≦ n number satisfying ^EX10 ≦ 0.6, and a number satisfying the 0 ≦ n ^ex11 ≦ 0.97, and a number satisfying ^{n ex8 + n ex9 + n ex10} + n ex11 = 1. ]

  When the 2,2′-bipyridinediyl group-containing polymer compound and the 2,2′-bipyridinediyl group-free hole transporting polymer compound are included in the hole transport layer, the preferred ratio of each is as described above. It is as follows.

  The 2,2′-bipyridinediyl group-containing polymer compound and the 2,2′-bipyridinediyl group-free hole-transporting polymer compound may be produced by any method, but the polymerization reactivity to be a monomer If necessary, a compound having a plurality of groups can be produced by dissolving in an organic solvent and reacting at a temperature not lower than the melting point of the organic solvent and not higher than the boiling point using an alkali or a suitable catalyst. This is described in “Organic Reactions”, Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965, “Organic Syntheses”, Collective No. 6 (Collective Volume VI), 407-411, John Wiley & Sons, Inc., 1988, Chemical Review (Chem. Rev.), 95, 2457 (1995), Journal of Organometallic Chemistry (J. Organomet. Chem.), 576, 147 (1999), Macromolecular Chemistry Mac Molecular Symposium (Macromol.Chem., Macromol.Symp.), Are listed in Vol. 12, page 229 (1987) and JP 2009-108313 Patent Publication.

The method for producing the 2,2′-bipyridinediyl group-containing polymer compound will be described with reference to the 2,2′-bipyridinediyl group-containing polymer compound represented by the formula (1) as an example: Formula: Y-Bpy ^It can be produced by subjecting a compound represented by ^1p- Y, a compound represented by the formula: Y- ^Am1p- Y, and a compound represented by the formula: Y- ^Ar1p- Y to condensation polymerization. In these formulas, Bpy ^1p, Am ^1p and Ar ^1p has Bpy ^1p of the formula (1) is the same as the Am ^1p and Ar ^1p, Y represents a polymerizable reactive group. Two Ys in the formula may be the same or different.

The 2,2′-bipyridinediyl group-free hole transporting polymer compound can also be produced in the same manner as the 2,2′-bipyridinediyl group-containing polymer compound represented by the formula (1). it can. Here, the 2,2′-bipyridinediyl group-free hole transporting polymer compound represented by the polymer compound represented by the formula (2) will be described as an example. The formula: Y—Am ^2p —Y And a compound represented by the formula: Y—Ar ^2p —Y can be produced by condensation polymerization. In these formulas, Am ^2p and Ar ^2p are the same as Am ^2p and Ar ^2p in the formula (2).

Examples of the polymerization reactive group include a halogen atom, an alkylsulfonyloxy group, an arylsulfonyloxy group, an arylalkylsulfonyloxy group, a boric acid ester residue, a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, and a monohalogenated methyl group. , Boric acid residue (—B (OH) ₂ ), formyl group, cyano group, and vinyl group.

  Examples of the halogen atom that is the polymerization reactive group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkylsulfonyloxy group that is the polymerization reactive group include a methanesulfonyloxy group, an ethanesulfonyloxy group, and a trifluoromethanesulfonyloxy group.

  Examples of the arylsulfonyloxy group that is the polymerization reactive group include a benzenesulfonyloxy group and a p-toluenesulfonyloxy group.

  Examples of the arylalkylsulfonyloxy group that is the polymerization reactive group include a benzylsulfonyloxy group.

  Examples of the boric acid ester residue that is the polymerization reactive group include groups represented by the following formulae.

（式中、Ｍｅはメチル基、Ｅｔはエチル基を表し、以下、同様である。）

(In the formula, Me represents a methyl group, Et represents an ethyl group, and the same applies hereinafter.)

  Examples of the sulfonium methyl group that is the polymerization reactive group include groups represented by the following formulae.

_{^{-CH 2 S + Me 2 X -}} , -CH 2 S + Ph 2 X -
(In the formula, X represents a halogen atom. Ph represents a phenyl group, and the same shall apply hereinafter.)

  Examples of the phosphonium methyl group that is the polymerization reactive group include groups represented by the following formulas.

-CH ₂ P ⁺ Ph ₃ X ^-
(In the formula, X is the same as described above.)

  Examples of the phosphonate methyl group which is the polymerization reactive group include groups represented by the following formula.

-CH ₂ PO (OR ') ₂
(In the formula, R 'represents an unsubstituted or substituted alkyl group or an unsubstituted or substituted aryl group. Two R's may be the same or different.)

  Examples of the monohalogenated methyl group that is the polymerization reactive group include a fluoromethyl group, a chloromethyl group, a bromomethyl group, and an iodomethyl group.

  The polymerization reactive group is a halogen atom, an alkylsulfonyloxy group, an arylsulfonyloxy group, an arylalkylsulfonyloxy group or the like when a nickel zero-valent complex such as a Yamamoto coupling reaction is used, and a Suzuki coupling reaction or the like. In the case of using a nickel catalyst or palladium catalyst, an alkylsulfonyloxy group, a halogen atom, a boric acid ester residue, a boric acid residue or the like.

  The purity of the 2,2′-bipyridinediyl group-containing polymer compound and the 2,2′-bipyridinediyl group-free hole-transporting polymer compound affects the performance of the device such as light emission characteristics. It is preferable to polymerize a compound having a plurality of polymerization-reactive groups to be monomers after purification by a method such as distillation, sublimation purification, or recrystallization. Further, after polymerization, the obtained 2,2′-bipyridinediyl group-containing polymer compound and the 2,2′-bipyridinediyl group-free hole-transporting polymer compound are subjected to reprecipitation purification and fractionation by chromatography. It is preferable to perform a purification treatment such as the above.

Next, a method for forming the hole transport layer will be described.
As a method of forming the hole transport layer, for example,
A) a mixture of the 2,2′-bipyridine and / or 2,2′-bipyridine derivative and a 2,2′-bipyridinediyl group-free hole transporting polymer compound, and an organic solvent, Composition of the
B) From the group consisting of the structural unit consisting of the unsubstituted or substituted 2,2′-bipyridinediyl group, the structural unit consisting of a divalent aromatic amine residue, and the structural unit consisting of an unsubstituted or substituted arylene group. A second composition comprising a 2,2′-bipyridinediyl group-containing polymer compound having at least one selected structural unit, and an organic solvent;
Or a combination thereof [ie, a combination of A) and B)
The method using is mentioned.

  Thus, a method for forming a hole transport layer as a first composition or a second composition containing an organic solvent (hereinafter collectively referred to as “solution”) applies the solution. Then, the organic solvent only has to be removed by drying, which is advantageous in production.

  The organic solvent may be any solvent that can dissolve the solid content contained in the solution. Examples of the organic solvent include chlorine solvents such as chloroform, methylene chloride and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate and acetic acid. Examples are ester solvents such as butyl and ethyl cellosolve acetate, and chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, and n-butylbenzene are preferred. In addition, as these solvent, what can dissolve solid content contained in the said solution 0.1weight% or more is especially preferable.

  As for the kind of the solvent in a solution, 2 or more types are preferable from viewpoints of film formability, element characteristics, etc., 2-3 types are more preferable, and 2 types are especially preferable.

  When two kinds of solvents are contained in the solution, one of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, one kind of solvent is preferably a solvent having a boiling point of 180 ° C. or higher, and more preferably 200 ° C. or higher. Further, from the viewpoint of viscosity, both of the two solvents are at a concentration of 1% by weight or more at 60 ° C., 2,2′-bipyridinediyl group-free hole transporting polymer compound or 2,2′-bipyridinediyl It is preferable that the group-containing polymer compound can be dissolved, and one of the two solvents contains 2,2′-bipyridinediyl at a concentration of 1% by weight or more at 25 ° C. It is more preferable that the group-free hole-transporting polymer compound or the 2,2′-bipyridinediyl group-containing polymer compound can be dissolved.

  The hole transport layer is formed by spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, cap coating. Application methods such as a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an ink jet printing method, a nozzle coating method, and the like can be employed.

  When the printing method is adopted, the 2,2′-bipyridine and / or the 2,2′-bipyridine derivative and the 2,2′-, when the component other than the organic solvent in the first composition is 100 parts by weight. The ratio of the mixture with the bipyridinediyl group-free hole transporting polymer compound is usually 20 to 100 parts by weight, preferably 40 to 100 parts by weight.

  In the case where the printing method is adopted, when the component other than the organic solvent in the second composition is 100 parts by weight, the structural unit composed of the unsubstituted or substituted 2,2′-bipyridinediyl group and the divalent aroma The proportion of the 2,2′-bipyridinediyl group-containing polymer compound having a structural unit consisting of a group amine residue and at least one structural unit selected from the group consisting of a structural unit consisting of an unsubstituted or substituted arylene group is as follows: Usually, it is 20-100 weight part, Preferably it is 40-100 weight part.

  The ratio of the organic solvent contained in the solution is usually 1 to 99.9 parts by weight, preferably 60 to 99.5 parts by weight, more preferably 80, when the total weight of the solution is 100 parts by weight. ~ 99.0 parts by weight.

  The viscosity of the solution varies depending on the printing method, but when the solution such as the ink jet printing method is a solution used for a method via a discharge device, in order to prevent clogging and flight bending at the time of discharge at 25 ° C. 1 to 20 mPa · s.

  The solution may contain a stabilizer, an additive for adjusting viscosity and surface tension, and an antioxidant. Examples of the additive include a high molecular weight compound (thickener) for increasing the viscosity, a poor solvent, a low molecular weight compound for decreasing the viscosity, and a surfactant for decreasing the surface tension.

The high molecular weight compound may be any compound that is soluble in the organic solvent and does not inhibit light emission or charge transport, and includes polystyrene, polymethyl methacrylate, and the like. The polystyrene equivalent weight average molecular weight of the high molecular weight compound is preferably 5 × 10 ⁵ or more, and more preferably 1 × 10 ⁶ or more.

  A poor solvent can also be used as a thickener. When a poor solvent is used as a thickener, the type and amount of the organic solvent may be adjusted within a range in which the solid content in the solution does not precipitate. Considering the stability during storage of the solution, the amount of the poor solvent is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the total weight of the solution.

  The antioxidant may be any compound that is soluble in the organic solvent and does not inhibit light emission or charge transport, and examples thereof include phenol-based antioxidants and phosphorus-based antioxidants.

  The solution may contain water, silicon, phosphorus, fluorine, chlorine, bromine, metal, or a salt thereof in the range of 1 to 1000 ppm (weight basis). A smaller content is preferred.

  Examples of the metal include lithium, sodium, calcium, potassium, iron, copper, nickel, aluminum, zinc, chromium, manganese, cobalt, platinum, and iridium.

  The thickness of the hole transport layer may be adjusted so that the driving voltage and the light emission efficiency have appropriate values, but the thickness that does not cause pinholes is required. If the hole transport layer is too thick, the driving voltage tends to increase. Therefore, the thickness of the hole transport layer is preferably 1 to 500 nm, more preferably 2 to 200 nm, still more preferably 2 to 100 nm, and particularly preferably 5 to 50 nm.

  In addition to the materials 1 and 2, the hole transport layer constituting the organic electroluminescence device of the present invention may contain other hole transport materials. Other hole transport materials can be classified into low molecular weight hole transport materials and high molecular weight hole transport materials.

