JP2010171373A - Organic electroluminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescent element having a long lifetime until the luminance of which is reduced to 80 where the luminance at the start of driving is supposed to be 100. <P>SOLUTION: The organic electroluminescent element is obtained by forming a light-emitting layer including a high-molecular light-emitting material and an ion pair on an anode, wherein the anion of the ion pair is expressed by formula (1a), formula (1b), formula (2), or formula (3), a cathode is formed on the light-emitting layer, and conduction processing is performed to cause a current to flow from the anode to the cathode by applying a voltage of 10 V or higher between the anode and the cathode. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic electroluminescence element.

  Unlike organic electroluminescent devices using low molecular weight light emitting materials, organic electroluminescent devices using high molecular weight light emitting materials can be used to form the light emitting layer of organic electroluminescent devices using a coating method. ing. For example, an organic electroluminescence element having a light emitting layer containing polyfluorene which is a conjugated polymer compound is described (Non-Patent Document 1). Moreover, in order to lengthen the luminance half life of the organic electroluminescent element, an organic electroluminescent element having a light emitting layer containing a polymeric fluorescent substance and an ion pair is described (Patent Document 1).

Advanced Materials Vol.12 1737-1750 (2000)

International Publication No. 2004/99340 Pamphlet

  However, the organic electroluminescence element has a problem that the lifetime until the luminance reaches 80 is not always sufficient when the luminance at the start of driving is set to 100.

  Accordingly, an object of the present invention is to provide an organic electroluminescence element having a long lifetime until the luminance reaches 80 when the luminance at the start of driving is set to 100.

（式中、Ｙ¹は１３族の原子を表し、Ａｒ¹は電子吸引性基を有するアリール基又は電子吸引性基を有する１価の複素環基を表し、Ｑ¹は酸素原子又は直接結合を表し、Ｘ¹はハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、置換アミノ基、アミド基、酸イミド基、アシルオキシ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、シアノ基又はニトロ基を表し、ａは１〜３の整数を表し、ｋは１〜４の整数を表し、Ｖ¹は１６族の原子、２価の脂肪族炭化水素基、２価の芳香族炭化水素基、２座の複素環基、−Ｃ≡Ｎ−、−Ｎ＝Ｎ＝Ｎ−又は直接結合を表し、ｂは２〜６の整数を表し、Ｚ¹は
−Ｍ’（＝Ｏ）_p− （式中 Ｍ’は、３族、４族、５族、６族、７族、８族、９族、１０族、１１族、１２族、１３族、１４族、１５族、１６族、又は１７族の原子を表し、ｐは０〜２の整数を表す。）を表すか、ｂ価の脂肪族炭化水素基、ｂ価の芳香族炭化水素基、ｂ座の複素環基、−Ｃ≡Ｎ−、−Ｎ＝Ｎ＝Ｎ−、−ＮＨ−、−ＮＨ₂−、−ＯＨ−又は直接結合を表す。ただし、Ｚ¹が−Ｍ’（＝Ｏ）_p−、−Ｃ≡Ｎ−、−Ｎ＝Ｎ＝Ｎ−、−ＮＨ−、−ＮＨ₂−又は−ＯＨ−の場合、ｂ＝２である。Ｚ¹とＶ¹とは相異なり、Ｙ¹、Ｑ¹、Ａｒ¹及びＸ¹が複数個存在する場合、それらは同一でも異なっていてもよく、複数存在するａ及びＶ¹は、それぞれ同一であっても相異なっていてもよく、ｃは１〜６の整数を表す。）

（式中、Ｙ²は１３族の原子を表し、Ａｒ²は電子吸引性基を有するアリール基又は電子吸引性基を有する１価の複素環基を表し、Ｑ²は酸素原子又は直接結合を表し、Ｘ²はハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、置換アミノ基、アミド基、酸イミド基、アシルオキシ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、シアノ基又はニトロ基を表し、ｄ及びｄ’は、同一又は相異なり、１又は２を表し、Ｖ²は１６族の原子、２価の脂肪族炭化水素基、２価の芳香族炭化水素基、２座の複素環基、−Ｃ≡Ｎ−又は−Ｎ＝Ｎ−を表し、複数個のＹ²、Ａｒ²、Ｑ²及びＶ²は、それぞれ同一でも相異なっていてもよく、Ｘ²が複数個存在する場合、それらは同一であっても相異なっていてもよく、ｅは１〜６の整数を表す。）

（式中、Ｙ³は１３族の原子を表し、Ａｒ³は電子吸引性基を有するアリール基又は電子吸引性基を有する１価の複素環基を表し、Ｑ³は酸素原子又は直接結合を表し、Ｖ³は１６族の原子、２価の脂肪族炭化水素基、２価の芳香族炭化水素基、２座の複素環基、−Ｃ≡Ｎ−又は−Ｎ＝Ｎ−を表し、複数個のＹ³、Ａｒ³、Ｑ³及びＶ³は、それぞれ同一であっても相異なっていてもよく、ｆは１〜６の整数を表す。） That is, in the present invention, a light emitting layer including a polymer light emitter and an ion pair is formed on an anode, and an anion of the ion pair is expressed by the formula (1a), the formula (1b), the formula (2), or the formula ( 3) an anion represented by 3), in which a cathode is formed on the light emitting layer, and a current of flowing from the anode to the cathode is applied by applying a voltage of 10 V or more between the anode and the cathode. The organic electroluminescent element obtained by this is provided.

(Wherein Y ¹ represents a Group 13 atom, Ar ¹ represents an aryl group having an electron-withdrawing group or a monovalent heterocyclic group having an electron-withdrawing group, and Q ¹ represents an oxygen atom or a direct bond. It represents, X ¹ is a halogen atom, an alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group , Arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acid imide group, acyloxy group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, cyano group Or a nitro group, a represents an integer of 1 to 3, k represents an integer of 1 to 4, and V ¹ represents a group 16 element. A divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a bidentate heterocyclic group, —C≡N—, —N═N═N— or a direct bond; Represents an integer of 6, Z ¹ is —M ′ (═O) _p — (wherein M ′ is 3, 4, 5, 6, 7, 8, 9, 9, 10 or 11). Group, group 12, group 13, group 14, group 15, group 16 or group 17 and p represents an integer of 0 to 2) or b-valent aliphatic hydrocarbon group, b A valent aromatic hydrocarbon group, a b-dentate heterocyclic group, —C≡N—, —N═N═N—, —NH—, —NH ₂ —, —OH— or a direct bond, provided that Z ^{When 1} is —M ′ (═O) _p —, —C≡N—, —N═N═N—, —NH—, —NH ₂ — or —OH—, b = 2, and Z ¹ Unlike phase and V ^1, if Y ^1, Q ^1, Ar ¹ and X ¹ are present a plurality, they May be different even one, a and V ¹ there are a plurality each of which represents a phase be the same, c is an integer of 1-6.)

(Wherein, Y ² is represents the group 13 atoms, Ar ² represents a monovalent heterocyclic group having an aryl group or an electron withdrawing group having an electron-withdrawing group, Q ² is an oxygen atom or a direct bond X ² is a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group , Arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acid imide group, acyloxy group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, cyano group or a nitro group, d and d 'are the same or different, represent 1 or 2, V ² is a group 16 original , Divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, bidentate heterocyclic group, -C≡N- or -N = N-a represents a plurality of Y ^2, Ar ^2, Q ² and V ² may be the same or different, and when a plurality of X ² are present, they may be the same or different, and e represents an integer of 1 to 6.)

(Wherein Y ³ represents a Group 13 atom, Ar ³ represents an aryl group having an electron-withdrawing group or a monovalent heterocyclic group having an electron-withdrawing group, and Q ³ represents an oxygen atom or a direct bond. V ³ represents a group 16 atom, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a bidentate heterocyclic group, —C≡N— or —N═N—, Y ³ , Ar ³ , Q ³ and V ³ may be the same or different from each other, and f represents an integer of 1 to 6.

  The organic electroluminescence device of the present invention has a long lifetime until the luminance reaches 80 when the luminance at the start of driving is set to 100. Therefore, the present invention is extremely useful industrially.

  Hereinafter, the present invention will be described in detail.

  The organic electroluminescence device of the present invention has a light emitting layer containing an ion pair containing an anion represented by formula (1a), formula (1b), formula (2) or formula (3) and a polymer light emitter.

Y ¹ in Formula (1a) and Formula (1b) represents a Group 13 atom, preferably a boron atom, an aluminum atom, or a gallium atom, and more preferably a boron atom.

Ar ¹ in formula (1a) and formula (1b) represents an aryl group having an electron-withdrawing group or a monovalent heterocyclic group having an electron-withdrawing group.
Here, the electron-withdrawing group represents an atom or an atomic group that attracts electrons by a resonance effect or an inductive effect, and examples thereof include a halogen atom, a nitro group, a nitroso group, a cyano group, an acyl group, a carboxyl group, an alkyloxy group. Examples include a carbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group, and a perfluoroalkyl group.

  In the electron-withdrawing group, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

  The acyl group usually has about 2 to 20 carbon atoms, and specific examples thereof include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, trifluoroacetyl group, pentafluorobenzoyl group and the like. Is done.

  The alkyloxycarbonyl group usually has about 2 to 20 carbon atoms. Specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, i-propyloxycarbonyl group, butoxycarbonyl group, i-butoxy. Carbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl Group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, lauryloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, Fluoro-butoxycarbonyl group, perfluorohexyloxy carbonyl group, such as perfluorooctyl oxycarbonyl groups.

Aryloxycarbonyl group has a carbon number of usually about 7 to 60, and specific examples thereof include phenoxycarbonyl group, C ₁ -C ₁₂ alkoxy phenoxy group (C ₁ -C ₁₂ is a 1 to 12 carbon atoms the same is true. below indicate that.), C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxycarbonyl group, 2-naphthyloxy group, pentafluorophenyl oxycarbonyl groups.
Arylalkyloxycarbonyl group has usually about 8 to 60 carbon atoms, and specific examples thereof include a phenyl -C ₁ -C ₁₂ alkoxycarbonyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxycarbonyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxycarbonyl group, 1-naphthyl -C ₁ -C ₁₂ alkoxycarbonyl group, 2-naphthyl -C ₁ -C ₁₂ alkoxycarbonyl groups.

The heteroaryloxycarbonyl group (group represented by Q ⁴ —O (C═O) —, Q ⁴ represents a monovalent heterocyclic group) usually has about 2 to 60 carbon atoms, specifically is thienyl oxycarbonyl group, C ₁ -C ₁₂ alkyl thienyl alkyloxycarbonyl group, pyrrolyl oxycarbonyl group, furyloxy group, pyridyloxy carbonyl group, C ₁ -C ₁₂ alkyl pyridyloxycarbonyl group, imidazolyloxy group, Examples include pyrazolyloxycarbonyl group, triazolyloxycarbonyl group, oxazolyloxycarbonyl group, thiazoleoxycarbonyl group, thiadiazoleoxycarbonyl group and the like.

  A perfluoroalkyl group represents a group obtained by substituting all hydrogen atoms of a linear or branched alkyl group or cycloalkyl group with fluorine atoms, and usually has about 1 to 20 carbon atoms. Fluoromethyl group, perfluoroethyl group, perfluoropropyl group, heptafluoro-i-propyl group, perfluorobutyl group, nonafluoro-i-butyl group, 1,1-bistrifluoromethyl-2,2,2-trifluoro Examples include an ethyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluorocyclohexyl group, a perfluoroheptyl group, a perfluorooctyl group, a perfluorononyl group, a perfluorodecyl group, and a perfluorolauryl group.

Next, an aryl group having an electron attractive group represented by Ar ₁ in the formula (1a) and the formula (1b), the monovalent heterocyclic group having an electron attractive group is described.

An aryl group having an electron withdrawing group is usually about 6 to 60 carbon atoms, and specific examples thereof include a phenyl group, C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ alkylphenyl group, 1- Examples thereof include groups in which one or more hydrogen atoms contained in a naphthyl group, 2-naphthyl group and the like are substituted with the electron-withdrawing group.

