JP4696641B2 - Polymer composition - Google Patents

Description

  The present invention relates to a polymer composition, a polymer solution composition, and a polymer light emitting device (polymer LED) using the polymer composition.

  Unlike a low molecular weight compound, a high molecular compound having a light emitting property and / or conductivity is soluble in a solvent and can form a light emitting layer, a charge transport layer, a charge injection layer, etc. in a light emitting device by a coating method. It meets the requirements of Therefore, in recent years, polymer compounds having various luminescent properties and / or conductivity have been proposed (for example, Non-Patent Document 1).

Advanced Materials Vol.12 1737-1750 (2000)

By the way, it is desired that the light emitting element has a long lifetime, that is, the degree of decrease in luminance over time due to driving is small.
However, when a light-emitting and / or conductive polymer compound is used as a material for a light-emitting layer, a charge transport layer, a charge injection layer, or the like of a light-emitting element, the lifetime of the element has not been sufficient.
An object of the present invention is to provide a composition capable of providing a light-emitting element having a longer lifetime when used in a light-emitting element.

（式中、Ｙ¹は１３族の原子を表し、Ａｒ¹は電子吸引基を有するアリール基または電子吸引基を有する１価の複素環基を表し、Ｑ¹は酸素原子または直接結合を表し、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、シアノ基またはニトロ基を表し、ａは１〜３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−または直接結合を表し、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族もしくは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−または直接結合を表す。ただし、Ｚ¹が−Ｃ≡Ｎ−、−Ｎ＝Ｎ＝Ｎ−、−ＮＨ−、−ＮＨ₂−または−ＯＨ−の場合、ｂ＝２である。Ｚ¹とＶ¹とは相異なり、Ｑ¹およびＡｒ¹が複数存在する場合、それらは同一でも異なっていてもよく、複数のＶ¹はそれぞれ同一であっても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は電子吸引基を有するアリール基または電子吸引基を有する１価の複素環基を表し、Ｑ²は酸素原子または直接結合を表し、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、シアノ基またはニトロ基を表し、ｄおよびｄ’はそれぞれ独立に１または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−または−Ｎ＝Ｎ−を表し、複数のＹ²、Ａｒ²、Ｑ²およびＶ²は同一でも異なっていてもよく、Ｘ²が複数存在する場合、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は電子吸引基を有するアリール基または電子吸引基を有する１価の複素環基を表し、Ｑ³は酸素原子または直接結合を表し、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−または−Ｎ＝Ｎ−を表し、複数のＹ³、Ａｒ³、Ｑ³およびＶ³はそれぞれ同一であっても異なっていてもよく、ｆは１〜６の整数を表す。） As a result of intensive studies to solve the above-mentioned problems, the present inventors have, as a negative ion, a polymer compound having luminescent property and / or conductivity having two or more group 13 atoms, and all of the atoms are present. A composition containing an ion pair having an anion having a specific structure that is bonded directly or via a linking group to an aryl group having an electron withdrawing group or a heterocyclic group having an electron withdrawing group, respectively. When it was used as a material for a light emitting device, it was found that the lifetime of the device was prolonged, and the present invention was achieved.

That is, the present invention provides a polymer composition containing a light-emitting and / or conductive polymer compound and an ion pair, wherein the anion of the ion pair is represented by the following formulas (1) and (2): Or a polymer composition characterized by being represented by (3).

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, Q ¹ represents an oxygen atom or a direct bond, X ¹ 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, aryl Alkynyl 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 nitro Represents a group, a represents an integer of 1 to 3, V ¹ represents a group 16 atom, a divalent aliphatic hydrocarbon. Represents a prime group, a divalent aromatic hydrocarbon group, a bidentate heterocyclic group, —C≡N—, —N═N═N— or a direct bond, b represents an integer of 2 to 6, Z ¹ Is M ′ (═O) p (wherein M ′ is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 12, 13) Represents a group 15, group 16 or group 17 atom, and p represents an integer of 0 to 2.), a b-valent aliphatic hydrocarbon group, a b-valent aromatic hydrocarbon group, A heterocyclic group, —C≡N—, —N═N═N—, —NH—, —NH ₂ —, —OH— or a direct bond, wherein Z ¹ is —C≡N—, —N═ When N = N—, —NH—, —NH ₂ — or —OH—, b = 2, unlike Z ¹ and V ¹ , they are the same when there are a plurality of Q ¹ and Ar ^1. But may be different, each of the plurality of V ¹ are the same Or c may be different, and c represents an integer of 1 to 6.)

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, 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, aryl Alkynyl 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 nitro It represents a group, represents 1 or 2 d and d 'each independently, 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, 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, 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—, and a plurality of Y ³ , Ar ³ , Q ³ and V ³ may be the same or different, and f represents an integer of 1 to 6.)

  The present invention also relates to a polymer solution composition containing a solvent in addition to the polymer composition.

  By including the polymer composition of the present invention in a light emitting layer of a light emitting device, the lifetime of the device can be extended. Accordingly, the polymer LED using the polymer composition of the present invention is a device such as a curved or flat light source for backlight or illumination of a liquid crystal display, a segment type display element, a dot matrix flat panel display, etc. Can be preferably used.

  The ion pair used in the composition of the present invention is characterized in that the anion is represented by the above formula (1), (2) or (3).

Y ¹ in the formula (1) represents a Group 13 (IIIB group) atom, preferably boron, aluminum, or gallium, and more preferably boron.

Ar ¹ in the formula (1) 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, and specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, i-propyloxycarbonyl group, butoxycarbonyl group, i-butoxy Carbonyl 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, perfluorobutoxycarbo 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 alkoxyphenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyl Examples include an oxycarbonyl group, 2-naphthyloxycarbonyl group, pentafluorophenyloxycarbonyl group and the like.

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.