  Examples of the high molecular weight hole transport material include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in side chains or main chains, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine. Derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof are exemplified. Examples of the high molecular weight hole transport material include JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, and JP-A-2-209998. Examples thereof include materials described in Japanese Patent Laid-Open Nos. 3-37992 and 3-152184. Among these, high molecular weight hole transport materials include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine compound group in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof. Derivatives, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof are preferred, polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, aromatic amines in the side chain or main chain The polysiloxane derivative is more preferable.

  Examples of the low molecular weight hole transport material include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, and triphenyldiamine derivatives. When the hole transport layer contains a low molecular weight hole transport material, a polymer binder may coexist.

  As the polymer binder, a compound which does not extremely inhibit hole transport and does not strongly absorb visible light is preferable. Examples of the polymer 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, Examples include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  As said polyvinyl carbazole and its derivative (s), the compound obtained from a vinyl monomer by cationic polymerization or radical polymerization is preferable.

  Examples of the polysilane and derivatives thereof include compounds described in Chemical Review No. 89, 1359 (1989), British Patent 2300196 published specification. Although the method described in these can be used also for the synthesis method of polysilane and its derivative (s), the Kipping method is used suitably.

  Since the polysiloxane and its derivative have almost no hole transporting property in the siloxane skeleton structure, a compound having the structure of the low molecular hole transporting material in the side chain or main chain is preferable. As polysiloxane and derivatives thereof, compounds having a hole transporting aromatic amine in the side chain or main chain are preferred.

<Light emitting layer>
As the material for forming the light emitting layer (hereinafter referred to as “light emitting material”), a known compound can be used. There are two types of light emitting materials: fluorescent light emitting materials and triple light emitting materials (phosphorescent light emitting materials), which can be classified into low molecular weight light emitting materials and high molecular weight light emitting materials, respectively. In the case of a triple light emitting material, it may be a low molecular weight or high molecular weight light emitting material.

  When the triple light emitting material is a low molecular weight light emitting material, the ratio of the triplet light emitting material contained in the light emitting layer is preferably 1 to 50% by weight, and preferably 2 to 45% by weight, because the device life is improved. %, More preferably 5 to 40% by weight.

  When the triple light emitting material is a high molecular weight light emitting material, the ratio of the central metal atom of the triplet light emitting material contained in the light emitting layer is 0.02 to 10% by weight because the device lifetime is good. Preferably, the content is 0.05 to 9% by weight, more preferably 0.1 to 8% by weight.

  The light-emitting material is preferably a triplet light-emitting material because the light-emitting material has excellent light-emitting efficiency when used for manufacturing an element.

  Examples of the low molecular weight light-emitting material include naphthalene derivatives, anthracene and derivatives thereof, perylene and derivatives thereof, polymethine-based, xanthene-based, coumarin-based, and cyanine-based pigments, 8-hydroxyquinoline and its metal complexes, and aromatics. In addition to aromatic amines, tetraphenylcyclopentadiene and derivatives thereof, tetraphenylbutadiene and derivatives thereof, compounds described in JP-A-57-51781, JP-A-59-194393, triplet light-emitting complexes, etc. Can be mentioned.

Triplet light-emitting complexes include Ir (ppy) ₃ (for example, Appl. Phys. Lett., (1999), 75 (1), 4 and Jpn. J. Appl. Phys., 34 , 1883 (1995)), Btp ₂ Ir (acac) (for example, Appl. Phys. Lett., (2001), 78 (11), 1622), FIrpic (for example, Inorg. Chem., 2007, 46, 11082), luminescent material A, luminescent material B, luminescent material C, luminescent material D, luminescent material E, ADS066GE commercially available from American Dice Source, PtOEP with platinum as the central metal (eg Nature, (1998), 395, 151), Eu (TTA) ₃ phen with europium as the central metal, Proc. SPIE-Int. Soc. Opt. Eng. (2001), 4105 (Organic Light-Emitting Materials and Devices IV), 119, J. Am. Chem. Soc., (2001), 123, 4304, Appl. Phys. Lett., (1997), 71 (18), 2596, Syn. Met., (1998) , 97 (2), 113, Syn. Met., (1999), 99 (2), 127, Adv. Mater., (1999), 11 (10), 852, etc., and derivatives thereof Raised It is done.

  Examples of the high-molecular-weight light-emitting material include WO99 / 13692, WO99 / 48160, GB2340304A, WO00 / 53656, WO01 / 19834, WO00 / 55927, GB2348316, WO00 / 46321, WO00 / 064653, WO99 / 54943, WO99 / 54385, US5777070. WO98 / 06773, WO97 / 05184, WO00 / 35987, WO00 / 53655, WO01 / 34722, WO99 / 24526, WO00 / 22027, WO00 / 22026, WO98 / 27136, US573636, WO98 / 12262, US5741921, WO97 / 09394, WO96 / 29356, WO96 / 10617, EP07007020, WO95 / 07955, JP-A-2 01-181618, JP-A-2001-123156, JP-A-2001-3045, JP-A-2000-351967, JP-A-2000-303066, JP-A-2000-299189, JP-A-2000-252065, JP-A-2000-136379, JP-A-2000-2000 104057, JP 2000-80167, JP 10-324870, JP 10-114891, JP 9-111233, JP 9-45478, and the like, polyfluorenes, derivatives thereof and fluorene copolymers, Examples include polyarylene, its derivatives and arylene copolymers, polyarylene vinylene, its derivatives and arylene vinylene copolymers, and (co) polymers of aromatic amines and their derivatives.

  The light emitting layer may further contain the other hole transport material described above and an electron transport material described later.

  The thickness of the light emitting layer may be adjusted so that the driving voltage and the light emission efficiency are moderate values, but is usually 1 nm to 1 μm, preferably 2 to 500 nm, and more preferably 5 to 200 nm. .

  Examples of the method for forming the light emitting layer include a method in which a solution containing a light emitting material or the like is prepared and a film is formed using the solution. The film formation method includes spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, flexographic printing. Coating methods such as the printing method, offset printing method, and ink jet printing method can be used, but the screen printing method, flexographic printing method, offset printing method, ink jet printing are easy in that pattern formation and multi-color coating are easy. A printing method such as a method is preferred.

<Anode, cathode>
At least one of the anode and the cathode is preferably transparent or translucent, and the anode side is more preferably transparent or translucent.

  Examples of the material of the anode include a conductive metal oxide film, a translucent metal thin film, and the like, but indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO) that is a composite thereof. Films made of conductive inorganic compounds made of indium, zinc, oxide, etc., NESA, gold, platinum, silver, copper, polyaniline and derivatives thereof, polythiophene and derivatives thereof are preferable, ITO, indium zinc oxide Tin oxide is more preferable.

  Examples of the method for forming the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.

  The thickness of the anode may be adjusted in consideration of light transmittance and electrical conductivity, preferably 10 nm to 10 μm, more preferably 20 nm to 1 μm, still more preferably 50 to 500 nm, and particularly preferably 50 to 200 nm. preferable.

  In order to facilitate charge injection, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided on the anode. .

  The material of the cathode is preferably a material having a small work function, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium. , Europium, terbium, ytterbium, etc., and two or more alloys thereof, or one or more of them, and among gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin More preferred are alloys with one or more of these, graphite, or graphite intercalation compounds.

  Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

  The cathode may have a laminated structure of two or more layers.

  The thickness of the cathode may be adjusted in consideration of electric conductivity and durability, but is preferably 10 nm to 10 μm, more preferably 20 nm to 1 μm, still more preferably 50 to 500 nm, and particularly preferably 50 to 200 nm.

  Examples of the method for forming the cathode include a vacuum deposition method, a sputtering method, and a laminating method in which a metal thin film is thermocompression bonded.

<Other layers>
A layer made of a conductive polymer, a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like, or an electron transport layer may be provided between the cathode and the light emitting layer.

  As the electron transport material used for the electron transport layer, known compounds can be used, but oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and Derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene And its derivatives, as well as JP-A 63-70257, JP-A 63-175860, JP-A 2-135359, JP 2-135361, JP 2-20988, JP The compounds described in JP-A-37992 and JP-A-3-152184 are preferred, and oxadiazole derivatives, benzoquinone and derivatives thereof, anthraquinones and derivatives thereof, 8-hydroxyquinoline and metal complexes of derivatives thereof, polyquinoline and derivatives thereof. Derivatives, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof are more preferred, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, Tris (8-quinolinol) aluminum and polyquinoline are particularly preferred.

  As a method for forming the electron transport layer, when a low molecular weight electron transport material is used, a vacuum deposition method from powder, a method by film formation from a solution or a molten state, and a high molecular weight electron transport material are used. In some cases, a method by film formation from a solution or a molten state can be mentioned. When forming a film from a solution or a molten state, a polymer binder may be used in combination.

  When the electron transport layer is formed by a solution, an organic solvent capable of dissolving the electron transport material and / or polymer binder, for example, a chlorinated solvent such as chloroform, methylene chloride, dichloroethane, or an ether type such as tetrahydrofuran. Solvents, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone and methyl ethyl ketone, and ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate can be used.

  Examples of the method for forming the electron transport layer include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, and cap coating. Examples thereof include coating methods such as a coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an ink jet printing method, and a nozzle coating method.

  The polymer binder that can be used for forming the electron transport layer is preferably a compound that does not extremely inhibit charge transport and does not strongly absorb visible light, such as poly (N-vinylcarbazole) and 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, poly More preferred are vinyl chloride and polysiloxane.

  The thickness of the electron transport layer may be adjusted so that the drive voltage and the light emission efficiency are appropriate values, but it needs to have a thickness that does not cause pinholes. If the electron transport layer is too thick, the driving voltage tends to increase. Therefore, the thickness of the electron transport layer is preferably 1 nm to 1 μm, more preferably 2 to 500 nm, and still more preferably 5 to 200 nm.

  In the organic electroluminescence device of the present invention, when a plurality of organic layers are laminated, for example, when a light emitting layer adjacent to a hole transport layer is formed, particularly when both layers are formed by a coating method, 2 The materials of the two layers can mix and adversely affect device characteristics. When the light emitting layer is formed by the coating method after the hole transport layer is formed by the coating method, as a method for suppressing the mixing of the materials of the two layers, the positive transport layer is formed after the hole transport layer is formed by the coating method. A method of forming the light emitting layer after heating the hole transporting layer and insolubilizing it in an organic solvent used for producing the light emitting layer can be mentioned. The heating temperature is usually 150 to 300 ° C., and the time is usually 1 minute to 1 hour. In this case, in order to remove components that have not been insolubilized by heating, the hole transport layer may be rinsed with an organic solvent used for forming the light emitting layer after heating and before forming the light emitting layer. When the insolubilization is sufficiently performed, rinsing with a solvent can be omitted. In order for the insolubilization to be sufficiently performed, a 2,2′-bipyridinediyl group-free hole transporting polymer compound or a 2,2′-bipyridinediyl group-containing polymer compound used for the hole transport layer is used as a molecule. A compound containing at least one polymerizable reactive group therein, among them, a compound in which the number of the polymerizable reactive group is 5% or more with respect to the number of repeating units in the molecule may be used.