The monovalent heterocyclic group having an electron-withdrawing group usually has about 2 to 60 carbon atoms, and specific examples thereof include thienyl group, C _{1 to} C ₁₂ alkylthienyl group, pyrrolyl group, furyl group, pyridyl group. group, C ₁ -C ₁₂ alkyl pyridyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, an oxazolyl group, a thiazole group, a group in which one or more hydrogen atoms contained in the thiadiazole group is substituted with the electron withdrawing group Illustrated. As the monovalent heterocyclic group, a monovalent aromatic heterocyclic group is preferable.

（ＩＩ）電子吸引性基を有する１価の複素環基：

（ＩＩＩ）フッ素原子又はトリフルオロメチル基を電子吸引性基として有するアリール基：

（ＩＶ）フッ素原子又はトリフルオロメチル基を電子吸引性基として有する１価の複素環基：

（Ｖ）パーフルオロアリール基：
パーフルオロアリール基としては、ペンタフルオロフェニル基、ヘプタフルオロ−１−ナフチル基、ヘプタフルオロ−２−ナフチル基、ノナフルオロ−１−ビフェニル基、ノナフルオロ−２−ビフェニル基、ノナフルオロ−１−アントラセニル基、ノナフルオロ−２−アントラセニル基、ノナフルオロ−９−アントラセニル基が例示される。 Specific examples of Ar ¹ include the following groups (I) to (V). In formula (1a) and the formula (1b), if Ar ¹ there are a plurality, they may be the same or different.
(I) Aryl group having electron-withdrawing group:

(II) Monovalent heterocyclic group having an electron-withdrawing group:

(III) Aryl group having fluorine atom or trifluoromethyl group as electron withdrawing group:

(IV) A monovalent heterocyclic group having a fluorine atom or a trifluoromethyl group as an electron-withdrawing group:

(V) Perfluoroaryl group:
Perfluoroaryl groups include pentafluorophenyl, heptafluoro-1-naphthyl, heptafluoro-2-naphthyl, nonafluoro-1-biphenyl, nonafluoro-2-biphenyl, nonafluoro-1-anthracenyl, nonafluoro Examples include a 2-anthracenyl group and a nonafluoro-9-anthracenyl group.

  The monovalent heterocyclic group having an aryl group having a fluorine atom or a trifluoromethyl group, an aryl group having a fluorine atom or a trifluoromethyl group, or a monovalent heterocyclic group having an electron withdrawing group A perfluoroaryl group is preferred (formulas (III), (IV) and (V)), and a perfluoroaryl group (formula (V)) is more preferred.

Q ¹ in formula (1a) and formula (1b) represents an oxygen atom or a direct bond. When a plurality of Q ¹ are present, they may be the same or different.

X ¹ in formula (1a) and (1b), a halogen atom, an alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl Group, alkynyl group, arylalkenyl group, arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acid imide group, acyloxy group, monovalent heterocyclic group, heteroaryloxy group Represents a heteroarylthio group, a cyano group or a nitro group.

Examples of the halogen atom in X ¹ 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 and usually has about 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, i -Butyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group , A trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, and the like.

  The alkyloxy group may be linear or branched, and may be a cycloalkyloxy group. The alkyloxy group may have a substituent and usually has about 1 to 20 carbon atoms. Specific examples thereof include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group. Group, i-butoxy group, s-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3 , 7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group, methoxymethyloxy group, 2-methoxyethyloxy group, etc. Illustrated.

  The alkylthio group may be linear or branched, and may be a cycloalkylthio group. The alkylthio group may have a substituent and usually has about 1 to 20 carbon atoms. Specific examples thereof include a methylthio group, an ethylthio group, a propylthio group, an i-propylthio group, a butylthio group, an i -Butylthio group, s-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group , Laurylthio group, trifluoromethylthio group and the like.

The aryl group may have a substituent and usually has about 6 to 60 carbon atoms. Specific examples thereof include a phenyl group, a C _{1 to} C ₁₂ alkoxyphenyl group, and a C _{1 to} C ₁₂ alkylphenyl. Group, 1-naphthyl group, 2-naphthyl group and the like are exemplified.

The aryloxy group may have a substituent on the aromatic ring and usually has about 6 to 60 carbon atoms. Specific examples thereof include a phenoxy group, a C _{1 to} C ₁₂ alkoxyphenoxy group, and a C _1. -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group and the like.

Arylthio group may have a substituent on the aromatic ring has a carbon number of usually about 6 to 60, and specific examples thereof include a phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group, pentafluorophenylthio group and the like.

The arylalkyl group may have a substituent and usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl-C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxyphenyl- C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl group exemplified Is done.

Arylalkyloxy group may have a substituent, and the carbon number is usually about 7 to 60, and specific examples thereof include a phenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl -C ₁ -C ₁₂ alkoxy groups, 2-naphthyl -C ₁ -C ₁₂ alkoxy group Illustrated.

The arylalkylthio group may have a substituent and usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl-C ₁ -C ₁₂ alkylthio group, a C ₁ -C ₁₂ alkoxyphenyl- C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group, 1-naphthyl -C ₁ -C ₁₂ alkylthio group, 2-naphthyl -C ₁ -C ₁₂ alkylthio group are exemplified Is done.

The alkenyl group usually has about 2 to 20 carbon atoms. Specific examples thereof include a vinyl group, a 1-propylenyl group, a 2-propylenyl group, a 3-propylenyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group. Octenyl group and cyclohexenyl group.
Alkenyl groups also include alkadienyl groups such as 1,3-butadienyl groups.

  The alkynyl group usually has about 2 to 20 carbon atoms, and specific examples thereof include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptenyl group, octynyl group, cyclohexylethynyl. Groups. In addition, the alkynyl group includes an alkydenyl group such as a 1,3-butadiynyl group.

  The arylalkenyl group usually has about 8 to 50 carbon atoms, and the aryl group and alkenyl group in the arylalkenyl group are the same as the above-described aryl group and alkenyl group, respectively. Specific examples thereof include 1-arylvinyl group, 2-arylvinyl group, 1-aryl-1-propylenyl group, 2-aryl-1-propylenyl group, 2-aryl-2-propylenyl group, and 3-aryl-2. -A propylenyl group etc. are mentioned. Also included are aryl alkadienyl groups such as 4-aryl 1,3-butadienyl groups.

  The arylalkynyl group usually has about 8 to 50 carbon atoms, and the aryl group and alkynyl group in the arylalkynyl group are the same as the above aryl group and alkynyl group, respectively. Specific examples thereof include an arylethynyl group, a 3-aryl-1-propionyl group, and a 3-aryl-2-propionyl group. Also included are arylalkadiynyl groups such as 4-aryl-1,3-butadiynyl.

The substituted silyloxy group, an alkyl group, aryl group, arylalkyl group and monovalent silyloxy group in which a hydrogen atom is substituted with 1, 2 or 3 groups selected from the group consisting of heterocyclic groups (H ₃ SiO- ). The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
The substituted silyloxy group usually has about 1 to 60 carbon atoms, preferably 3 to 30 carbon atoms. Specific examples thereof include trimethylsilyloxy group, triethylsilyloxy group, tri-n-propylsilyloxy group, tri- i-propylsilyloxy group, t-butyldimethylsilyloxy group, triphenylsilyloxy group, tri-p-xylylsilyloxy group, tribenzylsilyloxy group, diphenylmethylsilyloxy group, t-butyldiphenylsilyloxy group And a dimethylphenylsilyloxy group.

As the substituted silylthio group, a silylthio group (H ₃ SiS—) in which a hydrogen atom is substituted with 1, 2 or 3 groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. ). The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
The substituted silylthio group usually has about 1 to 60 carbon atoms, preferably 3 to 30 carbon atoms. Specific examples thereof include trimethylsilylthio group, triethylsilylthio group, tri-n-propylsilylthio group, tri- i-propylsilylthio group, t-butyldimethylsilylthio group, triphenylsilylthio group, tri-p-xylylsilylthio group, tribenzylsilylthio group, diphenylmethylsilylthio group, t-butyldiphenylsilylthio group And dimethylphenylsilylthio group.

The substituted silylamino group, an alkyl group, aryl group, arylalkyl group and monovalent silylamino group in which a hydrogen atom in the 1-6 group selected from the group consisting of heterocyclic group is substituted (H ₃ SiNH- or ( H ₃ Si) ₂ N—). The alkyl group, aryl group, arylalkyl group, and monovalent heterocyclic group may have a substituent.
The substituted silylamino group usually has about 1 to 120 carbon atoms, preferably 3 to 60 carbon atoms. Specific examples thereof include trimethylsilylamino group, triethylsilylamino group, tri-n-propylsilylamino group, tri- i-propylsilylamino group, t-butyldimethylsilylamino group, triphenylsilylamino group, tri-p-xylylsilylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, t-butyldiphenylsilylamino group , Dimethylphenylsilylamino group, di (trimethylsilyl) amino group, di (triethylsilyl) amino group, di (tri-n-propylsilyl) amino group, di (tri-i-propylsilyl) amino group, di (t- Butyldimethylsilyl) amino group, di (triphenylsilyl) amino group, di Examples include tri-p-xylylsilyl) amino group, di (tribenzylsilyl) amino group, di (diphenylmethylsilyl) amino group, di (t-butyldiphenylsilyl) amino group, and di (dimethylphenylsilyl) amino group. The

Examples of the substituted amino group include an amino group in which a hydrogen atom is substituted with one or two groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group, and the alkyl group , Aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The substituted amino group usually has about 1 to 40 carbon atoms, and specific examples thereof include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropyl. Amino group, butylamino group, isobutylamino group, s-butylamino group, t-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino Group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamine Amino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group , pentafluorophenyl group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, Pirajiruamino group, triazyl amino group, phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ ~ C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino groups, 1-naphthyl -C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ alkylamino group Etc. are exemplified.

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

The acid imide group includes a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide, and usually has about 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms. Specific examples of the acid imide group include the groups shown below.

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

The monovalent heterocyclic group means a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 2 to 60 carbon atoms. Specific examples thereof include a thienyl group, C _1- C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, an oxazolyl group, a thiazole group, a thiadiazole group and the like. As the monovalent heterocyclic group, a monovalent aromatic heterocyclic group is preferable.

A heteroaryloxy group (a group represented by Q ⁵ —O—, Q ⁵ represents a monovalent heterocyclic group) usually has about 2 to 60 carbon atoms. Specific examples thereof include a thienyloxy group, C ₁ -C ₁₂ alkyl thienyl group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C ₁ -C ₁₂ alkyl pyridyl group, imidazolyloxy group, pyrazolyloxy group, triazolyl group, benzoxazolyl group, Examples include a thiazoleoxy group and a thiadiazoleoxy group. Q ⁵ is preferably a monovalent aromatic heterocyclic group.

(The .Q ⁶ represented by Q ⁶ -S- represents a monovalent heterocyclic group.) Heteroarylthio group has a carbon number in usually about 2 to 60, and specific examples thereof include thienylmercapto group, C ₁ -C ₁₂ alkyl thienylmercapto group, pyrrolyl mercapto group, a furyl mercapto group, pyridyl mercapto group, C ₁ -C ₁₂ alkyl pyridyl mercapto group, imidazolylmethyl mercapto group, a pyrazolyl mercapto group, benzotriazolyl mercapto group, oxazolyl Examples include mercapto group, thiazole mercapto group, thiadiazole mercapto group and the like. Q ⁶ is preferably a monovalent aromatic heterocyclic group.