The perfluoroalkyl group represents a group in which all hydrogen atoms on a linear, branched or cyclic alkyl group are substituted with fluorine, and usually has about 1 to 20 carbon atoms. Specific examples thereof include trifluoromethyl. Group, perfluoroethyl group, perfluoropropyl group, heptafluoro-i-propyl group, perfluorobutyl group, nonafluoro-i-butyl group, 1,1-bistrifluoromethyl-2,2,2-trifluoroethyl group Perfluoropentyl group, perfluorohexyl group, perfluorocyclohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group, 3,7-dimethyloctyl group, perfluorolauryl group, etc. Illustrated.

Next, an aryl group having an electron-withdrawing group, a monovalent heterocyclic group having an electron-withdrawing group, an aryloxy group having an electron-withdrawing group, and a monovalent group having an electron-withdrawing group in Ar ₁ in formula (1) The heteroaryloxy group of will be described.

The aryl group having an electron-withdrawing group usually has about 6 to 60 carbon atoms, and specific examples thereof include a phenyl group, a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ have 1 to The same applies to the following.), C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl group, 2-naphthyl group and the like substituted with one or more of the above electron-withdrawing groups. It is done.

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, thiazole group, one or more of the above electron-withdrawing groups on the thiadiazole group and the like are obtained by substituting.

Specific examples of Ar ¹ include the following groups (I) to (V).

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

(V) Perfluoroaryl group, perfluoroaryloxy 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.
Perfluoroaryloxy groups include pentafluorophenyloxy group, heptafluoro-1-naphthyloxy group, heptafluoro-2-naphthyloxy group, nonafluoro-1-biphenyloxy group, nonafluoro-2-biphenyloxy group, nonafluoro- Examples include 1-anthracenyloxy group, nonafluoro-2-anthracenyloxy group, and nonafluoro-9-anthracenyloxy group.

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

Q ¹ in the formula (1) represents an oxygen atom or a direct bond. Q ¹ is preferably a direct bond.

X ¹ in the formula (1) 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 Represents a cyano group or a nitro group.

Examples of the halogen atom in X ¹ include fluorine, chlorine, bromine and iodine.

  The alkyl group may be linear, branched or cyclic, and may have a substituent, and usually has about 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, and a propyl group. I-propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyl Examples include octyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group and the like.

  The alkyloxy group may be linear, branched or cyclic, and may have a substituent, and usually has about 1 to 20 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, and a propyl group. Oxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group Decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group, methoxymethyloxy group, 2-methoxy Examples include an ethyloxy group.

  The alkylthio group may be linear, branched or cyclic, and may have a substituent, and usually has about 1 to 20 carbon atoms. Specific examples thereof include a methylthio group, an ethylthio group, and a propylthio group. I-propylthio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7 -A dimethyloctylthio group, a laurylthio group, a trifluoromethylthio group, etc. are illustrated.

The aryl group may have a substituent and usually has about 3 to 60 carbon atoms. Specific examples thereof include a phenyl group, a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ are indicates a C1-12. the same applies is less.), C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl group, 2-naphthyl group, pentafluorophenyl group and the like.

The aryloxy group may have a substituent on the aromatic ring and usually has about 3 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, and the carbon number is usually about 3 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.

The arylalkyloxy group may have a substituent and usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl-C ₁ -C ₁₂ alkoxy group and a 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 arylalkenyl 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.

Examples of the substituted silyloxy group include a silyloxy group (H ₃ SiO—) substituted with 1, 2 or 3 groups selected from 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 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-butylsilyldimethylsilyloxy group, triphenylsilyloxy group, tri-p-xylylsilyloxy group, tribenzylsilyloxy group, diphenylmethylsilyloxy group, t-butyldiphenylsilyloxy group Group, dimethylphenylsilyloxy group and the like are exemplified.

Examples of the substituted silylthio group include a silylthio group (H ₃ SiS—) substituted with 1, 2 or 3 groups selected from 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-butylsilyldimethylsilylthio group, triphenylsilylthio group, tri-p-xylylsilylthio group, tribenzylsilylthio group, diphenylmethylsilylthio group, t-butyldiphenylsilylthio group Group, dimethylphenylsilylthio group and the like are exemplified.

The substituted silylamino group includes a silylamino group (H ₃ SiNH— or (H ₃ Si) ₂ N substituted with 1 to 6 groups selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. -). 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-butylsilyldimethylsilylamino 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 -Butylsilyldimethylsilyl) amino group, di (triphenylsilyl) Mino group, di (tri-p-xylylsilyl) amino group, di (tribenzylsilyl) amino group, di (diphenylmethylsilyl) amino group, di (t-butyldiphenylsilyl) amino group, di (dimethylphenylsilyl) amino Examples include groups.

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl The group or the 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, 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, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, dipheny 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 Etc. groups.

  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.

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 equation (1),
Z ¹ is M ′ (═O) p (wherein M ′ is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 12, 13) Represents a group 14, 15, 16, or 17 atom, and p represents an integer of 0 to 2.), a b-valent aliphatic hydrocarbon group, a b-valent aromatic hydrocarbon group, b It represents a heterocyclic group at the site, —C≡N—, —N═N═N—, —NH—, —NH ₂ —, —OH— or a direct bond.
As described above, b represents an integer of 2 to 6, but when Z ¹ is —C≡N—, —N═N═N—, —NH—, —NH ₂ — or —OH—, b = 2. It is. Further, when Z ¹ is M ′ (═O) p, b does not exceed the number of bonds that M ′ can take.

3 (IIIA), 4 (IVA), 5 (VA), 6 (VIA), 7 (VIIA), 8 and 9 in M ′ when Z ¹ is M ′ (═O) p Group 10 (Group VIII), 11 (IB), 12 (IIB), 13 (IIIB), 14 (IVB), 15 (VB), 16 (VIB) or 17 (VIIB) Specifically, the atoms of 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 the following cases atomic weight 50.