When the organic electroluminescence device of the present invention has a charge injection layer, and the charge injection layer is a layer containing the conductive polymer, the electrical conductivity of the conductive polymer is 10 ⁻⁵ to 10 ³ S. / Cm is preferable, and in order to reduce the leakage current between the light emitting pixels, 10 ⁻⁵ to 10 ² S / cm is more preferable, and 10 ⁻⁵ to 10 ¹ S / cm is still more preferable. In order to set the electric conductivity of the conductive polymer to 10 ⁻⁵ to 10 ³ S / cm, the conductive polymer is usually doped with an appropriate amount of ions.

  The ions to be doped are anions for the hole injection layer and cations for the electron injection layer.

  Examples of the anion include polystyrene sulfonate ion, alkylbenzene sulfonate ion, camphor sulfonate ion, and the like.

  Examples of the cation include lithium ion, sodium ion, potassium ion, and tetrabutylammonium ion.

  The thickness of the charge injection layer is preferably 1 to 100 nm, and more preferably 2 to 50 nm.

  The material used for the charge injection layer may be selected in relation to the material of the electrode and the adjacent layer. For example, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythieny. Lembinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanine (copper phthalocyanine, etc.), carbon, etc. It is done. A known manufacturing method can be employed for manufacturing the charge injection layer.

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

As the organic electroluminescence device of the present invention, a first composition, a second composition,
Or, an organic electroluminescence element produced by a production process including a step of forming a hole transport layer by a coating method using a combination thereof is preferable, and after forming the hole transport layer by a coating method, An organic electroluminescent element manufactured by a manufacturing process including a step of heating the hole transport layer and insolubilizing the organic solvent used for the preparation of the light emitting layer is more preferable. An organic electroluminescence device manufactured by a manufacturing process including a step of forming a light emitting layer using a solution containing the light emitting material adjacent to the insolubilized hole transport layer is more preferable.

  The organic electroluminescence element of the present invention can be used as a backlight for a planar light source, a segment display device, a dot matrix display device, and a liquid crystal display device. In order to obtain planar light emission using the organic electroluminescence element of the present invention, the planar anode and cathode may be arranged so as to overlap each other. Also, in order to obtain pattern-like light emission, a method of installing a mask having a pattern-like window on the surface of the planar organic electroluminescence element, the organic layer of the non-light-emitting part is formed extremely thick In addition, there are a method of making no light emission, and a method of forming either the anode or the cathode, or both electrodes in a pattern. By forming a pattern by any one of these methods and arranging several electrodes so that they can be turned on and off independently, a segment type display element capable of displaying numbers, letters, simple symbols and the like can be obtained. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multi-color display are possible by a method of separately coating a plurality of types of polymer phosphors having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix element can be driven passively, or may be actively driven in combination with a TFT or the like. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like. Further, the planar organic electroluminescence element is self-luminous and thin, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source or display device.

  Hereinafter, examples will be shown to describe the present invention in more detail, but the present invention is not limited thereto.

  For the number average molecular weight and the weight average molecular weight, the number average molecular weight and the weight average molecular weight in terms of polystyrene were determined by size exclusion chromatography (SEC). Gel permeation chromatography whose mobile phase is an organic solvent in SEC is called gel permeation chromatography (GPC). The molecular weight was measured by GPC under the following (GPC-condition 1) or (GPC-condition 2).

(GPC-Condition 1)
The polymer to be measured was dissolved in tetrahydrofuran at a concentration of about 0.05% by weight, and 30 μL was injected into GPC (manufactured by Shimadzu Corporation, trade name: LC-10Avp). Tetrahydrofuran was used as the mobile phase of GPC, and flowed at a flow rate of 0.6 mL / min. As for the column, two TSKgel SuperHM-H (manufactured by Tosoh) and one TSKgel SuperH2000 (manufactured by Tosoh) were connected in series. A differential refractive index detector (manufactured by Shimadzu Corporation, trade name: RID-10A) was used as the detector.

(GPC-Condition 2)
The polymer to be measured was dissolved in tetrahydrofuran to a concentration of about 0.05% by weight, and 10 μL was injected into GPC (manufactured by Shimadzu Corporation, trade name: LC-10Avp). Tetrahydrofuran was used as the mobile phase of GPC and was allowed to flow at a flow rate of 2.0 mL / min. As a column, PLgel MIXED-B (manufactured by Polymer Laboratories) was used. A UV-VIS detector (manufactured by Shimadzu Corporation, trade name: SPD-10Avp) was used as the detector.

  The measurement of LC-MS was performed by the following method. The measurement sample was dissolved in chloroform or tetrahydrofuran to a concentration of about 2 mg / mL, and 1 μL was injected into LC-MS (manufactured by Agilent Technologies, trade name: 1100LCMSD). For the mobile phase of LC-MS, ion-exchanged water, acetonitrile, tetrahydrofuran and a mixed solution thereof were used, and acetic acid was added as necessary. As the column, L-column 2 ODS (3 μm) (manufactured by Chemicals Evaluation and Research Institute, inner diameter: 2.1 mm, length: 100 mm, particle size: 3 μm) was used.

TLC-MS was measured by the following method. The measurement sample was dissolved in chloroform, toluene or tetrahydrofuran, and the resulting solution was applied in small amounts onto the surface of a TLC glass plate (trade name: Silica gel 60 F ₂₅₄ manufactured by Merck) that had been cut in advance. This was measured with TLC-MS (trade name: JMS-T100TD, manufactured by JEOL Ltd.) using helium gas heated to 240 to 350 ° C.

  NMR measurement was performed by dissolving 5 to 20 mg of a measurement sample in about 0.5 mL of deuterated chloroform, and using NMR (trade name MERCURY 300, manufactured by Varian, Inc.).

  <Synthesis Example 1> (Synthesis of Compound M-1)

To a 2 L four-necked flask purged with argon, 20 g (109 mmol) of 5,5′-dimethyl-2,2′-bipyridine and 400 mL of dehydrated THF were added and cooled to −78 ° C. while stirring. A solution obtained by diluting 105 mL (113 mmol) of a 1.08 M hexane / THF mixed solution of lithium diisopropylamide (LDA) with 100 mL of dehydrated THF was added dropwise thereto. After completion of dropping, the mixture was stirred at 0 ° C. for 1.5 hours. The reaction solution was cooled again to -78 ° C, and then a solution of 11.9 g (45.2 mmol) of 1,4-bis (bromomethyl) benzene dissolved in 100 mL of dehydrated THF was added dropwise. Stir for 2 hours. Then, it stirred at room temperature for 1 hour, about 20 mL of ion-exchange water was added, and reaction was stopped. The solvent was distilled off from the reaction solution under reduced pressure, the resulting residue was dispersed in ion-exchanged water, and an insoluble red solid was collected by filtration. This red solid was washed with methanol, and only insoluble components were taken out. This was purified by medium pressure preparative chromatography (eluent CHCl ₃ : hexane: Et ₃ N = 90: 9: 1 (volume ratio), stationary phase: silica gel) and further contained 5% by volume of ethylenediamine. Separation operation was performed with toluene and ion-exchanged water. The organic layer was dehydrated with anhydrous sodium sulfate and then filtered. Activated charcoal was added to the filtrate, heated and stirred at 80 ° C. for 30 minutes, and suction filtration was performed while hot. The obtained filtrate was distilled off under reduced pressure to obtain 4 g of a white powder. This white powder was dispersed in 100 mL of acetonitrile, and the insoluble matter was collected by filtration and dried under reduced pressure at 60 ° C. to obtain 3 g of Compound M-1.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 2.38 (s, 6H), 2.94 (br, 8H), 7.07 (s, 4H), 7.54 (d, J = 8.1 Hz) 2H), 7.60 (d, J = 8.1 Hz, 2H), 8.25 (d, J = 8.1 Hz, 4H), 8.45 (s, 2H), 8.49 (s, 2H)
¹³ C-NMR (75.5 MHz, CDCl ₃ ): δ 18.47, 34.89, 37.14, 120.46, 120.49, 128.71, 133.19, 136.84, 137.04, 137.53, 138.75, 149.42, 149.69, 153.85, 154.34
TLC-MS (DART, positive): m / z ⁺ = 471 [M + H] ⁺

  <Synthesis Example 2> (Synthesis of Compound M-2)

9.0 g (49 mmol) of 5,5′-dimethyl-2,2′-bipyridine and 430 mL of dehydrated THF were added to a 2 L four-neck flask purged with argon, and the mixture was cooled to −78 ° C. while stirring. Thereto was added dropwise a solution obtained by diluting 100 mL (107 mmol) of a 1.08 M hexane / THF mixed solution of lithium diisopropylamide with 100 mL of dehydrated THF. After completion of dropping, the mixture was stirred at 0 ° C. for 1.5 hours. The reaction solution was cooled again to −78 ° C., and a solution obtained by diluting 11.9 g (107 mmol) of 1-bromohexane with 100 mL of dehydrated THF was added dropwise. After completion of the dropwise addition, the mixture was stirred at −78 ° C. for 2 hours. Then, it stirred at room temperature for 1 hour, about 20 mL of ion-exchange water was added, and reaction was stopped. The solvent was distilled off from the reaction solution under reduced pressure, and the resulting residue was dispersed in 50 mL of diethyl ether and washed three times with an aqueous sodium chloride solution. The organic layer was dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a pale yellow viscous liquid. The viscous liquid was purified by medium pressure preparative chromatography (eluent: CHCl ₃ , stationary phase: silica gel) to obtain about 6.3 g of a yellowish viscous solid. This viscous solid is dissolved in 10 mL of ethanol, cooled to about −30 ° C., and the precipitated crystals are collected by filtration and dried under reduced pressure at room temperature to give 6 g of compound M-2 (melting point: 47 ° C.) as colorless plate crystals. Obtained (yield 35%).

¹ H-NMR (300 MHz, CDCl ₃ ): δ 0.88 (t, J = 6.5 Hz, 6H), 1.26-1.37 (m, 16H), 1.60-1.70 (m, 4H), 2.65 (t, J = 7.5 Hz, 4H), 7.60 (d, J = 8.1 Hz, 2H), 8.26 (d, J = 8.1 Hz, 2H), 8. 48 (s, 2H)
¹³ C-NMR (75.5 MHz, CDCl ₃ ): δ 14.07, 22.62, 29.08, 31.09, 31.76, 32.83, 120.35, 136.70, 137.85, 149.25, 153.99
TLC-MS (DART, positive): m / z ⁺ = 353 [M + H] ⁺

  <Synthesis Example 3> (Synthesis of Compound M-3)

  Into a 500 mL three-necked round bottom flask purged with nitrogen (replacement of the atmosphere in the container from air to nitrogen hereinafter), 196 mg of palladium (II) acetate, tris (2-methylphenyl) 731 mg of phosphine and 100 mL of toluene were taken and stirred at room temperature. To the reaction solution was added 20.0 g of diphenylamine, 23.8 g of 3-bromobicyclo [4.2.0] octa-1,3,5-triene and 400 mL of toluene, followed by 22.8 g of sodium tert-butoxide. Heated to reflux for 22 hours. The reaction was stopped by adding 30 mL of 1 M hydrochloric acid thereto. The obtained reaction mixture was washed with 100 mL of 2M aqueous sodium carbonate solution, the organic layer was passed through alumina, and the eluate was collected, from which the solvent was distilled off under reduced pressure. Isopropyl alcohol was added to the resulting yellow oily residue and stirred, and the resulting precipitate was collected by filtration. The precipitate was recrystallized from isopropyl alcohol to obtain 3-N, N-diphenylaminobicyclo [4.2.0] octa-1,3,5-triene. In a 250 mL round bottom flask, dimethylformamide (DMF) containing 3-N, N-diphenylaminobicyclo [4.2.0] octa-1,3,5-triene (8.00 g) and 5 drops of glacial acetic acid. 100 mL was taken and stirred. N-bromosuccinimide (NBS) (10.5 g) was added thereto and stirred for 5 hours. The obtained reaction mixture was poured into 600 mL of methanol / water (volume ratio 1: 1), and when the reaction was stopped, precipitation occurred. This precipitate was collected by filtration and recrystallized from isopropyl alcohol to obtain Compound M-3.