In the formula (1a), Z ¹ is —M ′ (═O) _p — (wherein M ′ is 3, 4, 5, 6, 7, 8, 9, 9, 10 or 11). Group, group 12, group 13, group 14, group 15, group 16 or group 17 and p represents an integer of 0 to 2) or b-valent aliphatic hydrocarbon group, b A valent aromatic hydrocarbon group, a b-dentate heterocyclic group, —C≡N—, —N═N═N—, —NH—, —NH ₂ —, —OH— or a direct bond. However, when Z ¹ is —M ′ (═O) _p —, —C≡N—, —N═N═N—, —NH—, —NH ₂ — or —OH—, b = 2. Although —C≡N—, —N═N═N—, —NH ₂ — and —OH— alone are positively charged, description of the charge is omitted. (See Chem. Commun., 1999, 1533)
Group 3, Group 4, Group 5, Group 6, Group 8, Group 8, Group 10, Group 11, Group 12, Group 13 in M 'when Z ¹ is -M' (= O) _p- , Group 14, group 15, group 16 or group 17 specifically includes boron atom, carbon atom, nitrogen atom, oxygen atom, fluorine atom, aluminum atom, silicon atom, phosphorus atom, sulfur atom, Chlorine atom, scandium atom, titanium atom, vanadium atom, chromium atom, manganese atom, iron atom, cobalt atom, nickel atom, copper atom, zinc atom, gallium atom, germanium atom, selenium atom, bromine atom, yttrium atom, zirconium atom , Molybdenum atom, palladium atom, hafnium atom, tungsten atom, platinum atom and the like, preferably an atom having an atomic weight of 50 or less.
M ′ is 3, 4, 5, 6, 7, 8, 9, 9, 10, 11, 12, 13, 15, 15, 16, excluding oxygen, or In the case of a group 17 atom, p = 1 can be obtained, and in the case where M ′ is a group 5, 6, or 7 atom, p = 2.
As specific examples in the case of p = 1, 2, -Ti (= O)-, -V (= O)-, -Cr (= O)-, -Cr (= O) _2- , -Zr (= O)-, -Mo (= O)-, -W (= O)-and the like.

The b-valent aliphatic hydrocarbon group for Z ¹ represents an atomic group obtained by removing b hydrogen atoms from an aliphatic hydrocarbon, which may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms is usually about 1-20. b is an integer of 2 to 6, but b does not exceed the number of hydrogen of the aliphatic hydrocarbon.
Specific examples of the aliphatic hydrocarbon include methane, ethane, propane, cyclopropane, butane, cyclobutane, 2-methylpropane, pentane, cyclopentane, 2-methylbutane, 2,2-dimethylpropane, hexane, cyclohexane, heptane, Examples include octane, 2-ethylhexane, nonane, decane, and 3,7-dimethyloctane.
Specific examples of the divalent aliphatic hydrocarbon group (when b = 2) include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a 1,3-cyclopentylene group, Examples include 1,4-cyclohexylene group.
Moreover, the following groups are illustrated as a specific example in case b is 3-6.

The b-valent aromatic hydrocarbon group in Z ¹ represents an atomic group obtained by removing b hydrogen atoms from the aromatic ring of the aromatic hydrocarbon, and may have a substituent on the aromatic ring, Is usually about 6-60. However, b does not exceed the number of hydrogens on the aromatic ring of the aromatic hydrocarbon.
Specific examples of the aromatic hydrocarbon include benzene, C _{1 to} C ₁₂ alkoxybenzene (C _{1 to} C ₁₂ indicate that the number of carbon atoms is ₁ to ₁₂ , and the same applies to the following), C ₁ to C. Examples include ₁₂ alkylbenzenes, naphthalene, anthracene, phenanthrene, tetracene, pentacene and the like.
As a specific example of b = 2 (divalent aromatic hydrocarbon group), it represents an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and usually has 6 to 60 carbon atoms, preferably 6 to 20, phenylene group (for example, formulas 1 to 3 in the figure below), naphthalenediyl group (formulas 4 to 13 in the figure below), anthracenylene group (formulas 14 to 19 in the figure below), biphenylene group (formulas 20 to 20 in the figure below) 25), a triphenylene group (formulas 26 to 28 in the lower figure), a condensed ring compound group (formulas 29 to 38 in the lower figure) and the like. The carbon number of the divalent aromatic hydrocarbon group does not include the carbon number of the substituent R ′ ″.

A plurality of R ′ ″ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group. Group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acid imide group, acyloxy group, monovalent heterocyclic group, hetero Aryloxy group, heteroarylthio group, acyl group, imine residue, substituted silyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl group, carboxyl group, cyano group or nitro group The table .
Alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, substituted silyloxy group , a substituted silylthio group, a substituted amino group, amide group, acid imide group, an acyloxy group, a monovalent heterocyclic group, heteroaryloxy group, defined heteroarylthio group, specific examples and the like, the X ¹ Are the same as those definitions, specific examples, and the like.
The definitions, specific examples and the like of the halogen atom, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group and heteroaryloxycarbonyl group are the same as those of the electron-withdrawing group.

（式中、波線は結合手を表す。） The imine residue refers to an imine compound (an organic compound having —N═C— in the molecule. For example, aldimine, ketimine, and hydrogen atoms on these N are substituted with alkyl groups or the like. And a residue obtained by removing one hydrogen atom from the compound, usually having about 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms. Specific examples include groups represented by the following structural formulas.

(In the formula, a wavy line represents a bond.)

  The substituted silyl group represents a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. Carbon number is about 1-60 normally, Preferably it is C3-C30. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. Examples of substituted silyl groups include trimethylsilyl, triethylsilyl, tri-n-propylsilyl, tri-i-propylsilyl, t-butylsilyldimethylsilyl, triphenylsilyl, tri-p-xylylsilyl, Examples include benzylsilyl group, diphenylmethylsilyl group, t-butyldiphenylsilyl group, dimethylphenylsilyl group and the like.

  As the b-valent aromatic hydrocarbon group when b is 3 to 6, from the examples (1 to 38) of the divalent aromatic hydrocarbon group shown above, further (b-2) R ″ Residues without 'are included.

The b-position heterocyclic group in Z ¹ is a group derived from a heterocyclic compound and having b binding sites. Examples of the binding site include a site that binds to the adjacent atom by a covalent bond (covalent bond site), and a site that binds by a coordinate bond (coordination bond site).
Examples of the b-position heterocyclic group include an atomic group having b coordination sites obtained by removing at least one hydrogen atom from a heterocyclic compound. It may have a substituent, and the carbon number is usually about 2 to 60, preferably 2 to 20.
As a bidentate heterocyclic group (when b = 2), one having two covalent bonding sites (divalent heterocyclic group), one covalent bonding site and one coordination bonding site (Monovalent bidentate heterocyclic group). Specific examples of the divalent heterocyclic group include the following compounds.
A divalent heterocyclic group containing nitrogen as a hetero atom; a pyridinediyl group (formulas 39 to 44 in the following figure), a diazaphenylene group (formulas 45 to 48 in the figure below), a quinoline diyl group (formulas 49 to 63 in the figure below), A quinoxaline diyl group (formulas 64-68 in the lower figure), an acridine diyl group (formulas 69-72 in the lower figure), a bipyridyldiyl group (formulas 73-75 in the lower figure), a phenanthroline diyl group (formulas 76-78 in the lower figure), and the like.
Groups having a fluorene structure containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom (formulas 79 to 93 in the following figure). Moreover, it is desirable from the point of luminous efficiency that it has aromatic amine monomers, such as carbazole of formula 82-84 containing a nitrogen atom, and a triphenylamine diyl group.
5-membered heterocyclic groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom: (formulae 94 to 98 in the following figure).
5-membered condensed heterocyclic groups containing silicon, nitrogen, sulfur, selenium, etc. as heteroatoms: (formula 99-109 in the figure below), benzothiadiazole-4,7-diyl group or benzooxadiazole-4,7- And diyl group.
A 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom and bonded in the α-position of the heteroatom to form a dimer or oligomer: (Formulas 110 to 118 in the figure below) Can be mentioned.
Examples include 5-membered ring heterocyclic groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom and bonded to a phenyl group at the α-position of the hetero atom (formulas 112 to 118 in the following figure).

（式中、Ｍｅはメチル基を表す。）

(In the formula, Me represents a methyl group.)

Here, R is the same or different and is a hydrogen atom, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, Alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acid imide group, acyloxy group, monovalent heterocyclic group, heteroaryloxy Represents a group, heteroarylthio group, acyl group, imine residue, substituted silyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl group, carboxyl group, cyano group or nitro group
Alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, substituted silyloxy group , a substituted silylthio group, a substituted amino group, amide group, acid imide group, an acyloxy group, a monovalent heterocyclic group, heteroaryloxy group, defined heteroarylthio group, specific examples and the like, the X ¹ Are the same as those definitions, specific examples, and the like.
The definitions, specific examples and the like of the halogen atom, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group and heteroaryloxycarbonyl group are the same as those of the electron-withdrawing group.
Definitions, specific examples, and the like of the imine residue and the substituted silyl group are the same as those definitions, specific examples, and the like in R ′ ″.

Specific examples of the monovalent bidentate heterocyclic group include groups in which one of the bonds of the divalent heterocyclic group exemplified in 39 to 118 above is substituted with R, and further has a coordination bond on the hetero atom, And the like.

  When b is 3 to 6, as the b-valent heterocyclic group (having b covalent bonding sites), (b-2) hydrogen atoms are removed from the examples of the divalent heterocyclic group shown above. Residue.

In formula (1a), V ¹ represents a group 16 atom, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a bidentate heterocyclic group, —C≡N—, —N═N═N. -Or represents a direct bond, and a plurality of V ^{1 s} may be the same or different. Z ¹ and V ¹ are not the same.
Examples of the group 16 atom in V ¹ include an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom, and preferably an oxygen atom and a sulfur atom.
The definition and specific examples of the divalent aliphatic hydrocarbon group for V ¹ are the same as those for Z ¹ .
The definition and specific examples of the divalent aromatic hydrocarbon group for V ¹ are the same as those for Z ¹ .
The definition and specific examples of the bidentate heterocyclic group in V ¹ are the same as those in Z ¹ above.

  In the formula (1a), a represents an integer of 1 to 3, a is preferably 2 or 3, and more preferably a is 3. A plurality of a's may be the same or different.

  In the formula (1b), k represents an integer of 1 or more and 4 or less, and from the viewpoint of extending the life when used in an organic electroluminescence device, k is preferably 3 or more, and more preferably k is 4 This is the case.

In the formula (1a), b represents an integer of 2 or more and 6 or less. Where V ¹ is —C≡N—
In the case of -N = N = N- or a direct bond, b is 2.
In formula (1a), c represents an integer of 1 or more and 6 or less.

  Specific examples of the anion represented by the formula (1a) include anions represented by the following VI or VII.

（式中、Ａｒ¹、ａは前述と同じ意味を表す。ＸはＸ¹と同じ意味を表す。ＹはＹ¹と同じ意味を表す。）

(In the formula, Ar ¹ and a represent the same meaning as described above. X represents the same meaning as X ^1. Y represents the same meaning as Y ^1. )

（式中、Ａｒ¹、ａは前述と同じ意味を表す。ＸはＸ¹と同じ意味を表す。ＹはＹ¹と同じ意味を表す。）

(In the formula, Ar ¹ and a represent the same meaning as described above. X represents the same meaning as X ^1. Y represents the same meaning as Y ^1. )

  In formula (VI) and formula (VII), it may have a substituent on the aromatic hydrocarbon ring, heterocyclic ring or hydrocarbon chain.

Among the anions represented by the formula (1a), from the viewpoint of extending the life of the organic electroluminescence device, Ar ¹ is preferably a perfluoroaryl group, and more preferably, a is 2 or 3. is there.

（式中、Ｍはニッケル原子又はパラジウム原子を表す。） In the anion represented by the formula (1a), it is more preferable that Z ¹ or V ¹ is —C≡N—. Specifically, the anion shown by Formula VII is illustrated.
More preferably, the anion represented by formula (1a) is an anion represented by formula (5-1) or formula (5-2).

(In the formula, M represents a nickel atom or a palladium atom.)

Among the anion of the formula (1b), from the viewpoint of lifetime of the organic electroluminescent device, preferably when Ar ¹ is a perfluoroaryl group, more preferably, Ar ¹ is perfluoro aryl group Yes, and k is 3 or 4.