M ′ is 3, 4, 5, 6, 7, 8, 9, 9, 10, 11, 12, 13, 14, 15, 15, 16 or 17 excluding oxygen. In the case of a group atom, p = 1 may be obtained, and in the case where M ′ is a group 5, 6 or 7 atom, p = 2.
Specific examples in the case of p = 1, 2 include Ti (= O), V (= O), Cr (= O), Cr (= O) ₂ , Zr (= O), Mo (= O), W (= O).

The b-valent aliphatic hydrocarbon group in 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 ′ ″.

R ′ ″ each independently represents 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, or 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, 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.

Examples of the b-valent aromatic hydrocarbon group when b is 3 to 6 include (b-2) R ′ ″ from the examples (1 to 38) of the divalent aromatic hydrocarbon group shown above. Excluded residues are mentioned.

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),
Examples thereof include those having two covalent bond sites (divalent heterocyclic group), those having one covalent bond site and one coordination bond site (monovalent bidentate heterocyclic group). Specific examples of the divalent heterocyclic group include the following.

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 to 68 in the lower figure), an acridine diyl group (formulas 69 to 72 in the lower figure), a bipyridyldiyl group (formulas 73 to 75 in the lower figure), a phenanthroline diyl group (formulas 76 to 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).

ここで、Ｒは、それぞれ独立に水素原子、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、シアノ基またはニトロ基を表す。

Here, R is independently 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, 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, 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.

Specific examples of the monovalent bidentate heterocyclic group include a group 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 heteroatom. The following groups are mentioned.

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 (1), 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 (1), a represents an integer of 1 to 3, a is preferably 2 or 3, and more preferably a is 3.

In Formula (1), b represents an integer of 2 or more and 6 or less. However, when Z ¹ is —C≡N—, —N═N═N—, —NH—, —NH ₂ — or —OH—, b = 2.

  In Formula (1), c represents an integer of 1 or more and 6 or less.

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

Among the anions represented by the above formula (1), Ar ¹ is preferably a perfluoroaryl group, and more preferably a is 2 or 3, from the viewpoint of extending the lifetime.

More preferably, Z ¹ or V ¹ is —C≡N—. Specifically, the anion represented by the formula VII is exemplified.

（式中、Ｍはニッケル原子またはパラジウム原子を表す。） More preferably, the above formula (1) is the following formula (5-1) or (5-2).

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

（式中、Ｙ²は１３族の原子を表し、Ａｒ²は電子吸引基を有するアリール基または電子吸引基を有する１価の複素環基を表し、Ｑ²は酸素原子または直接結合を表し、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、シアノ基またはニトロ基を表し、ｄおよびｄ’はそれぞれ独立に１または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−または−Ｎ＝Ｎ−を表し、複数のＹ²、Ａｒ²、Ｑ²およびＶ²は同一でも異なっていてもよく、Ｘ²が複数存在する場合、それらは同一であっても異なっていてもよく、ｅは１〜６の整数を表す。）

である。 The ion pair used in the composition of the present invention is characterized in that the anion is represented by the above formula (1), (2) or (3).
Among them, the anion of 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, 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, aryl Alkynyl 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 nitro It represents a group, represents 1 or 2 d and d 'each independently, 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, 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.

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 aryl group having an electron withdrawing group and the monovalent heterocyclic group having an electron withdrawing group in Ar ² , Examples and the like are the same as those in Ar ¹ ,
X ² 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, aryl Definition, specific examples of alkynyl 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 heteroarylthio group And the like are the same as those in X ² , and the definitions, specific examples, etc. of the group 16 atom, divalent aliphatic hydrocarbon group, divalent aromatic hydrocarbon group, and bidentate heterocyclic group in V ² Is the same as that in V ¹ . Q ² represents an oxygen atom or a direct bond, and is preferably a direct bond.

  Specific examples of the anion represented by the above formula (2) include an anion represented by the following formula VIII.

Among the anions represented by the above formula (2), Ar ² is preferably a perfluoroaryl group, more preferably Ar ² is a perfluoroaryl group, and more preferably d and d. This is the case where 'is 2.

（式中、Ｙ³は１３族の原子を表し、Ａｒ³は電子吸引基を有するアリール基または電子吸引基を有する１価の複素環基を表し、Ｑ³は酸素原子または直接結合を表し、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−または−Ｎ＝Ｎ−を表し、複数のＹ³、Ａｒ³、Ｑ³およびＶ³はそれぞれ同一であっても異なっていてもよく、ｆは１〜６の整数を表す。）
である。 The ion pair used in the composition of the present invention is characterized in that the anion is represented by the above formula (1), (2) or (3), in which the anion of formula (3) is:

(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, 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—, and a plurality of Y ³ , Ar ³ , Q ³ and V ³ may be the same or different, and f represents an integer of 1 to 6.)
It is.

Specific examples of Group 13 atoms in Y ³ are the same as those in Y ¹ above. Definitions, specific examples, and the like of aryl groups having an electron withdrawing group and monovalent heterocyclic groups having an electron withdrawing group in Ar ³ are as follows. , The same as in Ar ¹ , the definition of the group 16 atom in V ³ , a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a bidentate heterocyclic group, specific examples, etc. It is the same as that in V ¹ . Q ³ represents an oxygen atom or a direct bond, and is preferably a direct bond.

  Specific examples of the anion represented by the above formula (3) include an anion represented by the following formula IX.

上記式中ＶＩ〜ＩＸ式中、芳香族炭化水素環、複素環または炭化水素鎖上に置換基を有していてもよい。

In the above formulas VI to IX, a substituent may be present on the aromatic hydrocarbon ring, heterocyclic ring or hydrocarbon chain.

Among the anions represented by the above formula (3), Ar ³ is preferably a perfluoroaryl group from the viewpoint of extending the life.

  Of the anions represented by the above formulas (1), (2) and (3), an ion pair containing the anion represented by (1) is preferred.