¹ H NMR (300 MHz, CDCl ₃ ): δ 3.11-3.15 (m, 4H), 6.80 (br, 1H), 6.87-6.92 (m, 5H), 6.96 (d 1H), 7.27-7.33 (m, 4H)

  <Synthesis Example 4> (Synthesis of Compound M-4)

  In a reactor purged with nitrogen, 0.90 g of palladium (II) acetate, 2.435 g of tris (2-methylphenyl) phosphine, and 125 mL of toluene were stirred at room temperature for 15 minutes. 27.4 g of 2,7-dibromo-9,9-dioctylfluorene, 22.91 g of (4-methylphenyl) phenylamine, and 19.75 g of sodium tert-butoxide were added thereto, and the mixture was heated to reflux overnight. Then, the mixture was cooled to room temperature and washed with 300 mL of water. The organic layer was taken out and the solvent was distilled off under reduced pressure. The residue was dissolved in 100 mL of toluene, and the resulting solution was passed through an alumina column. The eluate was concentrated under reduced pressure, and methanol was added thereto to form a precipitate. The precipitate was collected by filtration and recrystallized from p-xylene. The crystals were redissolved in 100 mL of toluene, and the resulting solution was passed through an alumina column. The eluate was concentrated to 50 to 100 mL and then poured into 250 mL of stirred methanol, resulting in precipitation. The precipitate was collected and dried at room temperature under reduced pressure for 18 hours. As a result, white 2,7-bis [N- (4-methylphenyl) -N-phenyl] amino-9,9-dioctylfluorene (25.0 g) was collected. )was gotten.

  To the nitrogen-substituted reactor, 12.5 g of 2,7-bis [N- (4-methylphenyl) -N-phenyl] amino-9,9-dioctylfluorene and 95 mL of dichloromethane were added, and the reaction solution was stirred while stirring. Cooled to 10 ° C. There, the solution of N-bromosuccinimide 5.91g dissolved in DMF20mL was dripped slowly. After stirring for 3.5 hours, the mixture was mixed with 450 mL of cold methanol, and the resulting precipitate was collected by filtration and recrystallized from p-xylene. The obtained crystals were recrystallized again using toluene and methanol to obtain 12.1 g of Compound M-4 as a white solid.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 0.61-0.71 (m, 4H), 0.86 (t, J = 6.8 Hz, 6H), 0.98-1.32 (m, 20H) ) 1.72-1.77 (m, 4H), 2.32 (br, 6H), 6.98-7.08 (m, 16H), 7.29 (d, J = 8.3 Hz, 4H) ), 7.44 (br, 2H)

  <Synthesis Example 5> (Synthesis of Compound M-5)

  To a 3 L four-necked flask purged with nitrogen were added 1.10 g of palladium (II) acetate, 1.51 g of tris (2-methylphenyl) phosphine and 370 mL of toluene, and the mixture was stirred at room temperature for 30 minutes. Thereto, 143 g of phenoxazine, 97.1 g of sodium-tert-pentoxide and 800 mL of toluene were added and stirred, and then a solution of 133 mL of 1-bromo-4-butylbenzene dissolved in 60 mL of toluene was added dropwise to the reaction vessel. The reaction solution was stirred at 105 ° C. for 5 hours, cooled to room temperature, and filtered through a glass filter covered with alumina. The obtained filtrate was washed with 3.5% by weight hydrochloric acid, and then the solvent was distilled off under reduced pressure. The obtained residue was recrystallized using 30 mL of toluene and 700 mL of isopropyl alcohol to obtain 209 g of N- (4-butylphenyl) phenoxazine.

  N- (4-butylphenyl) phenoxazine (209 g) and dichloromethane (700 mL) were added to a nitrogen-substituted 3 L four-necked flask, and the mixture was stirred at room temperature. To this, 340 mL of a solution prepared by dissolving 190 g of 1,3-dibromo-5,5-dimethylhydantoin in 200 mL of DMF was added dropwise. Methanol was added to the resulting reaction mixture and stirred for 1 hour while slowly cooling to 10 ° C., and the deposited precipitate was collected by filtration and washed with methanol to obtain 284 g of Compound M-5 as a pale white green solid.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 0.97 (t, J = 7.3 Hz, 3H), 1.35 to 1.47 (m, 2H), 1.61-1.72 (m, 2H), 2.69 (t, J = 7.8 Hz, 2H), 5.76 (d, J = 8.6 Hz, 2H), 6.68 (dd, J = 2.2 Hz and 8.6 Hz, 2H) ), 6.79 (d, J = 2.2 Hz, 2H), 7.16 (d, J = 8.1 Hz, 2H), 7.38 (d, J = 8.1 Hz, 2H)

  <Synthesis Example 6> (Synthesis of Compound M-6)

To a 300 ml four-necked flask, 8.08 g of 1,4-dihexyl-2,5-dibromobenzene, 12.19 g of bis (pinacolato) diboron, and 11.78 g of potassium acetate were placed, and the atmosphere in the flask was replaced with argon. Thereto, 100 ml of dehydrated 1,4-dioxane was charged and deaerated with argon. [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (Pd (dppf) ₂ Cl ₂ ) (0.98 g) was charged, further deaerated with argon, and heated to reflux for 6 hours. Toluene was added thereto and washed with ion-exchanged water. To the organic layer after washing, anhydrous sodium sulfate and activated carbon were added, and the mixture was filtered through a funnel pre-coated with celite. The obtained filtrate was concentrated to obtain 11.94 g of dark brown crystals. The crystals were recrystallized from n-hexane and washed with methanol. The obtained crystals were dried under reduced pressure to obtain 4.23 g of white needle crystals of Compound M-6 (yield 42%).

¹ H-NMR (300 MHz, CDCl ₃ ): δ 0.88 (t, 6H), 1.23-1.40 (m, 36H), 1.47-1.56 (m, 4H), 2.81 (T, 4H), 7.52 (s, 2H)
LC-MS (ESI, positive): m / z ⁺ = 573 [M + K] ⁺

  <Synthesis Example 7> (Synthesis of Compound M-7)

  Under a nitrogen atmosphere, a solution of 27.1 g of 1,4-dibromobenzene in 217 ml of dehydrated diethyl ether was cooled using a dry ice / methanol mixed bath. To the obtained suspension, 37.2 ml of a 2.77M n-butyllithium hexane solution was slowly added dropwise, followed by stirring for 1 hour to prepare a lithium reagent.

  In a nitrogen atmosphere, a suspension of 10.0 g of cyanuric chloride in 68 ml of dehydrated diethyl ether was cooled using a dry ice / methanol mixed bath, the lithium reagent was slowly added, and the mixture was warmed to room temperature and reacted at room temperature. The resulting product was filtered and dried under reduced pressure. 16.5 g of the obtained solid was purified to obtain 13.2 g of acicular crystals.

窒素雰囲気下、マグネシウム１．３７ｇに脱水テトラヒドロフラン６５ｍｌを加えた懸濁液に、４−ヘキシルブロモベンゼン１４．２ｇの脱水テトラヒドロフラン １５ｍｌ溶液を少量ずつ加え、加熱して、還流下で攪拌した。放冷後、反応溶液にマグネシウム０．３９ｇを追加し、再び加熱して、還流下で反応させ、グリニャール試薬を調製した。

Under a nitrogen atmosphere, to a suspension obtained by adding 65 ml of dehydrated tetrahydrofuran to 1.37 g of magnesium, a solution of 14.2 g of 4-hexylbromobenzene in 15 ml of dehydrated tetrahydrofuran was added little by little, heated and stirred under reflux. After allowing to cool, 0.39 g of magnesium was added to the reaction solution, heated again, and reacted under reflux to prepare a Grignard reagent.

  Under a nitrogen atmosphere, the Grignard reagent was added to a suspension of 100 ml of dehydrated tetrahydrofuran of 12.0 g of the needle-like crystals with stirring and heated to reflux. After cooling, the reaction solution was washed with dilute hydrochloric acid aqueous solution. The organic layer and the aqueous layer were separated, and the aqueous layer was extracted with diethyl ether. The obtained organic layers were combined and washed again with water. The organic layer was dehydrated with anhydrous magnesium sulfate, filtered, and concentrated. The obtained white solid was purified with a silica gel column and further recrystallized to obtain 6.5 g of Compound M-7 as a white solid.

¹ H-NMR (300 MHz, CDCl ₃ ): δ 0.90 (t, J = 6.2 Hz, 3H), 1.25-1.42 (m, 6H), 1.63-1.73 (m, 2H), 2.71 (t, J = 7.6 Hz, 2H), 7.34 (d, J = 7.9 Hz, 2H), 7.65 (d, J = 7.9 Hz, 4H), 8. 53-8.58 (m, 6H)
LC-MS (APCI, positive): m / z ⁺ = 566 [M + H] ⁺

<Synthesis Example 8> (Synthesis of Luminescent Material A: Synthesis of Iridium Complex)
An iridium complex was synthesized according to the synthesis method described in WO02 / 066552. That is, Suzuki coupling of 2-bromopyridine and 1.2 equivalent of 3-bromophenylboric acid under a nitrogen atmosphere (catalyst: tetrakis (triphenylphosphine) palladium (0), base: 2M aqueous sodium carbonate solution, solvent : Ethanol, toluene), the following formula:

で表される２−（３'−ブロモフェニル）ピリジンを得た。

2- (3′-bromophenyl) pyridine represented by the formula:

  Next, Suzuki coupling of tribromobenzene and 2.2 equivalents of 4-tert-butylphenylboric acid under a nitrogen atmosphere (catalyst: tetrakis (triphenylphosphine) palladium (0), base: 2M aqueous sodium carbonate solution) , Solvent: ethanol, toluene) and the following formula:

で表されるブロモ化合物を得た。

The bromo compound represented by this was obtained.

After dissolving this bromo compound in dehydrated THF under a nitrogen atmosphere, the resulting solution was cooled to −78 ° C., and a small excess of tert-butyllithium was added dropwise. Under cooling, B (OC ₄ H ₉ ) ₃ was further added dropwise and reacted at room temperature. The reaction solution was post-treated with 3M hydrochloric acid to obtain the following formula:

で表されるホウ酸化合物を得た。

The boric acid compound represented by this was obtained.

  Suzuki coupling of 2- (3′-bromophenyl) pyridine and 1.2 equivalents of the boric acid compound (catalyst: tetrakis (triphenylphosphine) palladium (0), base: 2M aqueous sodium carbonate solution, solvent: ethanol , Toluene), the following formula:

で表される配位子（即ち、配位子となる化合物）を得た。

Was obtained (that is, a compound to be a ligand).