（式中、Ａｒ¹、Ｘ及びｋは上記と同じ意味を表す。） Among the anion of the formula (1b), preferably when Y ¹ is a boron atom, when an anion of the formula (1b-1) is, in view of the lifetime of the organic electroluminescence element Is more preferable.

(In the formula, Ar ¹ , X and k have the same meaning as described above.)

More preferably, the anion represented by the formula (1b-1) is the anion represented by the formula (1b-2).
[B (Ar ^{₄₎ 4] -} (1b-2)
(Wherein, Ar ⁴ is Ar ⁴ be present. Plurality represents a phenyl group wherein a hydrogen atom in the 2 or more substituents selected from the group consisting of fluoro group and a trifluoromethyl group is substituted, the phase in each identical May be different).

In the formula (1b-2), anions in which a plurality of Ar ⁴ are all the same are preferable.
Examples thereof include anions represented by formulas (12) and (13), and anions represented by formula (12) are preferred.

（式中、Ｘは上記と同じ意味を表す。Ａｒ^1cはパーフルオロアリール基を表し、ｋｃは３又は４の整数を表す。） Another preferred embodiment of the anion represented by the formula (1b-1) is an anion represented by the formula (1b-3).

(In the formula, X represents the same meaning as above. Ar ^1c represents a perfluoroaryl group, and kc represents an integer of 3 or 4.)

（式中、Ｍｅはメチル基を表す。） Specific examples of the anion represented by the formula (1b-3) include the following anions.

(In the formula, Me represents a methyl group.)

（式中、Ｙ²は１３族の原子を表し、Ａｒ²は電子吸引性基を有するアリール基又は電子吸引性基を有する１価の複素環基を表し、Ｑ²は酸素原子又は直接結合を表し、Ｘ²はハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、置換アミノ基、アミド基、酸イミド基、アシルオキシ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、シアノ基又はニトロ基を表し、ｄ及びｄ’は、同一又は相異なり、１又は２を表し、Ｖ²は１６族の原子、２価の脂肪族炭化水素基、２価の芳香族炭化水素基、２座の複素環基、−Ｃ≡Ｎ−又は−Ｎ＝Ｎ−を表し、複数個のＹ²、Ａｒ²、Ｑ²及びＶ²は、それぞれ同一でも相異なっていてもよく、Ｘ²が複数個存在する場合、それらは同一であっても相異なっていてもよく、ｅは１〜６の整数を表す。）
である。 The ion pair used in the present invention is characterized in that the anion is represented by formula (1a), formula (1b), formula (2) or formula (3).
Among them, the anion represented by the formula (2) is

(Wherein Y ² represents a group 13 atom, Ar ² represents an aryl group having an electron-withdrawing group or a monovalent heterocyclic group having an electron-withdrawing group, and Q ² represents an oxygen atom or a direct bond. X ² is a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group , Arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acid imide group, acyloxy group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, cyano group or a nitro group, d and d 'are the same or different, represent 1 or 2, V ² is a group 16 original , Divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, bidentate heterocyclic group, -C≡N- or -N = N-a represents a plurality of Y ^2, Ar ^2, Q ² and V ² may be the same or different, and when a plurality of X ² are present, they may be the same or different, and e represents an integer of 1 to 6.)
It is.

（式中、Ａｒ²、Ｘ²、Ｙ²、Ｑ²、ｄ、ｄ’は、前述と同じ意味を表す。） Here, specific examples of the Group 13 atom in Y ² are the same as those in Y ¹ above, and the definition of the monovalent heterocyclic group having an electron-withdrawing group and an aryl group having an electron-withdrawing group in Ar ² is provided. Specific examples and the like are the same as those in Ar ¹ , and the halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group in X ² , Arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acid imide group, acyloxy group, monovalent heterocyclic ring Group, heteroaryloxy group and heteroarylthio group definitions, specific examples, etc. The same as those in X ¹ , the definition of the group 16 atom in V ² , the divalent aliphatic hydrocarbon group, the divalent aromatic hydrocarbon group, the bidentate heterocyclic group, specific examples, etc. Examples of the anion represented by the formula (2) that are the same as those in the V ¹ include an anion represented by the formula VIII.

(In the formula, Ar ² , X ² , Y ² , Q ² , d, and d ′ represent the same meaning as described above.)

  In formula (VIII), it may have a substituent on the aromatic hydrocarbon ring, heterocyclic ring or hydrocarbon chain.

Among the anion of the formula (2), from the viewpoint of lifetime of the organic electroluminescent device, preferably when Ar ² is a perfluoroalkyl aryl group, more preferably Ar ² is located at perfluoro aryl group , And d and d ′ are 2.

（式中、Ｙ³は１３族の原子を表し、Ａｒ³は電子吸引性基を有するアリール基又は電子吸引性基を有する１価の複素環基を表し、Ｑ³は酸素原子又は直接結合を表し、Ｖ³は１６族の原子、２価の脂肪族炭化水素基、２価の芳香族炭化水素基、２座の複素環基、−Ｃ≡Ｎ−又は−Ｎ＝Ｎ−を表し、複数個のＹ³、Ａｒ³、Ｑ³及びＶ³は、それぞれ同一であっても相異なっていてもよく、ｆは１〜６の整数を表す。）
である。
Ｙ³における１３族の原子の具体例は、上記Ｙ¹におけるそれと同様であり、Ａｒ³における電子吸引性基を有するアリール基、電子吸引性基を有する１価の複素環基の定義、具体例等は、前記Ａｒ¹におけるそれらと同様であり、Ｖ³における１６族の原子、２価の脂肪族炭化水素基、２価の芳香族炭化水素基、２座の複素環基の定義、具体例等は、前記Ｖ¹におけるそれらと同様である。 The ion pair used in the present invention is characterized in that the anion is represented by the formula (1a), the formula (1b), the formula (2) or the formula (3). Anion

(Wherein Y ³ represents a Group 13 atom, Ar ³ represents an aryl group having an electron-withdrawing group or a monovalent heterocyclic group having an electron-withdrawing group, and Q ³ represents an oxygen atom or a direct bond. V ³ represents a group 16 atom, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a bidentate heterocyclic group, —C≡N— or —N═N—, Y ³ , Ar ³ , Q ³ and V ³ may be the same or different from each other, and f represents an integer of 1 to 6.
It is.
Specific examples of the group 13 atom in Y ³ are the same as those in Y ¹ above. Definition of aryl group having an electron withdrawing group and a monovalent heterocyclic group having an electron withdrawing group in Ar ³ , specific examples And the like are the same as those in Ar ¹ , and the definition of a group 16 atom, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, and a bidentate heterocyclic group in V ³ , specific examples Etc. are the same as those in V ¹ .

（式中、Ａｒ³、Ｑ³、Ｙ³は、前述と同じ意味を表す。） Specific examples of the anion represented by the formula (3) include an anion represented by the formula IX.

(In the formula, Ar ³ , Q ³ and Y ³ represent the same meaning as described above.)

  In formula (IX), it may have a substituent on the aromatic hydrocarbon ring, heterocyclic ring or hydrocarbon chain.

Among the anions represented by the formula (3), Ar ³ is preferably a perfluoroaryl group from the viewpoint of extending the lifetime of the organic electroluminescence element.

  The ion pair used in the present invention includes an anion represented by the formula (1a) among the anions represented by the formulas (1a), (1b), (2), and (3). preferable.

  Next, the cation of the ion pair used in the present invention will be described. The cation is a carbocation, a hydrogen ion or a metal cation, or an element selected from a nitrogen atom, oxygen atom, phosphorus atom, sulfur atom, chlorine atom, selenium atom, bromine atom, tellurium atom and iodine atom Of Onium.

  The carbocation may be monovalent or divalent or higher, and examples include methylium, ethylium, neopentylium, cyclopropenylium, phenylium, antrilium, and triphenylmethylium.

下記式に示す環状脂肪族アンモニウム塩、

下記式に示す芳香族アンモニウム塩、

下記式に示す窒素原子を含む複素環のオニウム、

（式中、ｎ’は自然数を表す。）
下記式（６）で示される陽イオンなどが例示される。

式中、Ｒ³及びＲ⁴は、同一又は相異なり、アルキル基、アルキルオキシ基、アリール基、アリールオキシ基、アリールアルキル基、アリールアルキルオキシ基、アシル基、アシルオキシ基、１価の複素環基又はヘテロアリールオキシ基を表す。Ｒ⁵及びＲ⁶は、同一又は相異なり、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、置換アミノ基、アミド基、酸イミド基、アシルオキシ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アシル基、イミン残基、置換シリル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アリールアルキルオキシカルボニル基、ヘテロアリールオキシカルボニル基、カルボキシル基、シアノ基又はニトロ基を表す。Ｔは、直接結合、２価の脂肪族炭化水素基、２価の芳香族炭化水素基、アルケニレン基、アルキニレン基又は２価の複素環基を表す。ｉ及びｊは、同一又は相異なり、０〜４の整数を表す。Ｒ⁵及びＲ⁶がそれぞれ複数存在する場合、それらは同一であっても異なっていてもよい。〕
Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶におけるハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、置換アミノ基、アミド基、酸イミド基、アシルオキシ基、１価の複素環基、ヘテロアリールオキシ基及びヘテロアリールチオ基の定義、具体例は、上記Ｘ¹、Ｘ²に記載のそれらと同様である。アシル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アルキルアルキルオキシカルボニル基及びヘテロアリールオキシカルボニル基の定義、具体例は、上記Ａｒ¹、Ａｒ²及びＡｒ³における電子吸引性基に記載のそれらと同様である。
式（６）のＴにおける２価の脂肪族炭化水素基、２価の芳香族炭化水素基の定義、具体例は、上記Ｖ¹、Ｖ²及びＶ³に記載のそれらと同様である。
２価の複素環基は、複素環化合物から水素原子２個を除いた残りの原子団をいい、炭素数が、通常２〜６０程度、好ましくは２〜２０である。なお２価の複素環基上に置換基を有していてもよく、２価の複素環の炭素数には、置換基の炭素数は含まれない。
２価の複素環基の具体例としては、上記Ｚ¹で例示した基が挙げられる。
アルケニレン基は、炭素数が通常２〜２０程度であり、ビニレン基、プロピレン基等が挙げられる。また、アルケニレン基には、１，３−ブタジエニレン基等のアルカジエニレン基も含まれる。
アルキニレン基は、炭素数が通常２〜２０程度であり、エチニレン基などが例示される。また、アルキニレン基には、三重結合を２個有する基も含まれ、例えば、１，３−ブタンジイニレン基があげられる。 The onium of the nitrogen atom may be monovalent or multivalent, and may be an aliphatic ammonium salt represented by the following formula:

A cycloaliphatic ammonium salt represented by the following formula:

An aromatic ammonium salt represented by the following formula:

A heterocyclic onium containing a nitrogen atom represented by the following formula,

(In the formula, n ′ represents a natural number.)
Examples include the cation represented by the following formula (6).

In the formula, R ³ and R ⁴ are the same or different and are an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkyloxy group, an acyl group, an acyloxy group, and a monovalent heterocyclic group. Or represents a heteroaryloxy group. R ⁵ and R ⁶ are the same or different and are a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group , Alkynyl group, arylalkenyl group, arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acid imide group, acyloxy group, monovalent heterocyclic group, heteroaryloxy group, It represents a heteroarylthio group, an acyl group, an imine residue, a substituted silyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group, a carboxyl group, a cyano group, or a nitro group. T represents a direct bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, an alkynylene group or a divalent heterocyclic group. i and j are the same or different and represent an integer of 0 to 4. When a plurality of R ⁵ and R ⁶ are present, they may be the same or different. ]
R ^3, R ^4, halogen atoms in R ⁵ and R ^6, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, an alkenyl group , Alkynyl group, arylalkenyl group, arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acid imide group, acyloxy group, monovalent heterocyclic group, heteroaryloxy group and The definition and specific examples of the heteroarylthio group are the same as those described in X ¹ and X ² above. Acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, the definition of alkyl alkyloxycarbonyl group and heteroaryloxy group, specific examples, and those described in the electron-withdrawing group in the Ar ^1, Ar ² and Ar ³ It is the same.
The definitions and specific examples of the divalent aliphatic hydrocarbon group and divalent aromatic hydrocarbon group in T of the formula (6) are the same as those described in V ¹ , V ² and V ³ above.
The divalent heterocyclic group refers to the remaining atomic group obtained by removing two hydrogen atoms from the heterocyclic compound, and usually has about 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms. In addition, you may have a substituent on a bivalent heterocyclic group, and carbon number of a substituent is not contained in carbon number of a bivalent heterocyclic ring.
Specific examples of the divalent heterocyclic group include the groups exemplified for Z ¹ above.
The alkenylene group usually has about 2 to 20 carbon atoms, and examples thereof include a vinylene group and a propylene group. Alkenylene groups also include alkadielenylene groups such as 1,3-butadienylene groups.
The alkynylene group usually has about 2 to 20 carbon atoms, and examples thereof include an ethynylene group. The alkynylene group also includes a group having two triple bonds, and examples thereof include a 1,3-butanediinylene group.