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

The carbocation may be monovalent or multivalent, and examples thereof include methylium, ethylium, neopentylium, cyclopropenylium, phenylium, anthryllium, 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、

下記式（６）などが例示される。 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,

The following formula (6) is exemplified.

In the formula, each of R ³ and R ⁴ independently represents an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkyloxy group, an acyl group, an acyloxy group, a monovalent heterocyclic group or a hetero group. Represents an aryloxy group. R ⁵ and R ⁶ are each independently 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, heteroary It represents a ruthio group, acyl group, imine residue, substituted silyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl group, carboxyl group, cyano group or nitro group. T represents a direct bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, an ethynylene group or a divalent heterocyclic group. i and j each independently represents 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 , R ⁵ and R ⁶ 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 and The definition and specific examples of the heteroarylthio group are the same as those described for X ¹ and X ² above. The definition and specific examples of the acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylalkyloxycarbonyl group, and heteroaryloxycarbonyl group are the same as those described above for the electron withdrawing groups in Ar ¹ , Ar ^2, and Ar ³ . .

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.

  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. Trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, tri-i-propylsilyl group, t-butylsilyldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilyl group, tribenzylsilyl group, diphenylmethyl Examples include silyl group, t-butyldiphenylsilyl group, dimethylphenylsilyl group and the like.

The definitions and specific examples of the divalent aliphatic hydrocarbon group and divalent aromatic hydrocarbon group in T of the above formula (6) are the same as those described in the above V ¹ , V ² and V ³ .

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 groups exemplified in 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 formula (6) include the following.

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

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

The onium of the phosphorus atom may be monovalent or multivalent, and tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, tetraphenylphosphonium, triphenylmethylphosphonium, methyltriphenylphosphonium. Is exemplified.

The onium of the sulfur atom may be monovalent or divalent or higher, and may be aliphatic sulfonium such as trimethylsulfonium, triethylsulfonium, tripropylsulfonium, tributylsulfonium, trihexylsulfonium, triphenylsulfonium, tri (4-methylphenyl). An aromatic sulfonium such as sulfonium, tri (4-t-butylphenyl) sulfonium, methyldiphenylsulfonium, dimethylphenylsulfonium, or an onium represented by the following formula is exemplified.

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 ( Examples include 4-t-butylphenyl) selenium, methyldiphenyl selenium, and dimethylphenyl selenium.

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 thereof include phenyl) telluronium, tri (4-tert-butylphenyl) telluronium, methyldiphenyltelluronium, and dimethylphenyltelluronium.

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

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, the atomic weight is preferably less than 50.
Specifically, 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 ions, magnesium ions, calcium ions, strontium ions, barium ions, (MgCl) ⁺ , (MgBr) ⁺ , (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. The

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

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

Examples of the cation whose cation is 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 aromatic ammonium salt-based compounds include the following ion pairs.

Examples of the aliphatic ammonium salt system include the following ion pairs.

Examples of aromatic aminium salt-based compounds include the following ion pairs.

Examples of aromatic diazonium salt-based compounds include the following ion pairs.

The following ion pairs are exemplified as those in which the cation is an onium having a phosphorus atom.

The following ion pairs are exemplified as those in which the cation is an onium having a sulfur atom.

Examples of the cation having an iodine atom of onium include the following ion pairs.

Examples of the cation being a metal cation include the following ion pairs.

The present invention also provides a novel ion pair characterized in that the anion is represented by the following structural formula (5-1) and the cation is a pyridinium cation, a phosphonium cation or an iodonium cation.

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

Examples of the ion pair in which the cation is a phosphonium cation include the following compounds.

Examples of ion pairs in which the cation is an iodonium cation include the following compounds.

Examples of the pyridinium salt, phosphonium salt, and iodonium salt include a compound represented by the following formula (7-1) and K [(C ₆ F ₅ ) ₃ B—C≡N—B (C ₆ F ₅ ) ₃ ]. It can manufacture by making these react.

式中、Ｅ¹⁺は、ピリジニウムカチオン、ホスホニウムカチオンまたはヨードニウムカチオンを表す。Ｘ^1-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。

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

In the present invention, the anion is represented by the following structural 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 to provide a pair.

（式中、Ｍはニッケル原子またはパラジウム原子を表す。）

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

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

Examples of ion pairs in which the cation is a quaternary ammonium cation include the following compounds.

Examples of the ion pair in which the cation is a phosphonium cation include the following compounds.

Examples of ion pairs in which the cation is an oxonium cation include the compounds exemplified below.

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

Examples of ion pairs in which the cation is an iodonium cation include the following compounds.

Examples of the pyridinium salt, phosphonium salt, and iodonium salt include reacting a compound represented by the following formula (7-2) with K ₂ [M {C≡NB (C ₆ F ₅ ) ₃ } ₄ ]. Can be manufactured.

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またはヨードニウムカチオンを表す。Ｘ^2-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。

In the formula, E ²⁺ represents a pyridinium cation, a quaternary ammonium cation, a phosphonium cation, an oxonium cation, a sulfonium cation or an iodonium cation. X ²⁻ represents a halide ion, an alkyl sulfonate ion, or an aryl sulfonate ion.

Specific examples of the halide ion, the alkyl sulfonate ion, and the aryl sulfonate ion include the ions exemplified in the above ^X1- .

One type or two or more types of ion pairs may be contained in the polymer composition of the present invention.

The polymer compound having luminescence and / or conductivity used in the present invention has a polystyrene-equivalent number average molecular weight of usually about 10 ³ to 10 ⁸ .
The following (A) to (C) may be mentioned as the polymer compound having luminescence and / or conductivity.

(A) Polymer compound having luminescence and no conductivity (B) Polymer compound having luminescence and conductivity (C) Polymer compound having conductivity and not luminescence (A) And (B) can be collectively referred to as a polymer light emitter, and (B) and (C) can be collectively referred to as a conductive polymer.