Under an argon atmosphere, IrCl ₃ .3H ₂ O, 2.2 equivalents of the ligand, 2-ethoxyethanol, and ion-exchanged water were charged and refluxed. The precipitated solid was suction filtered. The obtained solid was washed with ethanol and ion-exchanged water in this order and then dried, and the following formula:

で表される黄色粉体を得た。

A yellow powder represented by

  Under an argon atmosphere, 2 equivalents of the ligand and 2 equivalents of silver trifluoromethanesulfonate are added to the yellow powder and heated in diethylene glycol dimethyl ether to obtain the following formula:

で表されるイリジウム錯体（以下、「発光材料Ａ」と言う。）を得た。

Was obtained (hereinafter referred to as “light-emitting material A”).

¹ H-NMR (300 MHz, CDCl ₃ ): δ 1.38 (s, 54H), 6.93 (dd, J = 6.3 Hz / 6.6 Hz, 3H), 7.04 (br, 3H), 7 .30 (d, J = 7.9 Hz, 3H), 7.48 (d, J = 7.3 Hz, 12H), 7.61-7.70 (m, 21H), 7.82 (s, 6H) 8.01 (s, 3H), 8.03 (d, J = 7.9 Hz, 3H)
LC-MS (APCI, positive): m / z ⁺ = 1677 [M + H] ⁺

<Synthesis Example 9> (Synthesis of Polymer Compound P-1)
In a reaction vessel purged with nitrogen, 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene 17.57 g (33.13 mmol), bis (4-bromophenyl) (4 -Sec-butylphenyl) amine 12.88 g (28.05 mmol), compound M-3 2.15 g (5.01 mmol), methyltrioctylammonium chloride (trade name: Aliquat 336, manufactured by Aldrich) 3 g, and toluene 200 g were weighed. I took it. The reaction vessel was heated to 100 ° C., 7.4 mg of palladium (II) acetate, 70 mg of tris (2-methylphenyl) phosphine, and 64 g of an about 18 wt% aqueous sodium carbonate solution were added, and the mixture was heated for 3 hours or more and stirred. Thereafter, 400 mg of phenylboronic acid was added, and heating and stirring were further continued for 5 hours. The reaction solution was diluted with 1900 g of toluene, washed twice with 60 g of 3% by weight acetic acid aqueous solution and once with 60 g of ion-exchanged water, and then 1.5 g of sodium diethyldithiocarbamate trihydrate was added to the extracted organic layer. Stir for hours. The resulting solution was purified by column chromatography using an equal volume mixture of alumina and silica gel as the stationary phase. The obtained eluate was dropped into methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain polymer compound P-1. The number average molecular weight of polystyrene conversion of the high molecular compound P-1 was 8.9 * 10 < ⁴ >, and the weight average molecular weight of polystyrene conversion was 4.2 * 10 < ⁵ > (GPC-condition 1).

  The polymer compound P-1 has the following formula:

で表される繰り返し単位と、下記式：

And a repeating unit represented by the following formula:

で表される繰り返し単位と、下記式：

And a repeating unit represented by the following formula:

で表される繰り返し単位とが、５０：４２：８のモル比で含まれる共重合体である。

Is a copolymer contained in a molar ratio of 50: 42: 8.

<Synthesis Example 10> (Synthesis of Polymer Compound P-2)
In Synthesis Example 9, the use of Compound M-4 instead of bis (4-bromophenyl) (4-sec-butylphenyl) amine, 2,7-bis (1,3,2-dioxaborolan-2-yl) ) -9,9-Dioctylfluorene, Compound M-4, and Compound M-3 were synthesized in the same manner as in Synthesis Example 9 except that 50: 42: 8 molar ratio was used. . The number average molecular weight in terms of polystyrene of the polymer compound P-2 was 6.0 × 10 ⁴ , and the weight average molecular weight in terms of polystyrene was 4.0 × 10 ⁵ (GPC—Condition 1).

  Polymer compound P-2 has the following formula:

で表される繰り返し単位と、下記式：

And a repeating unit represented by the following formula:

で表される繰り返し単位と、下記式：

And a repeating unit represented by the following formula:

で表される繰り返し単位とが、５０：４２：８のモル比で含まれる共重合体である。

Is a copolymer contained in a molar ratio of 50: 42: 8.

<Synthesis Example 11> (Synthesis of Polymer Compound P-3)
In Synthesis Example 9, the use of Compound M-5 instead of bis (4-bromophenyl)-(4-sec-butylphenyl) -amine, 2,7-bis (1,3,2-dioxaborolane-2 -Yl) -9,9-dioctylfluorene, Compound M-5 and Compound M-3 were used in the same manner as in Synthesis Example 9 except that a molar ratio of 50: 42: 8 was used. -3 was synthesized. The polymer compound P-3 had a polystyrene-equivalent number average molecular weight of 6.0 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 2.3 × 10 ⁵ (GPC—Condition 1).

  The polymer compound P-3 has the following formula:

で表される繰り返し単位と、下記式：

And a repeating unit represented by the following formula:

で表される繰り返し単位と、下記式：

And a repeating unit represented by the following formula:

で表される繰り返し単位とが、５０：４２：８のモル比で含まれる共重合体である。

Is a copolymer contained in a molar ratio of 50: 42: 8.

<Synthesis Example 12> (Synthesis of Polymer Compound P-4)
Under nitrogen atmosphere, Compound M-6 (3.13 g), Compound M-7 (0.70 g), 2,7-dibromo-9,9-dioctylfluorene (2.86 g), palladium (II) acetate (2.1 mg), tris (2-methoxy) 13.4 mg of phenyl) phosphine and 80 mL of toluene were mixed and heated to 100 ° C. with stirring. To the reaction solution, 21.5 ml of 20 wt% tetraethylammonium hydroxide aqueous solution was added dropwise and refluxed for 5 hours. To the reaction solution, 78 mg of phenylboric acid, 2.1 mg of palladium (II) acetate, 13.3 mg of tris (2-methoxyphenyl) phosphine, 6 mL of toluene, and 21.5 ml of 20 wt% tetraethylammonium hydroxide aqueous solution were added. Refluxed for 5 hours. Next, 70 ml of a 0.2 M aqueous solution of sodium diethyldithiocarbamate was added thereto and stirred at 85 ° C. for 2 hours. The reaction solution was cooled to room temperature and washed 3 times with 82 ml of water, 3 times with 82 ml of a 3 wt% aqueous acetic acid solution and 3 times with 82 ml of water. When the organic layer was dropped into 1000 ml of methanol, a precipitate was formed. The precipitate was filtered and then dried to obtain a solid. This solid was dissolved in toluene and purified by passing through an alumina column and a silica gel column. The obtained eluate was dropped into 1500 ml of methanol, and the resulting precipitate was collected by filtration and dried to obtain 3.43 g of polymer compound P-4. The polymer compound P-4 had a polystyrene-equivalent number average molecular weight of 1.9 × 10 ⁵ and a polystyrene-equivalent weight average molecular weight of 5.7 × 10 ⁵ (GPC—Condition 1).

  The polymer compound P-4 has the following formula:

で表される繰り返し単位と、下記式：

And a repeating unit represented by the following formula:

で表される繰り返し単位と、下記式：

And a repeating unit represented by the following formula:

で表される繰り返し単位とが、５０：４０：１０のモル比で含まれる共重合体である。

Is a copolymer contained in a molar ratio of 50:40:10.

<Synthesis Example 13> (Synthesis of Polymer Compound P-5)
Under a nitrogen atmosphere, 3.13 g of compound M-6, 3.58 g of 2,7-dibromo-9,9-dioctylfluorene, 2.2 mg of palladium (II) acetate, 13.4 mg of tris (2-methoxyphenyl) phosphine, and 80 mL of toluene was mixed and heated to 100 ° C. To the reaction solution, 21.5 ml of a 20 wt% tetraethylammonium hydroxide aqueous solution was added dropwise and refluxed for 4.5 hours. After the reaction, 78 mg of phenylboric acid, 2.2 mg of palladium (II) acetate, 13.4 mg of tris (2-methoxyphenyl) phosphine, 20 mL of toluene, and 21.5 mL of 20 wt% tetraethylammonium hydroxide aqueous solution were further added. Refluxed for 15 hours. Next, 70 ml of a 0.2 M aqueous solution of sodium diethyldithiocarbamate was added thereto and stirred at 85 ° C. for 2 hours. The reaction solution was cooled to room temperature and washed 3 times with 82 ml of water, 3 times with 82 ml of a 3% by weight aqueous acetic acid solution and 3 times with 82 ml of water. When the organic layer was dropped into 1200 ml of methanol, a precipitate was formed. The precipitate was filtered and then dried to obtain a solid. This solid was dissolved in toluene and purified by passing through an alumina column and a silica gel column. When the obtained eluate was dropped into 1500 ml of methanol, 3.52 g of polymer compound P-5 was obtained. The polymer compound P-5 had a polystyrene-equivalent number average molecular weight of 3.0 × 10 ⁵ and a polystyrene-equivalent weight average molecular weight of 8.4 × 10 ⁵ (GPC—Condition 1).

  The polymer compound P-5 has the following formula:

で表される繰り返し単位からなる共重合体である。

It is a copolymer consisting of repeating units represented by

  <Synthesis Example 14> (Synthesis of Compound M-8)

Under an inert gas atmosphere, 37.0 g of bis (pinacolato) diboron, 103.5 g of 2,5-dibromopyridine, [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (Pd (dppf) ₂ Cl ₂ ) 7.14 g, 1,1′-bis (diphenylphosphino) ferrocene (dppf) 4.85 g, sodium hydroxide 35.0 g, and 1,4-dioxane 568 mL at 100-105 ° C. for 95 hours. Stir. After cooling the reaction solution to room temperature, 460 mL of toluene was added and stirred at room temperature for 20 minutes. The obtained solution was filtered through a filter packed with silica gel, and the filtrate was concentrated to dryness to obtain a solid. The solid was repeatedly recrystallized, and then the obtained solid was filtered with acetonitrile (650 mL) while hot, and the resulting filtrate was concentrated to dryness. The obtained solid was recrystallized from chloroform to obtain 1.17 g of Compound M-8 (yield 3%, HPLC area percentage 99.5%, GC area percentage 99.2%).

¹ H-NMR (299.4 MHz, CDCl ₃ ): 7.94 (d, 2H), 8.29 (d, 2H), 8.71 (s, 2H)
LC-MS (APPI (positive)): m / z ⁺ = 313 [M + H] ⁺

<Synthesis Example 15> (Synthesis of Polymer Compound P-6)
In a reaction vessel purged with nitrogen, 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (1.04 g, 1.62 mmol), bis (4-bromophenyl) (4 -Sec-butylphenyl) amine 0.48 g (1.05 mmol), Compound M-3 0.10 g (0.23 mmol), Compound M-8 0.10 g (0.32 mmol), Palladium acetate (II) 0.5 mg , 3.6 mg of tris (2-methoxyphenyl) phosphine, and 32 mL of toluene were mixed and heated to 100 ° C. To the reaction solution, 5.5 ml of a 20 wt% tetraethylammonium hydroxide aqueous solution was added dropwise and refluxed for 5 hours. After the reaction, 20 mg of phenylboric acid, 0.5 mg of palladium (II) acetate, 3.4 mg of tris (2-methoxyphenyl) phosphine, 3 mL of toluene, and 5.6 ml of 20% by weight tetraethylammonium hydroxide aqueous solution were further added. Refluxed for 17 hours. Next, 18 ml of a 0.2 M aqueous solution of sodium diethyldithiocarbamate was added thereto and stirred at 85 ° C. for 2 hours. The reaction solution was cooled to room temperature and washed twice with 25 ml of water, twice with 25 ml of a 3 wt% aqueous acetic acid solution and three times with 25 ml of water. When the organic layer was dropped into 200 ml of methanol, precipitation occurred. The precipitate was filtered and dried to obtain a solid. This solid was dissolved in toluene and purified by passing through an alumina column and a silica gel column. When the obtained eluate was dropped into 300 ml of methanol, 0.77 g of polymer compound P-6 was obtained. The polymer compound P-6 had a polystyrene-equivalent number average molecular weight of 1.8 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 6.6 × 10 ⁴ (GPC—Condition 2).