Specific examples of the cation represented by the formula (6) include the following cations.

  When the cation of the ion pair is a divalent cation represented by the formula (6), it is preferable from the viewpoint of emission intensity.

  The onium of the oxygen atom may be monovalent or multivalent, and trimethyloxonium, triethyloxonium, tripropyloxonium, tributyloxonium, trihexyloxonium, triphenyloxonium, pyririnium, chromenilium, xanthylium Etc. are exemplified.

  The onium of the phosphorus atom may be monovalent or divalent or higher, tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, tetraphenylphosphonium, triphenylmethylphosphonium, methyltriphenylphosphonium. Etc. are exemplified.

The onium of the sulfur atom may be monovalent or multivalent, and may be an aliphatic sulfonium such as trimethylsulfonium, triethylsulfonium, tripropylsulfonium, tributylsulfonium or trihexylsulfonium, triphenylsulfonium, tri (4-methylphenyl). Examples thereof include aromatic sulfoniums such as sulfonium and tri (4-t-butylphenyl) sulfonium, methyldiphenylsulfonium, dimethylphenylsulfonium, onium represented by the following formula, and the like.

  The onium of the chlorine atom may be monovalent or multivalent, and examples thereof include dimethylchloronium, diethylchloronium, dipropylchloronium, dibutylchloronium, diphenylchloronium, and methylphenylchloronium.

  The onium of the selenium atom may be monovalent or multivalent, and trimethyl selenium, triethyl selenium, tripropyl selenium, tributyl selenium, trihexyl selenium, triphenyl selenium, tri (4-methylphenyl) selenium, tri ( 4-t-butylphenyl) selenium, methyldiphenyl selenium, dimethylphenyl selenium and the like are exemplified.

  The onium of the bromine atom may be monovalent or multivalent, and examples thereof include dimethylbromonium, diethylbromonium, dipropylbromonium, dibutylbromonium, diphenylbromonium, and methylphenylbromonium.

  The onium of the tellurium atom may be monovalent or multivalent, and trimethyltelluronium, triethyltelluronium, tripropyltelluronium, tributyltelluronium, trihexyltelluronium, triphenyltelluronium, tri (4-methyl Examples include phenyl) telluronium, tri (4-t-butylphenyl) telluronium, methyldiphenyltelluronium, dimethylphenyltelluronium and the like.

The onium of the iodine atom may be a monovalent or divalent or higher polyvalent dimethyliodonium, diethyliodonium, dipropyliodonium, dibutyliodonium, diphenyliodonium, di (t-butylphenyl) iodonium, 4-methylphenyl-4- Examples include (1-methylethyl) phenyliodonium, methylphenyliodonium, onium represented by the following formula, and the like.

Examples of the metal cation include an alkali metal cation, an alkaline earth metal cation, a rare earth cation, and a transition metal cation. The metal cation may be monovalent or multivalent. Since quenching due to the heavy atom effect may occur, it is preferably a metal cation having an atomic weight of less than 50.
Specifically, examples of alkali metal cations include lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, and francium ions.
Examples of alkaline earth metal cations include beryllium ion, magnesium ion, calcium ion, strontium ion, barium ion, (MgCl) ⁺ , (MgBr) ⁺ , and (MgI) ⁺ .
Examples of rare earth cations include scandium ions and yttrium ions.
Transition metal cations include titanium ion, zirconium ion, hafnium ion, vanadium ion, chromium ion, [bis (η ⁵ -benzene) Cr] ⁺ , manganese ion, iron ion, [(η ⁵ -cyclopentadienyl) (Η ⁶ -benzene) Fe] ⁺ , [(η ⁵ -cyclopentadienyl) (η ⁶ -toluene) Fe] ⁺ , [(η ⁵ -cyclopentadienyl) (η ⁶ -1-methylnaphthalene) Fe ] ⁺ , [(Η ⁵ -cyclopentadienyl) (η ⁶ -cumene) Fe] ⁺ , [bis (η ⁵ -mesitylene) Fe] ⁺ , cobalt ion, nickel ion, copper ion, zinc ion, etc. .

  Specific examples of ion pairs used in the present invention include the following ion pairs.

Examples of the cation having a carbocation include the following ion pairs.

  Examples of ion pairs in which the cation is an onium having a nitrogen atom include aromatic ammonium salt-based compounds, aliphatic ammonium salt-based compounds, aromatic aminium salt-based compounds, and aromatic diazonium salt-based compounds.

  Examples of ion pairs in which the cation is an aromatic ammonium salt are 1-benzyl-2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 1-butyl-3-methylimidazolium tetrakis (pentafluorophenyl) borate, 1-ethyl-3-methylimidazolium tetrakis (pentafluorophenyl) borate 1-octyl-3-methylimidazolium tetrakis (pentafluorophenyl) borate, tris (4-bromophenyl) aminium tetrakis (pentafluorophenyl) borate and the like.

  Examples of the ion pair whose cation is an aliphatic ammonium salt type include tetrabutylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate and the like.

（式中、Ｍｅはメチル基を、Ｂｕはブチル基を表す。） Examples of ion pairs in which the cation is an aliphatic ammonium salt type include the following ion pairs in addition to the above ion pairs.

(In the formula, Me represents a methyl group, and Bu represents a butyl group.)

  Examples of ion pairs whose cation is an aromatic aminium salt include tris (4-bromophenyl) aminium tetrakis (pentafluorophenyl) borate, N, N, N ′, N′-tetraphenyl-4,4′-biphenylene. And diaminium bis (tetrakis (pentafluorophenyl) borate).

（式中、Ｐｈはフェニル基を表す。） Examples of the ion pair whose cation is an aromatic aminium salt type include the following ion pairs in addition to the above ion pairs.

(In the formula, Ph represents a phenyl group.)

  Examples include ion pairs in which the cation is an aromatic diazonium salt, and examples thereof include phenyldiazonium tetrakis (pentafluorophenyl) borate.

Examples of the ion pair whose cation is an aromatic diazonium salt type include the following ion pairs in addition to the above ion pairs.

（式中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、及びＴは、上記と同じ意味を表す。） Examples of the ion pair whose cation is an aromatic ammonium salt type include an ion pair represented by the formula (10).

(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , and T represent the same meaning as described above.)

Examples of ion pairs represented by the formula (10) include the ion pairs exemplified below.

〔式中、式中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、ｉ、ｊ及びＴは、上記と同じ意味を表す。Ｘ^3-及びＸ^4-は、同一又は相異なり、ハロゲン化物イオン、アルキルスルホネートイオン、アリールスルホネートイオンを表す。〕 The ion pair represented by the formula (10) can be produced, for example, by reacting the compound represented by the formula (11) with Li [B (C ₆ F ₅ ) ₄ ] · n (Et ₂ O). it can.

[Wherein, R ³ , R ⁴ , R ⁵ , R ⁶ , i, j and T represent the same meaning as described above. X ^3- and X ^4- are the same or different, represents a halide ion, alkylsulfonate ion, an arylsulfonate ion. ]

Examples of the halide ions include fluoride ions, chloride ions, bromide ions, and iodide ions.
Examples of the alkyl sulfonate ion include methane sulfonate ion, ethane sulfonate ion, and trifluoromethane sulfonate ion.
Examples of the aryl sulfonate ion include benzene sulfonate ion and p-toluene sulfonate ion.

（式中、Ｍｅはメチル基を、Ｐｈはフェニル基を表す。） Examples of the ion pair whose cation is an aromatic ammonium salt type include the following ion pairs in addition to the above ion pairs.

(In the formula, Me represents a methyl group, and Ph represents a phenyl group.)

  Examples of the ion pair in which the cation is an onium having a phosphorus atom include tetraphenylphosphonium tetrakis (pentafluorophenyl) borate.

Examples of ion pairs in which the cation is an onium having a phosphorus atom include the following ion pairs in addition to the above ion pairs.

  Examples of ion pairs in which the cation is an onium having a sulfur atom include aromatic sulfonium salt-based compounds. Examples thereof include bis [4- (diphenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl- 4- (phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis (Pentafluorophenyl) borate and the like.

Examples of ion pairs in which the cation is an onium having a sulfur atom include the following ion pairs in addition to the above ion pairs.

Examples of ion pairs in which the cation is an onium having an iodine atom include aromatic iodonium salts, such as diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl). ) Borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate [available from Rhodia under the name “RHODORSIL photoinitiator PI-2074”.
] Etc. are mentioned.

Examples of the ion pair whose cation is an onium of an iodine atom include the following ion pair in addition to the above ion pair.

  Examples of the ion pair whose cation is a metal cation include (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) tetrakis (pentafluorophenyl) borate.

Examples of ion pairs in which the cation is a metal cation include the following ion pairs in addition to the above ion pairs.

Another embodiment of the ion pair included in the present invention is characterized in that the anion is represented by the formula (5-1) and the cation is a pyridinium cation, a phosphonium cation, or an iodonium cation.

Specific examples of the ion pair are shown below.
Examples of ion pairs in which the cation is a pyridinium cation include the ion pairs exemplified below.

Examples of ion pairs in which the cation is a phosphonium cation include the ion pairs exemplified below.

Examples of ion pairs whose cation is an iodonium cation include the ion pairs exemplified below.

（式中、Ｅ¹⁺は、ピリジニウムカチオン、ホスホニウムカチオン又はヨードニウムカチオンを表す。Ｘ^5-はハロゲン化物イオン、アルキルスルホネートイオン、アリールスルホネートイオンを表す。） The pyridinium salt, phosphonium salt and iodonium salt include, for example, a compound represented by the formula (7-1) and K [(C ₆ F ₅ ) ₃ BC≡NB (C ₆ F ₅ ) ₃ ]. Can be made to react.

(In the formula, E ¹⁺ represents a pyridinium cation, a phosphonium cation or an iodonium cation. X ⁵⁻ represents a halide ion, an alkyl sulfonate ion and an aryl sulfonate ion.)

Examples of the halide ions include fluoride ions, chloride ions, bromide ions, and iodide ions.
Examples of the alkyl sulfonate ion include methane sulfonate ion, ethane sulfonate ion, and trifluoromethane sulfonate ion.
Examples of the aryl sulfonate ion include benzene sulfonate ion and p-toluene sulfonate ion.

（式中、Ｍはニッケル原子又はパラジウム原子を表す。） In another embodiment of the ion pair included in the present invention, the anion is represented by the formula (5-2), and the cation is a pyridinium cation, a quaternary ammonium cation, a phosphonium cation, an oxonium cation, a sulfonium cation, or an iodonium cation. It is characterized by being.

(In the formula, M represents a nickel atom or a palladium atom.)

Specific examples of the ion pair are shown below.
Examples of ion pairs in which the cation is a pyridinium cation include the ion pairs exemplified below.

Examples of ion pairs whose cation is a quaternary ammonium cation include the ion pairs exemplified below.

Examples of ion pairs in which the cation is a phosphonium cation include the ion pairs exemplified below.