Here, having a light emitting property means that, for example, a luminescence phenomenon can be exhibited,
Having conductivity means that the electric conductivity is about 10 ³ to 10 ⁻¹⁰ S / cm, for example.

The polymer compound having a light emitting property and / or conductivity used in the present invention may further have a charge injection property, a charge transport property and the like.

When used as a light emitting material, a polymer light emitter, that is, a light emitting material ((A), (B)) is preferred, and (B) is more preferred.

Among the polymer compounds having luminescent property and / or conductivity used in the present invention, those which are conjugated polymer compounds are preferable. 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.

The polymer compound used in the present invention may be a homopolymer or a copolymer. For example, polyfluorene [for example, Japanese Journal of Applied Physics (Jpn. J. Appl. Phys.) 30, L1941 (1991)], polyparaphenylene [for example, Advanced Materials (Adv. Mater.) 4, 36 (1992)], polyarylene such as polypyrrole, polypyridine, polyaniline, polythiophene, etc. Systems; polyarylene vinylene systems such as polyparaphenylene vinylene and polythienylene vinylene (for example, WO 98/27136 published specification)
Polyphenylene sulfide, polycarbazole and the like.
[For review, for example, "Advanced Materials Vol.12 1737-1750 (2000)" and "Organic EL Display Technology Monthly Display December issue P68-73")

Among these, polyarylene polymer compounds are preferable.
Examples of the repeating unit contained in the polyarylene polymer include a divalent aromatic hydrocarbon group (arylene group) and a divalent heterocyclic group.
Here, the number of carbon atoms constituting the ring of the divalent aromatic hydrocarbon group is usually about 6 to 60, and specific examples thereof include a phenylene group, a biphenylene group, a terphenylene group, a naphthalenediyl group, an anthracenediyl group, Phenanthrene diyl group, pentadiene diyl group, indene diyl group, heptadidiyl group, indacene diyl group, triphenylene diyl group, binaphthyl diyl group, phenyl naphthylene diyl group, stilbene diyl group, fluorenediyl group (for example, the following formula (4) And A = —C (R ′) (R ′) —).
The number of carbon atoms constituting the ring of the divalent heterocyclic group is usually about 3 to 60. Specific examples include pyridine-diyl group, diazaphenylene group, quinolinediyl group, quinoxalinediyl group, acridinediyl group, bipyridyldiyl. Group, phenanthrolinediyl group, in the following formula (4), X = —O—, —S—, —Se—, —NR ″ —, —C (R ′) (R ′) —, or —Si (R ') (R')-.

（式中、Ａは、式中の２個のベンゼン環上の４個の炭素原子と一緒になって５員環または６員環を完成させるための原子または原子群を表し、Ｒ^4a、Ｒ^4b、Ｒ^4c、Ｒ^5a、Ｒ^5bおよびＲ^5cは、それぞれ独立に、水素原子、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、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、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、シアノ基、ニトロ基、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またはカルボキシル基を表し、Ｒ^4bとＲ^4c、およびＲ^5bとＲ^5cは、それぞれ一緒になって環を形成していてもよい。） More preferably, it includes a repeating unit represented by the following formula (4).

(In the formula, A represents an atom or atomic group for completing a two 5- or 6-membered ring together with four carbon atoms on the benzene ring in the formula, R ^4a, R ^4b , R ^4c , R ^5a , R ^5b and R ^5c are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, aryl Alkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group Substituted silylthio group, substituted silylamino group, cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, heteroaryl Represents a thio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group or a carboxyl group, and R ^4b and R ^4c , and R ^5b and R ^5c are each taken together to form a ring May be formed.)

  A represents an atom or a group of atoms together with four carbon atoms on the two benzene rings in formula (4) to complete a 5-membered ring or a 6-membered ring, and specific examples include: Although shown below, it is not limited to these.

式中、Ｒはそれぞれ独立にハロゲン原子、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、アシルオキシ基、置換アミノ基、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、シアノ基または１価の複素環基を表す。Ｒ’はそれぞれ独立に水素原子、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、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、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、シアノ基、ニトロ基または１価の複素環基を表す。Ｒ''はそれぞれ独立に水素原子、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、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、アシル基、置換シリル基、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または１価の複素環基を表す。

In the formula, each R is independently 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, An arylalkenyl group, an arylalkynyl group, an acyloxy group, a substituted amino group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a cyano group, or a monovalent heterocyclic group is represented. R ′ is independently hydrogen atom, 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, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, cyano group, nitro Represents a monovalent heterocyclic group. R '' is independently hydrogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, aryl An alkenyl group, an arylalkynyl group, an acyl group, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, or a monovalent heterocyclic group is represented.

R, R ′, R ″ 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 groups, arylalkynyl groups, substituted silyloxy groups, substituted silylthio groups, substituted silylamino groups, substituted amino groups, amide groups, acid imide groups, acyl groups, acyloxy groups, monovalent heterocyclic groups, specific examples are , As described above for R ³ , R ⁴ , R ⁵ and R ⁶ .

In A, —O—, —S—, —Se—, —NR ″ —, —CR′R′— or —SiR′R′— are preferable, —O—, —S—, —CR ′. R'- is more preferred.

Examples of the repeating unit represented by the above formula (4) include the following structures.

式中、ベンゼン環上の水素原子は、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、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、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、シアノ基、ニトロ基または１価の複素環基に置換されていてもよい。ベンゼン環の隣接位に２つの置換基が存在する場合、それらが互いに結合して環を形成してもよい。

In the formula, a hydrogen atom on the benzene ring is 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, an alkenyl group, Alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, cyano group , A nitro group or a monovalent heterocyclic group may be substituted. When two substituents are present at adjacent positions of the benzene ring, they may be bonded to each other to form a ring.

The polymer compound used in the present invention may contain, for example, a repeating unit derived from an aromatic amine in addition to a divalent aromatic hydrocarbon group and a divalent heterocyclic group. In this case, hole injection property and transport property can be imparted.
In this case, the molar ratio of the repeating unit derived from an aromatic amine and a repeating unit composed of a divalent aromatic hydrocarbon group or divalent heterocyclic group is usually in the range of 99: 1 to 20:80.