  The polymer compound P-6 has the following formula:

で表される繰り返し単位と、下記式：

And a repeating unit represented by the following formula:

で表される繰り返し単位と、下記式：

And a repeating unit represented by the following formula:

で表される繰り返し単位と、下記式：

And a repeating unit represented by the following formula:

で表される繰り返し単位とが、５０：３２：７：１０のモル比で含まれる共重合体である。

Is a copolymer contained in a molar ratio of 50: 32: 7: 10.

<Example 1> (Production of organic electroluminescence element 1)
Poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (trade name: CLEVIOS P AI4083) (manufactured by HC Stark) (hereinafter referred to as “CLEVIOS P AI4083”) CLEVIOS P ") was applied, a film was formed to a thickness of about 65 nm by spin coating, and dried on a hot plate at 200 ° C for 10 minutes. Next, 0.7% by weight (by weight ratio, polymer compound P-1 / compound M) was added to polymer compound P-1 and compound M-1 in xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)). −1 = 90/10), the obtained xylene solution is placed on the film of CLEVIOS P, and formed into a film having a thickness of about 20 nm by a spin coating method. It was dried at 180 ° C. for 60 minutes under a nitrogen atmosphere of 10 ppm or less (weight basis). Next, 1.1% by weight (by weight ratio, polymer compound P-5 / luminescent material A) of polymer compound P-5 and luminescent material A in xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) = 70/30). The obtained xylene solution was placed on the polymer compound P-1 / compound M-1 film, and the light emitting layer 1 was formed to a thickness of about 80 nm by spin coating. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited on the light-emitting layer 1 film at about 5 nm as a cathode, and then aluminum was vapor-deposited on the barium layer at about 60 nm. The organic electroluminescent element 1 was produced by sealing using a glass substrate after vapor deposition.

When a voltage was applied to the organic electroluminescence element 1, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 26.8 cd / A, and the voltage at that time was 9.3 V. When a voltage was applied after the luminance was reduced by half, the voltage at a luminance of 1000 cd / m ² was 12.0V. The voltage increase at 1000 cd / m ² was 2.7V.

<Example 2> (Preparation of organic electroluminescence element 2)
A suspension of CLEVIOS P is placed on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering, and a film is formed to a thickness of about 65 nm by spin coating. Dried. Next, 0.7% by weight (by weight ratio, polymer compound P-1 / compound M) was added to polymer compound P-1 and compound M-1 in xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)). −1 = 90/10), the obtained xylene solution is placed on the film of CLEVIOS P, and formed into a film having a thickness of about 20 nm by a spin coating method. It was dried at 180 ° C. for 60 minutes under a nitrogen atmosphere of 10 ppm or less (weight basis). Next, the polymer compound P-4 and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.5 wt% (by weight ratio, the polymer compound P-4 / the light emitting material A). = 70/30). The obtained xylene solution was placed on the polymer compound P-1 / compound M-1 film, and the light emitting layer 2 was formed to a thickness of about 80 nm by spin coating. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited on the light-emitting layer 2 film at about 5 nm as a cathode, and then aluminum was vapor-deposited on the barium layer at about 60 nm. The organic electroluminescent element 2 was produced by sealing using a glass substrate after vapor deposition.

When a voltage was applied to the organic electroluminescence element 2, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 26.0 cd / A, and the voltage at that time was 6.6 V. When a voltage was applied after the luminance was reduced by half, the voltage at a luminance of 1000 cd / m ² was 8.1V. The voltage increase at 1000 cd / m ² was 1.5V.

<Example 3> (Preparation of organic electroluminescence element 3)
A suspension of CLEVIOS P is placed on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering, and a film is formed to a thickness of about 65 nm by spin coating. Dried. Next, 0.7% by weight (by weight ratio, polymer compound P-1 / compound M) was added to polymer compound P-1 and compound M-2 in xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)). -2 = 90/10), the obtained xylene solution is placed on the film of CLEVIOS P, and is formed to a thickness of about 20 nm by a spin coating method. It was dried at 180 ° C. for 60 minutes under a nitrogen atmosphere of 10 ppm or less (weight basis). Next, the polymer compound P-4 and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.5 wt% (by weight ratio, the polymer compound P-4 / the light emitting material A). = 70/30). The obtained xylene solution was placed on the polymer compound P-1 / compound M-2 film, and the light emitting layer 3 was formed to a thickness of about 80 nm by spin coating. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited on the light-emitting layer 3 film at about 5 nm as a cathode, and then aluminum was vapor-deposited on the barium layer at about 60 nm. The organic electroluminescent element 3 was produced by sealing using a glass substrate after vapor deposition.

When a voltage was applied to the organic electroluminescence element 3, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 32.2 cd / A, and the voltage at that time was 6.5V. When a voltage was applied after the luminance was reduced by half, the voltage at a luminance of 1000 cd / m ² was 9.0V. The voltage increase at 1000 cd / m ² was 2.5V.

<Example 4> (Preparation of organic electroluminescence element 4)
A suspension of CLEVIOS P is placed on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering, and a film is formed to a thickness of about 65 nm by spin coating. Dried. Next, the polymer compound P-1,3,3′-dihydroxy-2,2′-bipyridine was 0.7% by weight (by weight ratio) in xylene (manufactured by Kanto Chemical Co., Inc .: for electronic industry (EL grade)). The polymer compound P-1 / 3,3′-dihydroxy-2,2′-bipyridine = 90/10) was dissolved, and the resulting xylene solution was placed on the film of CLEVIOS P, and spin coating was used. A film was formed to a thickness of about 20 nm, and was dried at 180 ° C. for 60 minutes in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less (weight basis). Next, the polymer compound P-4 and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.5 wt% (by weight ratio, the polymer compound P-4 / the light emitting material A). = 70/30). The obtained xylene solution is placed on the film of the polymer compound P-1 / 3,3′-dihydroxy-2,2′-bipyridine, and the light emitting layer 4 is formed by spin coating so as to have a thickness of about 80 nm. Filmed. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was deposited on the light emitting layer 4 film at about 5 nm as a cathode, and then aluminum was deposited on the barium layer at about 60 nm. The organic electroluminescent element 4 was produced by sealing using a glass substrate after vapor deposition.

When a voltage was applied to the organic electroluminescence element 4, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 30.8 cd / A, and the voltage at that time was 6.1V. When a voltage was applied after the luminance was reduced by half, the voltage at a luminance of 1000 cd / m ² was 8.3V. The voltage increase at 1000 cd / m ² was 2.2V.

<Example 5> (Preparation of organic electroluminescence element 5)
A suspension of CLEVIOS P is placed on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering, and a film is formed to a thickness of about 65 nm by spin coating. Dried. Next, 0.7% by weight (by weight ratio, polymer compound P-2 / compound M) was prepared by adding polymer compound P-2 and compound M-1 to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)). −1 = 90/10), the obtained xylene solution is placed on the film of CLEVIOS P, and formed into a film having a thickness of about 20 nm by a spin coating method. It was dried at 180 ° C. for 60 minutes under a nitrogen atmosphere of 10 ppm or less (weight basis). Next, the polymer compound P-4 and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.5 wt% (by weight ratio, the polymer compound P-4 / the light emitting material A). = 70/30). The obtained xylene solution was placed on the polymer compound P-2 / compound M-1 film, and the light emitting layer 5 was formed to a thickness of about 80 nm by spin coating. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited on the light-emitting layer 5 film at about 5 nm as a cathode, and then aluminum was vapor-deposited on the barium layer at about 60 nm. The organic electroluminescent element 5 was produced by sealing using a glass substrate after vapor deposition.

When a voltage was applied to the organic electroluminescence element 5, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 20.1 cd / A, and the voltage at that time was 6.3 V. When a voltage was applied after the luminance was reduced by half, the voltage at a luminance of 1000 cd / m ² was 8.7V. The voltage increase at 1000 cd / m ² was 2.4V.

<Example 6> (Production of organic electroluminescence element 6)
A suspension of CLEVIOS P is placed on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering, and a film is formed to a thickness of about 65 nm by spin coating. Dried. Next, 0.7% by weight (by weight ratio, polymer compound P-2 / compound M) was prepared by adding polymer compound P-2 and compound M-2 to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)). -2 = 90/10), the obtained xylene solution is placed on the film of CLEVIOS P, and is formed to a thickness of about 20 nm by a spin coating method. It was dried at 180 ° C. for 60 minutes under a nitrogen atmosphere of 10 ppm or less (weight basis). Next, the polymer compound P-4 and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.5 wt% (by weight ratio, the polymer compound P-4 / the light emitting material A). = 70/30). The obtained xylene solution was placed on the polymer compound P-2 / compound M-2 film, and the light emitting layer 6 was formed to a thickness of about 80 nm by spin coating. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited on the light-emitting layer 6 film at about 5 nm as a cathode, and then aluminum was vapor-deposited on the barium layer at about 60 nm. The organic electroluminescent element 6 was produced by sealing using a glass substrate after vapor deposition.

When a voltage was applied to the organic electroluminescence element 6, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 27.4 cd / A, and the voltage at that time was 6.2V. When a voltage was applied after the luminance was reduced by half, the voltage at a luminance of 1000 cd / m ² was 8.8V. The voltage increase at 1000 cd / m ² was 2.6V.

<Example 7> (Preparation of organic electroluminescence element 7)
A suspension of CLEVIOS P is placed on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering, and a film is formed to a thickness of about 65 nm by spin coating. Dried. Next, 0.7% by weight (by weight ratio) of the polymer compound P-2,3,3′-dihydroxy-2,2′-bipyridine in xylene (manufactured by Kanto Chemical Co., Inc .: for electronic industry (EL grade)) The polymer compound P-2 / 3,3′-dihydroxy-2,2′-bipyridine = 90/10) was dissolved, and the resulting xylene solution was placed on the film of CLEVIOS P, and spin coating was used. A film was formed to a thickness of about 20 nm, and was dried at 180 ° C. for 60 minutes in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less (weight basis). Next, the polymer compound P-4 and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.5 wt% (by weight ratio, the polymer compound P-4 / the light emitting material A). = 70/30). The obtained xylene solution is placed on the film of the polymer compound P-2 / 3,3′-dihydroxy-2,2′-bipyridine, and the light emitting layer 7 is formed by spin coating so as to have a thickness of about 80 nm. Filmed. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited on the light-emitting layer 7 film at about 5 nm as a cathode, and then aluminum was vapor-deposited on the barium layer at about 60 nm. After vapor deposition, the organic electroluminescent element 7 was produced by sealing using a glass substrate.