Examples of ion pairs whose cation is an oxonium cation include the ion pairs exemplified below.

Examples of ion pairs in which the cation is a sulfonium cation include the compounds exemplified below.

Examples of ion pairs whose cation is an iodonium cation include the ion pairs exemplified below.

（式中、Ｅ²⁺は、ピリジニウムカチオン、４級アンモニウムカチオン、ホスホニウムカチオン、オキソニウムカチオン、スルホニウムカチオン又はヨードニウムカチオンを表す。
Ｘ^6-は、ハロゲン化物イオン、アルキルスルホネートイオン、アリールスルホネートイオンを表す。） For example, the pyridinium salt, phosphonium salt and iodonium salt may be obtained by reacting the compound represented by the formula (7-2) with K ₂ [M {C≡NB (C ₆ F ₅ ) ₃ } ₄ ]. Can be manufactured.

(Wherein, E ²⁺ represents a pyridinium cation, quaternary ammonium cation, phosphonium cation, an oxonium cation, a sulfonium cation or an iodonium cation.
X ⁶⁻ represents a halide ion, an alkyl sulfonate ion, or an aryl sulfonate ion. )

Specific examples of the halide ion, alkyl sulfonate ion, and aryl sulfonate ion include the ions exemplified in ^X5- above.
One type or two or more types of ion pairs may be used in the present invention.

Next, the polymer light emitter used in the present invention will be described.
The polymer light emitter used in the present invention has a polystyrene-equivalent number average molecular weight of usually 10 ³ to 10 ⁸ . Among the polymer light emitters of the present invention, those that are conjugated polymer compounds are preferred.
Here, the conjugated polymer compound means a polymer compound in which a delocalized π electron pair exists along the main chain skeleton of the polymer compound. As this delocalized electron, an unpaired electron or a lone electron pair may participate in resonance instead of a double bond.

<Conjugated polymer compound>
The conjugated polymer compound used in the present invention includes (1) a polymer compound substantially composed of a structure in which double bonds and single bonds are arranged alternately, and (2) a double bond and a single bond contain nitrogen atoms. (3) a structure in which double bonds and single bonds are arranged alternately and a structure in which double bonds and single bonds are arranged through nitrogen atoms. In the present specification, specifically, an unsubstituted or substituted fluorenediyl group, an unsubstituted or substituted benzofluorenediyl group, an unsubstituted or substituted dibenzofurandiyl group, Unsubstituted or substituted dibenzothiophenediyl group, unsubstituted or substituted carbazolediyl group, unsubstituted or substituted thiophenediyl group, unsubstituted or substituted furandyl group, unsubstituted or substituted pyrroldiyl group, unsubstituted or substituted Benzo Repeat one or more selected from the group consisting of an asiazole diyl group, an unsubstituted or substituted phenylene vinylene diyl group, an unsubstituted or substituted thienylene vinylene diyl group, and an unsubstituted or substituted triphenylamine diyl group A polymer compound in which the repeating units are bonded directly or via a linking group.

  In the conjugated polymer compound, when the repeating units are bonded via a linking group, examples of the linking group include phenylene, biphenylene, naphthalenediyl, anthracenediyl, and the like.

（８） （９）
〔式中、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶及びＲ¹⁷は、同一又は相異なり、水素原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基又はアリールアルキルチオ基を表す。〕 The conjugated polymer compound used in the present invention preferably has one or more repeating units selected from the group consisting of formula (8) and formula (9) from the viewpoint of charge transportability.

(8) (9)
[Wherein, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are the same or different and represent a hydrogen atom, an alkyl group, an alkyloxy group, An alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group or an arylalkylthio group is represented. ]

In the formula (8) and (9), the alkyl group represented by R ⁸ to R ^17, aryl group, alkyloxy group, alkylthio group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, aryl Specific examples of the alkylthio group are the same as those defined in X ¹ , specific examples, and the like.

The conjugated polymer compound preferably has a polystyrene-equivalent weight average molecular weight of 1 × 10 ³ to 1 × 10 ⁷ from the viewpoint of film forming ability and solubility in a solvent, and is preferably 1 × 10 ³ to 1 × 10 7. ⁶ is more preferable.

  The conjugated polymer compound contained in the organic layer of the organic electroluminescence device of the present invention may be one type or two or more types.

  The conjugated polymer compound is prepared by synthesizing a monomer having a functional group suitable for the polymerization reaction to be used, and then dissolved in an organic solvent as necessary, for example, using an alkali, an appropriate catalyst, or a ligand. Polymerization can be performed by a known polymerization method such as aryl coupling.

<Light emitting layer>
The light emitting layer of the organic electroluminescence device of the present invention includes an ion pair represented by the formula (1a), formula (1b), formula (2), or formula (3) and a polymer light emitter. The weight of the ion pair represented by formula (1a), formula (1b), formula (2) or formula (3) in the light emitting layer is preferably 0.001 to 10 with respect to 100 parts by weight of the polymer light emitter. Parts by weight, more preferably 0.01 to 1 part by weight.

  In the light emitting layer of the organic electroluminescence device of the present invention, ions represented by the formula (1a), the formula (1b), the formula (2), or the formula (3) are provided as long as the charge transport property and the charge injection property are not impaired. Components other than the pair may be included.

<Organic electroluminescence device>
The organic electroluminescence device of the present invention includes a pair of electrodes, at least one of which is transparent or translucent, a polymer light emitter, and the formula (1a), formula (1b), formula (2) or formula between the electrodes. It has a light emitting layer containing the ion pair represented by (3). One of the pair of electrodes is an anode, and the other is a cathode.

  In the organic electroluminescence device of the present invention, a light emitting layer including a polymer light emitter and an ion pair is formed on an anode, then a cathode is formed on the light emitting layer, and 10 V is provided between the anode and the cathode. It can be obtained by applying a voltage as described above and conducting an energization process in which a current flows from the anode to the cathode. The light emitting layer may be formed directly on the anode, or may be formed via a hole injection layer and / or a hole transport layer. The cathode may be formed directly on the light emitting layer, or may be formed via an electron injection layer and / or an electron transport layer.

  The light emitting layer contained in the organic electroluminescence device of the present invention is composed of a composition of an ion pair compound represented by the formula (1a), formula (1b), formula (2) or formula (3) and the polymer light emitter. Can be used.

  The weight of the ion pair compound represented by formula (1a), formula (1b), formula (2) or formula (3) in the composition is preferably 0.001 with respect to 100 parts by weight of the conjugated polymer compound. -10 parts by weight, more preferably 0.01-1 part by weight.

  The method for producing the light emitting layer is not particularly limited, and examples thereof include a method by film formation from a solution containing the composition and a solvent, but a thin film may be formed by vacuum deposition.

The solvent used for film formation from a solution is not particularly limited as long as it dissolves the ion pair compound and the conjugated polymer compound represented by formula (1a), formula (1b), formula (2), or formula (3). There is no.
Examples of the solvent include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, and t-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, Halogenated saturated hydrocarbon solvents such as dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene, tetrahydrofuran And ether solvents such as tetrahydropyran. The composition of the ion pair compound represented by the formula (1a), the formula (1b), the formula (2) or the formula (3) and the polymer light emitter used in the present invention is usually 0.1 wt. % Or more can be dissolved.

  For film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic method Coating methods such as a printing method, an offset printing method, an ink jet printing method, a dispenser printing method, a nozzle coating method, a capillary coating method can be used, and a spin coating method, a flexographic printing method, an ink jet printing method, and a dispenser printing method are preferable.

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

  The organic electroluminescence element of the present invention is energized. The voltage to be applied is preferably 10 V or more and 100 V or less, more preferably 10 V or more and 50 V or less. The voltage application may be constant, or the voltage may be increased or decreased in stages. The total energization time is preferably 0.01 seconds to 1 hour, more preferably 0.1 seconds to 30 minutes. By energizing to 10 V or more, the orientation of the ion pair in the light emitting layer can be controlled, and a long-life organic electroluminescence element can be obtained.

  As the organic electroluminescence device of the present invention, (1) an organic electroluminescence device provided with an electron transport layer between the cathode and the light emitting layer, and (2) a hole transport layer provided between the anode and the light emitting layer. Organic electroluminescent elements, (3) organic electroluminescent elements in which an electron transport layer is provided between the cathode and the light emitting layer, and a hole transport layer is provided between the anode and the light emitting layer.

The organic electroluminescence device of the present invention is usually formed on a substrate. This substrate may be any substrate that does not change when an electrode is formed and an organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon.
In the case of an opaque substrate, the opposite electrode (that is, the electrode far from the substrate) is preferably transparent or translucent.

Examples of the transparent or translucent electrode material include a conductive metal oxide film and a translucent metal thin film. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film thereof (NESA) manufactured using a conductive material made of indium / tin / oxide (ITO), indium / zinc / oxide, or the like. Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material. Furthermore, as the electrode material, a metal, a conductive polymer, or the like can be used. Preferably, one of the pair of electrodes is preferably a material having a small work function. For example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and two of them One or more alloys, or one or more of them and an alloy of one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite, or a graphite intercalation compound are used. It is done.
Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy and the like.

  Materials used for the electron transport layer include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, 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 derivatives thereof, and the like. The materials used for the hole transport layer include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives, polymer compounds having an aromatic amine residue, polyaniline and derivatives thereof, polythiophene and derivatives thereof, Examples thereof include poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof. The organic electroluminescent device of the present invention may further include a buffer layer, and examples of the material used as the buffer layer include alkali metals such as lithium fluoride, halides of alkaline earth metals, and oxides. . In addition, fine particles of inorganic semiconductor such as titanium oxide can be used for the buffer layer.

  The organic thin film contained in the light emitting layer has a film thickness of usually 1 nm to 100 μm, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and further preferably 20 nm to 200 nm.

<Application of device>
The organic electroluminescence element described above can be suitably used for a curved or flat illumination device, for example, a planar light source used as a light source of a scanner, and a display device.

  Examples of the display device including the organic electroluminescence element include a segment display device and a dot matrix display device. The dot matrix display device includes an active matrix display device and a passive matrix display device. An organic electroluminescent element is used as a light emitting element constituting each pixel in an active matrix display device and a passive matrix display device. In addition, the organic EL element is used as a light emitting element constituting each segment in the segment display device, and is used as a backlight in the liquid crystal display device.

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

-Method for measuring molecular weight-
In Examples, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined in terms of polystyrene by gel permeation chromatography (GPC). Specifically, using a column in which three TSKgel SuperHM-H (manufactured by Tosoh) are connected in series by GPC (manufactured by Tosoh, product name: HLC-8220GPC), the flow rate is 0.5 mL / min using tetrahydrofuran as a developing solvent. And measured at 40 ° C. A differential refractive index detector was used as the detector.