As the repeating unit derived from an aromatic amine, a repeating unit represented by the following formula (8) is preferable.

In the formula, Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ each independently represent a divalent aromatic hydrocarbon group or a divalent heterocyclic group. Ar ⁸ , Ar ⁹ and Ar ¹⁰ each independently represent an aryl group or a monovalent heterocyclic group. o and p each independently represent 0 or 1, and 0 ≦ o + p ≦ 2.

Here, the definition and specific examples of the divalent aromatic hydrocarbon group and divalent heterocyclic group are the same as described in T above. The definition and specific examples of the aryl group and the monovalent heterocyclic group are the same as those described for X ¹ and X ² above.

Specific examples of the repeating unit represented by the above formula (8) include the following structures.

  In the formula, the hydrogen atom on the aromatic ring 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, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, cyano group, A substituent selected from a nitro group, a monovalent heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group and a carboxyl group It may be conversion.

  Among the repeating units represented by the above formula (8), the repeating unit represented by the following formula (9) is particularly preferable.

In the formula, R ⁷ , R ⁸ and R ⁹ are each independently 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, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted Silylamino group, cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl group or carboxyl group The table The x and y each independently represents an integer of 0 to 4. z shows the integer of 0-2. w shows the integer of 0-5.

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

  Since the terminal group of the polymer compound used in the present invention may be protected with a stable group, if the polymerization active group is left as it is, there is a possibility that the light emission characteristics and life when the device is made may be reduced. good. Those having a conjugated bond continuous with the conjugated structure of the main chain are preferable, and examples thereof include a structure in which an aryl group or a heterocyclic group is bonded via a carbon-carbon bond. Specific examples include substituents described in Chemical formula 10 of JP-A-9-45478.

The polymer compound used in the present invention preferably has a number average molecular weight of about 10 ³ to 10 ^{8 in} terms of polystyrene, and more preferably has a number average molecular weight of about 10 ⁴ to 10 ^{6 in} terms of polystyrene. .

  In addition, since light emission from a thin film is used, a polymer light-emitting body having light emission in a solid state is preferably used.

Examples of the method for synthesizing the polymer compound used in the present invention include a method of polymerizing from a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a Ni (0) catalyst, and an oxidizing agent such as FeCl _3. Examples thereof include a method of polymerizing by oxidization, a method of electrochemically oxidative polymerization, a method of decomposing an intermediate polymer having an appropriate leaving group, and the like. Among these, a method of polymerizing by Suzuki coupling reaction, a method of polymerizing by Grignard reaction, and a method of polymerizing by Ni (0) catalyst are preferable because of easy reaction control.
When a polymer compound is used as a light emitting material of a polymer LED, the purity affects the light emission characteristics, and therefore it is preferable to polymerize after purifying the monomer before polymerization by a method such as distillation, sublimation purification, recrystallization, etc. Further, after the synthesis, it is preferable to carry out a purification treatment such as reprecipitation purification and fractionation by chromatography.

The polymer composition of the present invention is characterized in that it contains the above-described polymer compound having luminescence and / or conductivity and an ion pair, and each contains two or more kinds of the polymer compound and ion pair. May be.
The content of ion pairs is usually about 0.001 to 10 parts by weight, preferably 0.001 to 5 parts, when the total weight of the light emitting and / or conductive polymer compound is 100 parts by weight. Parts by weight, more preferably 0.001 to 1 part by weight, still more preferably 0.01 to 1 part by weight.

  The polymer solution composition of the present invention is characterized by containing a polymer compound having luminescence and / or conductivity, an ion pair, and a solvent. A light emitting layer or the like can be formed by a coating method using this solution composition. The light emitting layer or the like produced using this solution composition usually contains the polymer composition of the present invention.

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

  The amount of the solvent is usually about 1000 to 100000 parts by weight with respect to 100 parts by weight of the total weight of the polymer compound having luminescence and / or conductivity.

  The composition of the present invention may contain a dye, a charge transport material and the like, if necessary.

The polymer LED of the present invention is characterized by having a layer containing the polymer composition of the present invention between electrodes composed of an anode and a cathode.
The polymer LED of the present invention is characterized by having a layer formed using the polymer solution composition between electrodes composed of an anode and a cathode.
The layer containing the polymer composition of the present invention and the layer formed using the polymer solution composition are, for example, a light emitting layer, a charge transport layer, a charge injection layer, and the like, and preferably a light emitting layer.

  In addition, as the polymer LED of the present invention, a polymer LED having an electron transport layer provided between the cathode and the light emitting layer, a polymer LED having a hole transport layer provided between the anode and the light emitting layer, Examples include a polymer LED 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.

For example, the following structures a) to d) are specifically exemplified.
a) Anode / light emitting layer / cathode b) Anode / hole transport layer / light emitting layer / cathode c) Anode / light emitting layer / electron transport layer / cathode d) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (Here, / indicates that each layer is laminated adjacently. The same shall apply hereinafter.)

Here, the light emitting layer is a layer having a function of emitting light, the hole transporting layer is a layer having a function of transporting holes, and the electron transporting layer is a layer having a function of transporting electrons. It is. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer.
Two or more light emitting layers, hole transport layers, and electron transport layers may be used independently.

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

  Further, in order to improve adhesion with the electrode and charge injection from the electrode, the charge injection layer or an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode, and the adhesion at the interface may be improved. In order to prevent mixing, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.

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

  In the present invention, a polymer LED provided with a charge injection layer (electron injection layer, hole injection layer) includes a polymer LED provided with a charge injection layer adjacent to the cathode, and a charge injection layer adjacent to the anode. The provided polymer LED is mentioned.