When a voltage was applied to the organic electroluminescence element 7, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 26.3 cd / A, and the voltage at that time was 6.1 V. When a voltage was applied after the brightness was reduced by half, the voltage at a brightness of 1000 cd / m ² was 8.5V. The voltage increase at 1000 cd / m ² was 2.4V.

<Example 8> (Preparation of organic electroluminescence element 8)
A suspension of CLEVIOS P is placed on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering, and a film is formed to a thickness of about 65 nm by spin coating. Dried. Next, 0.7% by weight (by weight ratio, polymer compound P-3 / compound M) was added to polymer compound P-3 and compound M-1 in xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)). −1 = 90/10), the obtained xylene solution is placed on the film of CLEVIOS P, and formed into a film having a thickness of about 20 nm by a spin coating method. It was dried at 180 ° C. for 60 minutes under a nitrogen atmosphere of 10 ppm or less (weight basis). Next, the polymer compound P-4 and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.5 wt% (by weight ratio, the polymer compound P-4 / the light emitting material A). = 70/30). The obtained xylene solution was placed on the polymer compound P-3 / compound M-1 film, and the light emitting layer 8 was formed to a thickness of about 80 nm by spin coating. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vacuum evaporated on the light emitting layer 8 film at about 5 nm and aluminum was then vacuum evaporated on the barium layer at about 60 nm as the cathode. The organic electroluminescent element 8 was produced by sealing using a glass substrate after vapor deposition.

When a voltage was applied to the organic electroluminescence element 8, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 14.5 cd / A, and the voltage at that time was 7.2V. When a voltage was applied after the luminance was reduced by half, the voltage at a luminance of 1000 cd / m ² was 9.1V. The voltage increase at 1000 cd / m ² was 1.9V.

<Example 9> (Production of organic electroluminescence element 9)
A suspension of CLEVIOS P is placed on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering, and a film is formed to a thickness of about 65 nm by spin coating. Dried. Next, 0.7% by weight (by weight ratio, polymer compound P-3 / compound M) was prepared by adding polymer compound P-3 and compound M-2 to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)). -2 = 90/10), the obtained xylene solution is placed on the film of CLEVIOS P, and is formed to a thickness of about 20 nm by a spin coating method. It was dried at 180 ° C. for 60 minutes under a nitrogen atmosphere of 10 ppm or less (weight basis). Next, the polymer compound P-4 and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.5 wt% (by weight ratio, the polymer compound P-4 / the light emitting material A). = 70/30). The obtained xylene solution was placed on the polymer compound P-3 / compound M-2 film, and the light emitting layer 9 was formed to a thickness of about 80 nm by spin coating. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited on the light-emitting layer 9 film at about 5 nm as a cathode, and then aluminum was vapor-deposited on the barium layer at about 60 nm. The organic electroluminescent element 9 was produced by sealing using a glass substrate after vapor deposition.

When a voltage was applied to the organic electroluminescence element 9, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 18.9 cd / A, and the voltage at that time was 6.6 V. When a voltage was applied after the luminance was reduced by half, the voltage at a luminance of 1000 cd / m ² was 9.0V. The voltage increase at 1000 cd / m ² was 2.4V.

<Example 10> (Production of organic electroluminescence element 10)
A suspension of CLEVIOS P is placed on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering, and a film is formed to a thickness of about 65 nm by spin coating. Dried. Next, the polymer compound P-3,3,3′-dihydroxy-2,2′-bipyridine was added to xylene (manufactured by Kanto Chemical Co., Ltd .: for electronic industry (EL grade)) at 0.7 wt% (by weight ratio). The polymer compound P-3 / 3,3′-dihydroxy-2,2′-bipyridine = 90/10) was dissolved, and the resulting xylene solution was placed on the film of CLEVIOS P, and spin coating was used. A film was formed to a thickness of about 20 nm, and was dried at 180 ° C. for 60 minutes in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less (weight basis). Next, the polymer compound P-4 and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.5 wt% (by weight ratio, the polymer compound P-4 / the light emitting material A). = 70/30). The obtained xylene solution is placed on the film of the polymer compound P-3 / 3,3′-dihydroxy-2,2′-bipyridine, and the light emitting layer 10 is formed by spin coating so as to have a thickness of about 80 nm. Filmed. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited on the light-emitting layer 10 film at about 5 nm as a cathode, and then aluminum was vapor-deposited on the barium layer at about 60 nm. The organic electroluminescent element 10 was produced by sealing using a glass substrate after vapor deposition.

When a voltage was applied to the organic electroluminescence element 10, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 19.3 cd / A, and the voltage at that time was 5.9 V. When a voltage was applied after the brightness was reduced by half, the voltage at a brightness of 1000 cd / m ² was 8.5V. The voltage increase at 1000 cd / m ² was 2.6V.

<Example 11> (Production of organic electroluminescence element 11)
A suspension of CLEVIOS P is placed on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering, and a film is formed to a thickness of about 65 nm by spin coating. Dried. Next, the polymer compound P-6 was dissolved in xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at a concentration of 0.7% by weight, and the resulting xylene solution was deposited on the CLEVIOS P film. Then, a film having a thickness of about 20 nm was formed by spin coating, and dried at 180 ° C. for 60 minutes in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less (weight basis). Next, the polymer compound P-4 and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.5 wt% (by weight ratio, the polymer compound P-4 / the light emitting material A). = 70/30). The obtained xylene solution was placed on the film of the polymer compound P-6, and the light emitting layer 11 was formed to have a thickness of about 80 nm by spin coating. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited on the light-emitting layer 11 film at about 5 nm as a cathode, and then aluminum was vapor-deposited on the barium layer at about 60 nm. The organic electroluminescent element 11 was produced by sealing using a glass substrate after vapor deposition.

When a voltage was applied to the organic electroluminescence element 11, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 28.3 cd / A, and the voltage at that time was 7.2V. When a voltage was applied after the luminance was reduced by half, the voltage at a luminance of 1000 cd / m ² was 9.3V. The voltage increase at 1000 cd / m ² was 2.1V.

<Example 12> (Production of organic electroluminescence element 12)
A suspension of CLEVIOS P is placed on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering, and a film is formed to a thickness of about 65 nm by spin coating. Dried. Next, 0.7% by weight (by weight ratio, polymer compound P-6 / compound M) was prepared by adding polymer compound P-6 and compound M-1 to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)). −1 = 90/10), the obtained xylene solution is placed on the film of CLEVIOS P, and formed into a film having a thickness of about 20 nm by a spin coating method. It was dried at 180 ° C. for 60 minutes under a nitrogen atmosphere of 10 ppm or less (weight basis). Next, the polymer compound P-4 and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.5 wt% (by weight ratio, the polymer compound P-4 / the light emitting material A). = 70/30). The obtained xylene solution was placed on the polymer compound P-6 / compound M-1 film, and the light emitting layer 12 was formed to a thickness of about 80 nm by spin coating. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited on the light-emitting layer 12 film at about 5 nm as a cathode, and then aluminum was vapor-deposited on the barium layer at about 60 nm. The organic electroluminescent element 12 was produced by sealing using a glass substrate after vapor deposition.

When a voltage was applied to the organic electroluminescence element 12, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 21.7 cd / A, and the voltage at that time was 6.9 V. When a voltage was applied after the luminance was reduced by half, the voltage at a luminance of 1000 cd / m ² was 9.2V. The voltage increase at 1000 cd / m ² was 2.3V.

<Example 13> (Production of organic electroluminescence element 13)
A suspension of CLEVIOS P is placed on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering, and a film is formed to a thickness of about 65 nm by spin coating. Dried. Next, 0.7% by weight (by weight ratio, polymer compound P-6 / compound M) of polymer compound P-6 and compound M-2 in xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) -2 = 90/10), the obtained xylene solution is placed on the film of CLEVIOS P, and is formed to a thickness of about 20 nm by a spin coating method. It was dried at 180 ° C. for 60 minutes under a nitrogen atmosphere of 10 ppm or less (weight basis). Next, the polymer compound P-4 and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.5 wt% (by weight ratio, the polymer compound P-4 / the light emitting material A). = 70/30). The obtained xylene solution was placed on the polymer compound P-6 / compound M-2 film, and the light emitting layer 13 was formed to a thickness of about 80 nm by spin coating. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited on the light-emitting layer 13 film at about 5 nm as a cathode, and then aluminum was vapor-deposited on the barium layer at about 60 nm. The organic electroluminescent element 13 was produced by sealing using a glass substrate after vapor deposition.

When a voltage was applied to the organic electroluminescence element 13, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 22.8 cd / A, and the voltage at that time was 7.0 V. When a voltage was applied after the luminance was reduced by half, the voltage at a luminance of 1000 cd / m ² was 9.3V. The voltage increase at 1000 cd / m ² was 2.3V.

<Example 14> (Production of organic electroluminescence element 14)
A suspension of CLEVIOS P is placed on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering, and a film is formed to a thickness of about 65 nm by spin coating. Dried. Next, the polymer compound P-6,3,3′-dihydroxy-2,2′-bipyridine was added to xylene (manufactured by Kanto Chemical Co., Ltd .: for electronic industry (EL grade)) at 0.7 wt% (by weight ratio, The polymer compound P-6 / 3,3′-dihydroxy-2,2′-bipyridine = 90/10) was dissolved, and the resulting xylene solution was placed on the film of CLEVIOS P, and spin coating was used. A film was formed to a thickness of about 20 nm, and was dried at 180 ° C. for 60 minutes in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less (weight basis). Next, the polymer compound P-4 and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.5 wt% (by weight ratio, the polymer compound P-4 / the light emitting material A). = 70/30). The obtained xylene solution is placed on the film of the polymer compound P-6 / 3,3′-dihydroxy-2,2′-bipyridine, and the light emitting layer 14 is formed to a thickness of about 80 nm by spin coating. Filmed. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited on the light-emitting layer 14 film at about 5 nm and aluminum was then vapor-deposited on the barium layer at about 60 nm as the cathode. The organic electroluminescent element 14 was produced by sealing using a glass substrate after vapor deposition.

When a voltage was applied to the organic electroluminescence element 14, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 22.0 cd / A, and the voltage at that time was 7.0V. When a voltage was applied after the luminance was reduced by half, the voltage at a luminance of 1000 cd / m ² was 9.2V. The voltage increase at 1000 cd / m ² was 2.2V.

<Comparative example 1> (Preparation of organic electroluminescence element C1)
A suspension of CLEVIOS P is placed on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering, and a film is formed to a thickness of about 65 nm by spin coating. Dried. Next, the polymer compound P-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at a concentration of 0.7% by weight, and the resulting xylene solution was deposited on the CLEVIOS P film. Then, a film having a thickness of about 20 nm was formed by spin coating, and dried at 180 ° C. for 60 minutes in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less (weight basis). Next, 1.1% by weight (by weight ratio, polymer compound P-5 / luminescent material A) of polymer compound P-5 and luminescent material A in xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) = 70/30). The obtained xylene solution was placed on the film of the polymer compound P-1, and the light emitting layer C1 was formed to have a thickness of about 80 nm by spin coating. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vacuum evaporated on the light emitting layer C1 film at about 5 nm, and then aluminum was vacuum evaporated on the barium layer at about 60 nm as the cathode. After vapor deposition, the organic electroluminescent element C1 was produced by sealing using a glass substrate.