で表される化合物Ａ 6.2171g、下記式：

で表される化合物Ｂ 0.5085g、下記式：

で表される化合物Ｃ 6.2225g、及び下記式：

で表される化合物Ｄ 0.5487gを取り、窒素置換した。トルエン100mlを加え、ジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ） 7.6mg、炭酸ナトリウム水溶液24mlを加え、還流下で３時間攪拌した。その後、フェニルホウ酸0.40gを加え、終夜攪拌した。その後、ナトリウムＮ，Ｎ−ジエチルジチオカルバメート水溶液を加え、さらに還流下で３時間攪拌した。得られた反応液を分液し、有機相を酢酸水溶液及び水で洗浄した後、メタノール中に滴下したところ、沈殿が生じた。得られた沈殿を、ろ過し、減圧乾燥した後、トルエンに溶解させ、シリカゲル−アルミナカラムを通し、トルエンで洗浄した。得られたトルエン溶液をメタノール中に滴下したところ、沈殿が生じた。得られた沈殿を、ろ過し、減圧乾燥した後、トルエンに溶解させ、メタノールに滴下ところ、沈殿が生じた。得られた沈殿を、ろ過し、減圧乾燥して、7.72gの共役高分子化合物である高分子化合物１を得た。高分子化合物１のポリスチレン換算の数平均分子量Ｍｎは１．２×１０⁵であり、ポリスチレン換算の重量平均分子量Ｍｗは２．９×１０⁵であった。 <Synthesis Example 1> (Synthesis of Polymer Compound 1)
Triscaprylylmethylammonium chloride (trade name: Aliquat336 “registered trademark”, manufactured by Aldrich) 1.72 g in a 500 ml four-necked flask, the following formula:

6.2171 g of the compound A represented by the following formula:

Compound B 0.5085 g represented by the following formula:

6.2225 g of the compound C represented by the formula:

The compound D represented by the formula (0.5487 g) was taken and replaced with nitrogen. Toluene (100 ml) was added, dichlorobis (triphenylphosphine) palladium (II) (7.6 mg) and sodium carbonate aqueous solution (24 ml) were added, and the mixture was stirred under reflux for 3 hours. Thereafter, 0.40 g of phenylboric acid was added and stirred overnight. Thereafter, an aqueous sodium N, N-diethyldithiocarbamate solution was added, and the mixture was further stirred for 3 hours under reflux. The obtained reaction solution was separated, and the organic phase was washed with an acetic acid aqueous solution and water, and then dropped into methanol, resulting in precipitation. The obtained precipitate was filtered, dried under reduced pressure, dissolved in toluene, passed through a silica gel-alumina column, and washed with toluene. When the obtained toluene solution was dropped into methanol, precipitation occurred. The obtained precipitate was filtered, dried under reduced pressure, dissolved in toluene, and dropped into methanol, resulting in precipitation. The obtained precipitate was filtered and dried under reduced pressure to obtain 7.72 g of polymer compound 1 as a conjugated polymer compound. The number average molecular weight Mn in terms of polystyrene of the polymer compound 1 was 1.2 × 10 ⁵ , and the weight average molecular weight Mw in terms of polystyrene was 2.9 × 10 ⁵ .

で表される化合物Ｅ 234.06g、下記式：

で表される化合物Ｆ 172.06g、及び下記式：

で表される化合物Ｇ 28.5528gを取り、窒素置換した。アルゴンバブリングしたトルエン2620gを加え、攪拌しながら更に30分間バブリングした。酢酸パラジウム 99.1mg、トリス（ｏ−トリル）ホスフィン 937.0mgを加え、158gのトルエンで洗い流し、95℃に加熱した。17.5重量％炭酸ナトリウム水溶液855gを滴下後、バス温を110℃に昇温し、9.5時間攪拌した後、フェニルホウ酸5.39gをトルエン96mlに溶解して加え、14時間攪拌した。200mlのトルエンを加え、反応液を分液し、有機相を３重量％酢酸水溶液850mlで２回、さらに850mlの水とナトリウムＮ，Ｎ−ジエチルジチオカルバメート19.89gを加え、４時間攪拌した。分液後、シリカゲル−アルミナカラムを通し、トルエンで洗浄した。得られたトルエン溶液をメタノール５０Ｌに滴下したところ、沈殿が生じた。得られた沈殿を、メタノールで洗浄した。減圧乾燥後、１１Ｌのトルエンに溶解させ、得られたトルエン溶液をメタノール５０Ｌに滴下したところ、沈殿が生じた。得られた沈殿を、ろ過し、減圧乾燥して、278.39gの高分子化合物２を得た。高分子化合物２のポリスチレン換算の数平均分子量Ｍｎは７．７×１０⁴であり、ポリスチレン換算の重量平均分子量Ｍｗは３．８×１０⁵であった。 <Synthesis Example 2> (Synthesis of Polymer Compound 2)
Triscaprylylmethylammonium chloride (trade name: Aliquat336 “registered trademark”, manufactured by Aldrich) 40.18 g in a 5 L separable flask, the following formula:

Compound E 234.06 g represented by the following formula:

172.06 g of the compound F represented by the following formula:

28.5528 g of the compound G represented by the formula (1) was taken and replaced with nitrogen. Arranged bubbling toluene (2020 g) was added and bubbling was continued for another 30 minutes. 99.1 mg of palladium acetate and 937.0 mg of tris (o-tolyl) phosphine were added, washed with 158 g of toluene, and heated to 95 ° C. After dropwise addition of 855 g of 17.5 wt% sodium carbonate aqueous solution, the bath temperature was raised to 110 ° C. and stirred for 9.5 hours. Then, 5.39 g of phenylboric acid was dissolved in 96 ml of toluene and stirred for 14 hours. 200 ml of toluene was added, the reaction solution was separated, and the organic phase was added twice with 850 ml of 3% by weight acetic acid aqueous solution, and further 850 ml of water and 19.89 g of sodium N, N-diethyldithiocarbamate were added and stirred for 4 hours. After separation, the solution was passed through a silica gel-alumina column and washed with toluene. When the obtained toluene solution was dropped into 50 L of methanol, precipitation occurred. The resulting precipitate was washed with methanol. After drying under reduced pressure, the product was dissolved in 11 L of toluene, and the resulting toluene solution was dropped into 50 L of methanol, resulting in precipitation. The resulting precipitate was filtered and dried under reduced pressure to obtain 278.39 g of polymer compound 2. The number average molecular weight Mn in terms of polystyrene of the polymer compound 2 was 7.7 × 10 ⁴ , and the weight average molecular weight Mw in terms of polystyrene was 3.8 × 10 ⁵ .

（Ｈ） <Synthesis Example 3> (Synthesis of ion pair (H))
The 300 ml eggplant type flask was purged with nitrogen, 5.00 g of tris (pentafluorophenyl) borane was dissolved in 200 ml of dehydrated diethyl ether, and 0.31 g of potassium cyanide was added. After refluxing for 3 hours, the solvent was distilled off to obtain 5.71 g of an ion pair (H).
MS (ESI-negative)
m / z 1049.8 ([M−K] ⁻ )

(H)

（Ｉ） <Synthesis Example 4> (Synthesis of ion pair (I))
The 200 ml four-necked flask was purged with nitrogen, and 0.486 g of tri (4-t-butylphenylsulfonium) trifluoromethanesulfonate, 0.873 g of ion pair (H), 20 ml of ion-exchanged water, and 60 ml of diethyl ether were charged. After attaching a stir bar, thermometer and condenser, the reaction was carried out at 21-23 ° C. for 16 hours. After the reaction, the contents of the flask were transferred to a 200 ml separatory funnel and the aqueous layer was separated. The ether layer was washed 3 times with 30 ml of ion exchange water. The ether layer was transferred to a 200 ml Erlenmeyer flask and dehydrated by adding anhydrous sodium sulfate, and then anhydrous sodium sulfate was filtered off. The ether layer was concentrated with an evaporator and then dried at 70 to 75 ° C. with a vacuum pump until a constant weight was obtained. 1.19 g of ion pair (I) was obtained.
^{1 H-NMR (300MHz, DMSO} -D 6)
δ 7.78 (12H, m), 1.32 (27H, s)

(I)

（Ｊ） <Synthesis Example 5> (Synthesis of ion pair (J))
The 200 ml four-necked flask was purged with nitrogen and charged with 0.205 g of 1,1′-dibenzyl-4,4′-bipyridinium dichloride, 1.089 g of Compound H, 20 ml of ion-exchanged water, and 60 ml of diethyl ether. After attaching a stir bar, thermometer and condenser, the reaction was carried out at 21-23 ° C. for 18 hours. After the reaction, the contents of the flask were transferred to a 200 ml separatory funnel and the aqueous layer was separated. Next, the ether layer was washed 3 times with 30 ml of ion exchange water. The ether layer was transferred to a 200 ml Erlenmeyer flask and dehydrated by adding anhydrous sodium sulfate, and then anhydrous sodium sulfate was filtered off. The ether layer was concentrated with an evaporator. Furthermore, it dried until it became constant weight with a vacuum pump at 80-85 degreeC. 1.21 g of ion pair J was obtained.

¹ H-NMR (270 MHz, DMSO-D ₆ )
δ 9.501 (4H, d), 8.733 (4H, d), 7.606 (4H, m), 7.479 (6H, m)

(J)

（Ｋ） <Synthesis Example 6> (Synthesis of ion pair (K))
The 50 ml four-necked flask was purged with nitrogen, and 0.309 g of poly (1-n-butyl-4-vinylpyridinium trifluoromethanesulfonimide), 1.088 g of compound H, and 30 ml of dimethylformamide were charged. After attaching a stir bar, thermometer and condenser, the reaction was carried out at 21-23 ° C. for 16 hours. After the reaction, the contents of the flask were transferred to a 200 ml separatory funnel, charged with 90 ml of toluene, and DMF was extracted with 50 ml of ion-exchanged water. The toluene layer was washed 3 times with 50 ml of water. The toluene layer was transferred to a 200 ml Erlenmeyer flask and dehydrated by adding anhydrous sodium sulfate, and then anhydrous sodium sulfate was filtered off. The toluene layer was concentrated at 70 to 75 ° C. with an evaporator, and then dried with a vacuum pump until a constant weight was reached. 1.08 g of ion pair K was obtained.
¹ H-NMR (300 MHz, DMSO-D ₆ )
δ5.8, 7.4, 9.1
¹⁹ F-NMR (300 MHz, DMSO-D ₆ )
δ-132.7, -133.6, -134.8, -157.7, -159.8, -162.5, -164.0, -165.2, -166.0

(K)

（Ｌ） <Synthesis Example 7> (Synthesis of ion pair (L))
The 200 ml four-necked flask was purged with nitrogen, and 1.089 g of Compound H, 20 ml of ion-exchanged water, and 50 ml of diethyl ether were charged. After attaching a stir bar, thermometer and condenser, 11 g of 1% hydrochloric acid was added dropwise at 21-23 ° C. over 10 minutes with stirring. After stirring for 2 hours, the contents of the flask were transferred to a 200 ml separatory funnel and the aqueous layer was separated. Next, the ether layer was washed 3 times with 30 ml of ion exchange water. The ether layer was transferred to a 200 ml Erlenmeyer flask and dehydrated by adding anhydrous sodium sulfate, and then anhydrous sodium sulfate was filtered off. The organic layer was concentrated with an evaporator. Furthermore, it dried until it became constant weight with a vacuum pump at 80-85 degreeC. 1.06 g of ion pair L was obtained.
¹⁹ F-NMR (300 MHz, DMSO-D ₆ )
δ-132.7, −133.7, −134.3, −154.8, −157.8, −159.2, −161.0, −162.9, −164.3, −165.4 -165.6, -166.5

(L)

<Preparation of coating solution A>
The polymer compound 1 was dissolved in xylene at a concentration of 1.0% by weight, and then the ion pair (I) was mixed with the solution so that the weight was 0.2% with respect to the weight of the polymer compound 1. Subsequently, the solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.2 μm to prepare a coating solution A.

<Preparation of coating solution B>
The polymer compound 1 was dissolved in xylene at a concentration of 1.0% by weight, and then the solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.2 μm to prepare a coating solution B.

（Ｍ） <Preparation of coating solution C>
Polymer compound 1 was dissolved in xylene at a concentration of 1.0% by weight, and then ion pair M (N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (manufactured by STREM CHEMICALS)) represented by the following formula: Was mixed with the solution so that the weight was 0.2% with respect to the weight of the polymer compound 1. Subsequently, the solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.2 μm to prepare a coating solution C.

(M)

（Ｎ） <Preparation of coating solution D>
Polymer compound 1 was dissolved in xylene at a concentration of 1.0% by weight, and then ion pair N (4-isopropyl-4'-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate (Tokyo) represented by the following formula: Kasei) was mixed with the solution so that the weight was 0.2% with respect to the weight of the polymer compound 1. Subsequently, the solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.2 μm to prepare a coating solution D.

(N)

<Preparation of coating solution E>
The polymer compound 1 was dissolved in xylene at a concentration of 1.0% by weight, and then the ion pair (H) was mixed with the solution so that the weight was 0.2% with respect to the weight of the polymer compound 1. Subsequently, the solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.2 μm to prepare a coating solution E.