For example, the following structures e) to p) are specifically mentioned.
e) Anode / charge injection layer / light emitting layer / cathode
f) Anode / light emitting layer / charge injection layer / cathode
g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode
h) Anode / charge injection layer / hole transport layer / light emitting layer / cathode
i) Anode / hole transport layer / light emitting layer / charge injection layer / cathode
j) Anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode
k) Anode / charge injection layer / light emitting layer / electron transport layer / cathode
l) Anode / light-emitting layer / electron transport layer / charge injection layer / cathode
m) Anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode
n) Anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / cathode o) Anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode p) Anode / charge injection layer / Hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode

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

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

Usually, in order to set the electric conductivity of the conductive polymer to 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, the conductive polymer is doped with an appropriate amount of ions.

  The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and examples of cations include lithium ions, sodium ions, potassium ions, tetrabutylammonium ions, and the like.

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

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

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

Specific examples include the following structures q) to ab).
q) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / cathode r) Anode / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode s) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / film thickness 2 nm Insulating layer / cathode t) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / cathode
u) Anode / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode
v) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode
w) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / cathode
x) Anode / light-emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode
y) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode
z) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / cathode
aa) Anode / hole transport layer / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode
ab) Anode / insulating layer with a thickness of 2 nm or less / hole transporting layer / light emitting layer / electron transporting layer / insulating layer with a thickness of 2 nm or less / cathode

  For example, when the light emitting layer is formed using the polymer solution composition of the present invention, it is only necessary to remove the solvent by drying after coating this solution, and a charge transport material or other light emitting material is mixed. In this case, the same technique can be applied, which is very advantageous in manufacturing. As a film forming method from a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, Application methods such as a flexographic printing method, an offset printing method, and an ink jet printing method can be used.

  As the film thickness of the light emitting layer, the optimum value varies depending on the material to be used, and it may be selected so that the drive voltage and the light emission efficiency are appropriate values. For example, the thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm. More preferably, it is 5 nm-200 nm.

  In the polymer LED of the present invention, the light emitting layer may contain a light emitting material other than the polymer light emitter, and the light emitting layer containing a light emitting material other than the polymer light emitter may include the polymer light emitting. The light emitting layer including the body may be stacked.

  As the light emitting material, known materials can be used. Examples of the low molecular weight compound include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine dyes, xanthene dyes, coumarin dyes, cyanine dyes, 8-hydroxyquinoline or metal complexes of derivatives thereof, aromatic amines, and the like. , Tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used.

  Specifically, for example, known ones such as those described in JP-A-57-51781 and 59-194393 can be used.

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

  Specifically, as the hole transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, Examples described in JP-A-3-37992 and JP-A-3-152184 are exemplified.

  Among these, as a hole transport material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, polyaniline or a derivative thereof, Preferred is a polymer hole transport material such as polythiophene or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, or poly (2,5-thienylene vinylene) or a derivative thereof, more preferably polyvinyl carbazole or a derivative thereof, Polysilane or a derivative thereof, or a polysiloxane derivative having an aromatic amine in the side chain or main chain. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.

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

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

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

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

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transport material. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

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

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those showing no strong absorption against visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

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

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

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

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

  There are no particular restrictions on the method for forming the electron transport layer, but for low molecular weight electron transport materials, vacuum deposition from powder, or by film formation from a solution or molten state, and for polymer electron transport materials, solution or Each method is exemplified by film formation from a molten state. In film formation from a solution or a molten state, a polymer binder may be used in combination.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve an electron transport material and / or a polymer binder. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

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

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those not strongly absorbing visible light are suitably used. As the polymer binder, poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, poly (2,5-thienylenevinylene) or a derivative thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, or polysiloxane.

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

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

  In the polymer LED of the present invention, it is usually preferable that at least one of an electrode composed of an anode and a cathode is transparent or translucent, and the anode side is transparent or translucent. As the material for the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film made of conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Further, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.

  The film thickness of the anode can be appropriately selected in consideration of light transmittance and electrical conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. is there.

  Further, in order to facilitate charge injection on the anode, a layer made of a phthalocyanine derivative, a conductive polymer, carbon or the like, or an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like. A layer may be provided.

  As a material of the cathode used in the polymer LED of the present invention, a material having a small work function is preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and their Two or more of these alloys, or an alloy of one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite intercalation compound, etc. Is used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, and the like. The cathode may have a laminated structure of two or more layers.

  The film thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

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

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

Among the elements of the present invention, an element manufactured by heat treatment at a temperature of 50 ° C. or higher when forming a layer containing a polymer composition or a layer formed using a polymer solution composition is used. It is preferable from the viewpoint of life. The layer containing the polymer composition and the layer formed using the polymer solution composition are preferably light emitting layers.
The conditions for the heat treatment are usually those under which the onium salt is decomposed by the heat treatment, and the temperature of the heat treatment is 50 ° C. or higher, preferably in the range of 50 ° C. to 300 ° C.
The heat treatment time is usually about 1 second to 24 hours.
The heat treatment can be performed using, for example, a hot plate, an oven, an infrared lamp, or the like. Further, the heat treatment may be performed under reduced pressure.
The heat treatment is preferably performed after the light emitting layer is formed, and more preferably immediately after the light emitting layer is formed.

  Further, the element of the present invention may be manufactured by irradiating radiation when forming the light emitting layer or after forming the light emitting layer. Examples of radiation include ultraviolet rays, electron beams, and X-rays, and ultraviolet rays are preferable.

  The polymer LED of the present invention can be used as a planar light source, a segment display device, a dot matrix display device, a backlight of a liquid crystal display device, and the like.

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

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

EXAMPLES Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
Here, for the number average molecular weight, the number average molecular weight in terms of polystyrene was determined by gel permeation chromatography (GPC) using chloroform as a solvent.