When a voltage was applied to the organic electroluminescence element C1, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 29.8 cd / A, and the voltage at that time was 8.8 V. When a voltage was applied after the brightness was reduced by half, the voltage at a brightness of 1000 cd / m ² was 12.1V. The voltage increase at 1000 cd / m ² was 3.3V.

<Comparative example 2> (Preparation of organic electroluminescence element C2)
A suspension of CLEVIOS P is placed on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering, and a film is formed to a thickness of about 65 nm by spin coating. Dried. Next, the polymer compound P-1 was dissolved in xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at a concentration of 0.7% by weight, and the resulting xylene solution was deposited on the CLEVIOS P film. Then, a film having a thickness of about 20 nm was formed by spin coating, and dried at 180 ° C. for 60 minutes in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less (weight basis). Next, the polymer compound P-4 and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.5 wt% (by weight ratio, the polymer compound P-4 / the light emitting material A). = 70/30). The obtained xylene solution was placed on the film of the polymer compound P-1, and the light emitting layer C2 was formed to have a thickness of about 80 nm by spin coating. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited on the light-emitting layer C2 film at about 5 nm as a cathode, and then aluminum was vapor-deposited on the barium layer at about 60 nm. After vapor deposition, the organic electroluminescence element C2 was produced by sealing using a glass substrate.

When a voltage was applied to the organic electroluminescence element C2, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 30.8 cd / A, and the voltage at that time was 6.4 V. When a voltage was applied after the luminance was reduced by half, the voltage at a luminance of 1000 cd / m ² was 9.7V. The voltage increase at 1000 cd / m ² was 3.3V.

<Comparative example 3> (Preparation of organic electroluminescence element C3)
A suspension of CLEVIOS P is placed on a glass substrate having an ITO film with a thickness of 150 nm formed by sputtering, and a film is formed to a thickness of about 65 nm by spin coating. Dried. Next, the polymer compound P-2 was dissolved in xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at a concentration of 0.7% by weight, and the resulting xylene solution was deposited on the CLEVIOS P film. Then, a film having a thickness of about 20 nm was formed by spin coating, and dried at 180 ° C. for 60 minutes in a nitrogen atmosphere having an oxygen concentration and a water concentration of 10 ppm or less (weight basis). Next, the polymer compound P-4 and the light emitting material A were added to xylene (manufactured by Kanto Chemical Co., Inc .: for electronics industry (EL grade)) at 1.5 wt% (by weight ratio, the polymer compound P-4 / the light emitting material A). = 70/30). The obtained xylene solution was placed on the film of the polymer compound P-2, and a light emitting layer C3 was formed to have a thickness of about 80 nm by spin coating. And it dried at 130 degreeC for 10 minutes in nitrogen atmosphere whose oxygen concentration and water concentration are 10 ppm or less (weight basis). After reducing the pressure to 1.0 × 10 ⁻⁴ Pa or less, barium was vapor-deposited on the light-emitting layer C3 film at about 5 nm as a cathode, and then aluminum was vapor-deposited on the barium layer at about 60 nm. After vapor deposition, the organic electroluminescent element C3 was produced by sealing using a glass substrate.

When a voltage was applied to the organic electroluminescence element C3, green electroluminescence was observed. The luminous efficiency at a luminance of 1000 cd / m ² was 24.7 cd / A, and the voltage at that time was 6.1 V. When a voltage was applied after the luminance was reduced by half, the voltage at a luminance of 1000 cd / m ² was 9.2V. The voltage increase at 1000 cd / m ² was 3.1V.

Claims (15)

An organic electroluminescence device comprising an anode and a cathode, and a hole transport layer and a light emitting layer provided between the anode and the cathode,
The hole transport layer is
1) A mixture of a 2,2′-bipyridine and / or a 2,2′-bipyridine derivative and a 2,2′-bipyridinediyl group-free hole transporting polymer compound,
2) Selected from the group consisting of a structural unit composed of an unsubstituted or substituted 2,2′-bipyridinediyl group, a structural unit composed of a divalent aromatic amine residue, and a structural unit composed of an unsubstituted or substituted arylene group. 2,2′-bipyridinediyl group-containing polymer compound having at least one kind of structural unit,
Or
3) 2,2′-bipyridine and / or 2,2′-bipyridine derivative;
2,2′-bipyridinediyl group-free hole transporting polymer compound,
At least selected from the group consisting of a structural unit consisting of an unsubstituted or substituted 2,2′-bipyridinediyl group, a structural unit consisting of a divalent aromatic amine residue, and a structural unit consisting of an unsubstituted or substituted arylene group. An organic electroluminescent device comprising a mixture of a 2,2'-bipyridinediyl group-containing polymer compound having a kind of structural unit . The organic electroluminescence device according to claim 1, wherein the 2,2'-bipyridinediyl group-free hole transporting polymer compound is a polymer compound represented by the following formula (2).

(2)
[In formula (2), Am ^2p represents a divalent aromatic amine residue, and Ar ^2p represents an unsubstituted or substituted arylene group. n ^22p and n ^23p each independently represent the molar ratio of the divalent aromatic amine residue represented by Am ^2p and the unsubstituted or substituted arylene group represented by Ar ^2p in the polymer compound. is a number that represents ^{but, n 22p + n 23p = 1,0.001} ≦ n 22p ≦ 1, and a number satisfying 0 ≦ n ^23p ≦ 0.999. When there are a plurality of Am ^{2p s} , they may be the same or different. When there are a plurality of Ar ^{2p s} , they may be the same or different. ] The organic electroluminescence device according to claim 2, wherein the arylene group represented by Ar ^2p includes at least one selected from the group consisting of an unsubstituted or substituted fluorenediyl group and an unsubstituted or substituted phenylene group. The organic electroluminescence device according to any one of claims 1 to 3, wherein the 2,2'-bipyridine or the 2,2'-bipyridine derivative is a compound represented by the following formula (3).

(3)
[In formula (3), E ^3m and R ^3m each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, Unsubstituted or substituted alkoxy group, unsubstituted or substituted alkylthio group, unsubstituted or substituted alkylsilyl group, unsubstituted or substituted aryl group, unsubstituted or substituted aryloxy group, or unsubstituted or substituted arylsilyl Represents a group. X ^3m represents an unsubstituted or substituted arylene group, an unsubstituted or substituted alkanediyl group, an unsubstituted or substituted alkenediyl group, or an unsubstituted or substituted alkynediyl group. The plurality of E ^3m may be the same or different. A plurality of R ^3m may be the same or different. m ^31m represents an integer of 0 to 3. m ^32m represents an integer of 1 to 3. When m ^32m is 2 or 3, m ^31m attached to X ^3m may be the same or different. When there are a plurality of X ^{3m s} , they may be the same or different. ] In the formula (3), E ^3m is a hydrogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, or an unsubstituted or substituted aryl group. Luminescence element. The organic electroluminescent element according to claim 4 or 5, wherein R ^3m in the formula (3) is a hydrogen atom. The organic electroluminescence device according to any one of claims 4 to 6, wherein in the formula (3), X ^3m is an unsubstituted or substituted arylene group or an unsubstituted or substituted alkanediyl group. The organic electroluminescence device according to any one of claims 4 to 7, wherein the compound represented by the formula (3) is a compound represented by the following formula (4).

(4)
[In formula (4), E ^4m represents a hydrogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted alkoxy group. Plural E ^4m may be the same or different, but at least one E ^4m represents a hydroxyl group, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted alkoxy group. ] The organic electroluminescence device according to any one of claims 4 to 7, wherein the compound represented by the formula (3) is a compound represented by the following formula (5).

(5)
[In formula (5), E ^5m represents a hydrogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted alkoxy group. The plurality of E ^5m may be the same or different. X ^5m represents an unsubstituted or substituted arylene group or an unsubstituted or substituted alkanediyl group. m ^5m represents an integer of 1 to 3. When there are a plurality of X ^5m , they may be the same or different. ] The organic electro layer containing a mixture of a 2,2′-bipyridine and / or a 2,2′-bipyridine derivative and a 2,2′-bipyridinediyl group-free hole transporting polymer compound, wherein the hole transport layer is A luminescence element,
The ratio of the 2,2'-bipyridine and the 2,2'-bipyridine derivative contained in the hole transport layer is 0.01 to 50% by weight. Luminescence element. The organic electroluminescent device according to any one of claims 1 to 10, wherein the 2,2'-bipyridinediyl group-containing polymer compound is a polymer compound represented by the following formula (1).

(1)
[In Formula (1), Bpy ^1p represents an unsubstituted or substituted 2,2′-bipyridinediyl group. Am ^1p represents a divalent aromatic amine residue. Ar ^1p represents an unsubstituted or substituted arylene group. n ^11p , n ^12p and n ^13p are each independently an unsubstituted or substituted 2,2′-bipyridinediyl group represented by Bpy ^1p and a divalent fragrance represented by Am ^1p in the polymer compound. N ^11p + n ^12p + n ^13p = 1, 0.001 ≦ n ^11p ≦ 0.999, 0, which represents the molar ratio between the group amine residue and the unsubstituted or substituted arylene group represented by Ar ^1p .001 ≦ n ^12p ≦ 0.999 and 0 ≦ n ^13p ≦ 0.998. When there are a plurality of Bpy ^1p , they may be the same or different. When there are a plurality of Am ^1p , they may be the same or different. When there are a plurality of Ar ^{1p s} , they may be the same or different. ] The organic electroluminescent device according to claim 11, wherein Bpy ^1p in the formula (1) is a divalent group represented by the following formula (1-2).

(1-2)
[In the formula (1-2), R ^1p represents a hydrogen atom, a halogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkynyl group, an unsubstituted or substituted It represents an alkoxy group, an unsubstituted or substituted alkylthio group, an unsubstituted or substituted alkylsilyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, or an unsubstituted or substituted arylsilyl group. A plurality of R ^1p may be the same or different. ] The organic electroluminescence device according to claim 12, wherein R ^1p in the formula (1-2) is a hydrogen atom. The hole transport layer is
A) a mixture of the 2,2′-bipyridine and / or 2,2′-bipyridine derivative and a 2,2′-bipyridinediyl group-free hole transporting polymer compound, and an organic solvent, Composition of the
B) From the group consisting of the structural unit consisting of the unsubstituted or substituted 2,2′-bipyridinediyl group, the structural unit consisting of a divalent aromatic amine residue, and the structural unit consisting of an unsubstituted or substituted arylene group. A second composition comprising a 2,2′-bipyridinediyl group-containing polymer compound having at least one selected structural unit, and an organic solvent;
Or
C) the 2,2′-bipyridine and / or 2,2′-bipyridine derivative;
The 2,2′-bipyridinediyl group-free hole transporting polymer compound;
Selected from the group consisting of a structural unit composed of the unsubstituted or substituted 2,2′-bipyridinediyl group, a structural unit composed of a divalent aromatic amine residue, and a structural unit composed of an unsubstituted or substituted arylene group. A third composition comprising a mixture with a 2,2'-bipyridinediyl group-containing polymer compound having at least one structural unit, and an organic solvent. Organic electroluminescent element as described in any one of these.   The organic according to any one of claims 1 to 14, wherein the hole transport layer and the light emitting layer are in contact with each other, and a hole injection layer is provided between the hole transport layer and the anode. Electroluminescence element.