<Preparation of coating solution F>
The polymer compound 1 was dissolved in xylene at a concentration of 1.0% by weight, and then the ion pair (J) was mixed with the solution so that the weight was 0.2% with respect to the weight of the polymer compound 1. Subsequently, the solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.2 μm to prepare a coating solution F.

<Preparation of coating solution G>
The polymer compound 1 was dissolved in xylene at a concentration of 1.0% by weight, and then the ion pair (K) was mixed with the solution so that the weight was 0.2% with respect to the weight of the polymer compound 1. Next, the solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.2 μm to prepare a coating solution G.

<Preparation of coating solution H>
The polymer compound 1 was dissolved in xylene at a concentration of 1.0% by weight, and then the ion pair (L) was mixed with the solution so that the weight was 0.2% with respect to the weight of the polymer compound 1. Next, the solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.2 μm to prepare a coating solution H.

<Example 1>
(Production and evaluation of organic electroluminescence elements)
A hole injection layer solution (trade name: CLEVIOS AI4083, manufactured by H.C. Starck Co., Ltd.) is spin-coated on a glass substrate on which an indium tin oxide (ITO) film having a thickness of 150 nm is attached by sputtering. A hole injection layer (film thickness: 65 nm) was produced by applying the coating to dry the film at 200 ° C. for 10 minutes on a hot plate in the atmosphere. Next, the xylene solution of the polymer compound 2 was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm, and then applied onto the hole injection layer by spin coating, and 180 ° C. under a nitrogen atmosphere in a glove box. Was baked for 15 minutes to prepare a hole transport layer (film thickness: 20 nm).
Further, the coating solution A was applied onto the hole transport layer by spin coating to form a light emitting layer. In manufacturing the light emitting layer, the film thickness was adjusted to 80 nm.
Thereafter, after baking for 10 minutes on a hot plate at 130 ° C. under nitrogen, NaF was vapor-deposited with a thickness of 4 nm, and then Al was vapor-deposited with a thickness of 100 nm to form a cathode. The degree of vacuum at the time of vapor deposition was in the range of 1 × 10 ⁻⁴ Pa to 9 × 10 ⁻³ Pa. The shape of the element was a regular square of 2 mm × 2 mm. A voltage was applied stepwise from −5 V to 15 V to the obtained element to conduct an energization process, and an organic electroluminescence element was produced. The energization time for each voltage was 1 second.

Thereafter, a constant current driving life test was performed at an initial luminance of 5000 cd / m ² . The time until the initial luminance reached 4000 cd / m ² (80% of the initial luminance) (referred to as LT80) was measured. Table 1 shows the results. The voltage at the start of driving in the constant current driving life test was about 7.5V.

<Example 2>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescent element was produced in the same manner as in Example 1 except that the voltage applied to the element was 15 V and the energization time was once per second, and LT80 of the organic electroluminescent element was determined. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 7.6V.

<Example 3>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescence element was produced in the same manner as in Example 1 except that the voltage applied to the element was 20 V and the energization time was once per second, and LT80 of the organic electroluminescence element was determined. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 7.5V.

<Example 4>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescence device was prepared in the same manner as in Example 1 except that the coating solution C was used instead of the coating solution A, and LT80 of the organic electroluminescence device was obtained. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 9.8V.

<Example 5>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescence element was produced in the same manner as in Example 1 except that the coating solution D was used instead of the coating solution A, and LT80 of the organic electroluminescence element was obtained. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 6.6V.

<Example 6>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescence element was produced in the same manner as in Example 1 except that the coating solution E was used instead of the coating solution A, and LT80 of the organic electroluminescence element was obtained. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 6.7V.

<Example 7>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescence element was produced in the same manner as in Example 1 except that the coating solution F was used instead of the coating solution A, and LT80 of the organic electroluminescence element was obtained. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 7.2V.

<Example 8>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescence element was prepared in the same manner as in Example 1 except that the coating solution G was used instead of the coating solution A, and LT80 of the organic electroluminescence element was obtained. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 7.1V.

<Example 9>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescence element was produced in the same manner as in Example 1 except that the coating solution H was used instead of the coating solution A, and LT80 of the organic electroluminescence element was obtained. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 6.6V.

<Comparative Example 1>
(Production and evaluation of organic electroluminescence elements)
Prior to the start of driving in the constant current driving life test, an organic electroluminescence element was produced in the same manner as in Example 1 except that no voltage was applied to the element, and LT80 of the organic electroluminescence element was obtained. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 7.1 V, and the voltage after LT80 was about 8.8 V.

<Comparative example 2>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescence device was prepared in the same manner as in Example 1 except that the coating solution B was used instead of the coating solution A, and the device was not energized before starting the driving of the constant current driving life test. LT80 was obtained. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 4.0V, and the voltage after LT80 was about 4.5V.

<Comparative Example 3>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescence device was prepared in the same manner as in Example 1 except that the coating solution B was used in place of the coating solution A, the voltage applied to the device was 15 V, and the energization time was once per second. The LT80 of the electroluminescence element was determined. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 4.4V, and the voltage after LT80 was about 4.9V.

<Comparative example 4>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescence device was prepared in the same manner as in Example 1 except that the coating solution B was used in place of the coating solution A, the voltage applied to the device was 20 V, and the energization time was once per second. The LT80 of the electroluminescence element was determined. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 4.3 V, and the voltage after LT80 was about 4.9 V.

<Comparative Example 5>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescent device was prepared in the same manner as in Example 1 except that the coating solution C was used instead of the coating solution A, and the device was not energized before starting the constant current driving life test. LT80 was obtained. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 9.6V, and the voltage after LT80 was about 10.2V.

<Comparative Example 6>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescence device was prepared in the same manner as in Example 1 except that the coating solution D was used instead of the coating solution A, and the device was not energized before starting the constant current driving life test. LT80 was obtained. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 6.7V, and the voltage after LT80 was about 8.1V.

<Comparative Example 7>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescence device was prepared in the same manner as in Example 1 except that the coating solution E was used instead of the coating solution A, and the device was not energized before starting the driving of the constant current driving life test. LT80 was obtained. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 6.3 V, and the voltage after LT80 was about 7.4 V.

<Comparative Example 8>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescence device was prepared in the same manner as in Example 1 except that the coating solution F was used instead of the coating solution A and the device was not energized before starting the constant current driving life test. LT80 was obtained. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 6.9V, and the voltage after LT80 was about 7.9V.

<Comparative Example 9>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescence device was prepared in the same manner as in Example 1 except that the coating solution G was used instead of the coating solution A and the device was not energized before starting the constant current driving life test. LT80 was obtained. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 6.8 V, and the voltage after LT80 was about 7.9 V.

<Comparative Example 10>
(Production and evaluation of organic electroluminescence elements)
An organic electroluminescence device was prepared in the same manner as in Example 1 except that the coating solution H was used instead of the coating solution A, and the device was not energized before starting the constant current driving life test. LT80 was obtained. The measurement results are shown in Table 1. The voltage at the start of driving in the constant current driving life test was about 6.6V, and the voltage after LT80 was about 7.5V.

-Evaluation-
As can be seen from Table 1, a voltage is applied to the light-emitting layer formed using the composition containing the conjugated polymer compound (polymer compound 1) and the ion pairs (H) to (N) and subjected to an energization treatment. The organic electroluminescence device thus produced had a longer LT80 lifetime than the organic electroluminescence device that was not subjected to the energization treatment or the organic electroluminescence device that did not contain the ion pairs (H) to (N).

Claims (10)

A light emitting layer including a polymer light emitter and an ion pair is formed on the anode, and the anion of the ion pair is an anion represented by the formula (1a), the formula (1b), the formula (2), or the formula (3). An organic electrocatalyst obtained by forming a cathode on the light emitting layer, applying a voltage of 10 V or more between the anode and the cathode, and passing a current from the anode to the cathode. Luminescence element.

(Wherein Y ¹ represents a Group 13 atom, Ar ¹ represents an aryl group having an electron-withdrawing group or a monovalent heterocyclic group having an electron-withdrawing group, and Q ¹ represents an oxygen atom or a direct bond. It represents, X ¹ is a halogen atom, an alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group , Arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acid imide group, acyloxy group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, cyano group Or a nitro group, a represents an integer of 1 to 3, k represents an integer of 1 to 4, and V ¹ represents a group 16 element. A divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a bidentate heterocyclic group, —C≡N—, —N═N═N— or a direct bond; Represents an integer of 6, Z ¹ is —M ′ (═O) _p — (wherein M ′ is 3, 4, 5, 6, 7, 8, 9, 9, 10 or 11). Group, group 12, group 13, group 14, group 15, group 16 or group 17 and p represents an integer of 0 to 2) or b-valent aliphatic hydrocarbon group, b A valent aromatic hydrocarbon group, a b-dentate heterocyclic group, —C≡N—, —N═N═N—, —NH—, —NH ₂ —, —OH— or a direct bond, provided that Z ^{When 1} is —M ′ (═O) _p —, —C≡N—, —N═N═N—, —NH—, —NH ₂ — or —OH—, b = 2, and Z ¹ Unlike phase and V ^1, if Y ^1, Q ^1, Ar ¹ and X ¹ are present a plurality, they May be different even one, a plurality of a and V ¹ was, respectively may be different mutually be the same, c is an integer of 1-6.)

(Wherein, Y ² is represents the group 13 atoms, Ar ² represents a monovalent heterocyclic group having an aryl group or an electron withdrawing group having an electron-withdrawing group, Q ² is an oxygen atom or a direct bond X ² is a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group , Arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acid imide group, acyloxy group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, cyano group or a nitro group, d and d 'are the same or different, represent 1 or 2, V ² is a group 16 original , Divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, bidentate heterocyclic group, -C≡N- or -N = N-a represents a plurality of Y ^2, Ar ^2, Q ² and V ² may be the same or different, and when a plurality of X ² are present, they may be the same or different, and e represents an integer of 1 to 6.)

(Wherein Y ³ represents a Group 13 atom, Ar ³ represents an aryl group having an electron-withdrawing group or a monovalent heterocyclic group having an electron-withdrawing group, and Q ³ represents an oxygen atom or a direct bond. V ³ represents a group 16 atom, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a bidentate heterocyclic group, —C≡N— or —N═N—, Y ³ , Ar ³ , Q ³ and V ³ may be the same or different from each other, and f represents an integer of 1 to 6. Formula (1a), Ar ¹ in the formula (1b), an organic electroluminescence device according to claim 1 Ar ² in the formula (2), the Ar ³ in the formula (3) is a perfluoroalkyl aryl group.   In Formula (1a), a is 2 or 3, The organic electroluminescent element of Claim 1 or 2. In formula (1a), an organic electroluminescent device according to any one of claims 1 to 3 Z ¹ or V ¹ is a -C≡N-. The organic electroluminescence device according to any one of claims 1 to 4, wherein the anion represented by the formula (1a) is an anion represented by the formula (5-1) or the formula (5-2).

(In the formula, M represents a nickel atom or a palladium atom.)   In Formula (1b), k is 3 or more, The organic electroluminescent element of Claim 1 or 2. The organic electroluminescence device according to claim 6, wherein the anion represented by the formula (1b) is an anion represented by the formula (1b-2).
[B (Ar ^{₄₎ 4] -} (1b-2)
(In the formula, Ar ⁴ represents a phenyl group substituted with two or more groups selected from the group consisting of a fluoro group and a trifluoromethyl group. The plurality of Ar ⁴ may be the same or different. .)   The cation of the ion pair is a hydrogen ion, a metal cation or a carbocation, or a group consisting of a nitrogen atom, oxygen atom, phosphorus atom, sulfur atom, chlorine atom, selenium atom, bromine atom, tellurium atom and iodine atom The organic electroluminescent element according to claim 1, wherein the element is onium selected from the group consisting of   The organic electroluminescence device according to any one of claims 1 to 8, wherein the content of the ion pair is 0.001 to 10 parts by weight when the polymer light emitter is 100 parts by weight.   The organic electroluminescent element according to any one of claims 1 to 9, wherein a voltage of the energization treatment is 100 V or less.