Synthesis Example 1 (Synthesis of Compound A)
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 Compound A.
MS (ESI-negative)
m / z 1049.8 ([M−K] ⁻ )

Example 2 (Synthesis of Compound B)
The 25 ml Schlenk tube was purged with nitrogen, 40 mg of 1,1′-dimethyl-4,4′-bipyridinium dichloride was dissolved in 4.0 ml of water, and 400 mg of compound A was added. Chloroform 4.0ml was added and it stirred for 4.5 hours. Filtration, washing with water and evaporation of the solvent gave 288 mg of compound B.
¹ H-NMR (300 MHz, DMSO-d6)
δ 9.30 (4H, brs), 8.78 (4H, brs), 4.47 (6H, s)

δ−１３２．５、−１３３．６、−１３４．１、−１５７．８、−１５９．７、−１６４．１、−１６５．２ Example 3 (Synthesis of Compound C)
The 25 ml Schlenk tube was purged with nitrogen, and 150 mg of bis (4-t-butylphenyl) iodonium triflate was taken and suspended in 4 ml of water. When 392 mg of Compound A was added and further 3 ml of toluene was added, the insoluble matter was dissolved. After stirring for 8 hours, liquid separation was performed, and the aqueous phase was extracted with toluene. After drying with sodium sulfate, the solvent was distilled off to obtain 373 mg of Compound C.
¹ H-NMR (DMSO-d6, 300 MHz)
δ8.16 (4H, d), 7.55 (4H, m), 1.26 (18H, s)
¹⁹ F-NMR (DMSO-d6, 300 MHz)

δ-132.5, -133.6, -134.1, -157.8, -159.7, -164.1, -165.2

Synthesis Example 4 (Synthesis of Compound D)
The 25 ml Schlenk tube was purged with nitrogen, and 100 mg of triphenylsulfonium bromide was taken and dissolved in 4 ml of water. When 408 mg of Compound A was added, the solution became cloudy. 3 ml of toluene was added and stirred for 8 hours, followed by liquid separation. The aqueous phase was extracted with toluene and diethyl ether. After drying with sodium sulfate, the solvent was distilled off to obtain 449 mg of Compound D.
¹ H-NMR (DMSO-d6, 300 MHz)
δ 7.90-7.75 (15H, m)
¹⁹ F-NMR (DMSO-d6, 300 MHz)
δ-132.7, -133.7, -134.1, -157.9, -160.0, -164.2, -165.3

Synthesis example 5
<Synthesis of Polymer Compound 1>
2,7-dibromo-9,9-dioctylfluorene (26 g, 0.047 mol), 2,7-dibromo-9,9-diisopentylfluorene (5.6 g, 0.012 mol) and 2,2′-bipyridyl (22 g, 0.141 mol) was dissolved in 1600 mL of dehydrated tetrahydrofuran, and the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (40 g, 0.15 mol) was added to this solution, and the temperature was raised to 60 ° C. and allowed to react for 8 hours. It was. After the reaction, this reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 200 mL / methanol 1200 mL / ion-exchanged water 1200 mL and stirred for 30 minutes, and then the deposited precipitate was filtered. Air dried. Then, it melt | dissolved in 1100 mL of toluene, it filtered, and the filtrate was dripped at 3300 mL of methanol, and was stirred for 30 minutes. The deposited precipitate was filtered, washed with 1000 mL of methanol, and dried under reduced pressure for 5 hours. The yield of the obtained copolymer was 20 g (hereinafter referred to as polymer compound 1). The average molecular weight and weight average molecular weight in terms of polystyrene of the polymer compound 1 were Mn = 9.9 × 10 ⁴ and Mw = 2.0 × 10 ⁵ (mobile phase: chloroform), respectively.

不活性雰囲気下で、５００ｍｌの３つ口フラスコに酢酸２２５ｇを入れ、５−ｔ−ブチル−ｍ−キシレン２４．３ｇを加えた。続いて臭素３１．２ｇを加えた後、１５〜２０℃で３時間反応させた。
反応液を水５００ｍｌに加え析出した沈殿をろ過した。水２５０ｍｌで２回洗浄し、白色の固体３４．２ｇを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ(ｐｐｍ) ＝ １．３〔ｓ，９Ｈ〕、２．４〔ｓ，６Ｈ〕、７．１〔ｓ，２Ｈ〕
ＭＳ（ＦＤ⁺）Ｍ⁺ ２４１ Synthesis Example 6
<Synthesis of 4-t-butyl-2,6-dimethylbromobenzene>

Under an inert atmosphere, 225 g of acetic acid was placed in a 500 ml three-necked flask, and 24.3 g of 5-t-butyl-m-xylene was added. Then, after adding 31.2 g of bromine, it was made to react at 15-20 degreeC for 3 hours.
The reaction solution was added to 500 ml of water, and the deposited precipitate was filtered. This was washed twice with 250 ml of water to obtain 34.2 g of a white solid.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ (ppm) = 1.3 [s, 9H], 2.4 [s, 6H], 7.1 [s, 2H]
MS (FD ⁺ ) M ⁺ 241

不活性雰囲気下で、１００ｍｌの３つ口フラスコに脱気した脱水トルエン３６ｍｌを入れ、トリ（ｔ−ブチル）ホスフィン０．６３ｇを加えた。続いてトリス（ジベンジリデンアセトン）ジパラジウム０．４１ｇ、上記の４−ｔ−ブチル−２，６−ジメチルブロモベンゼン９．６ｇ、ｔ−ブトキシナトリウム５．２ｇ、Ｎ，Ｎ’−ジフェニル−１，４−フェニレンジアミン４．７ｇを加えた後、１００℃で３時間反応させた。
反応液を飽和食塩水３００ｍｌに加え、約５０℃に温めたクロロホルム３００ｍｌで抽出した。溶媒を留去した後、トルエン１００ｍｌを加えて、固体が溶解するまで加熱、放冷した後、沈殿をろ過し、白色の固体９．９ｇを得た。 Synthesis example 7
<Synthesis of N, N′-diphenyl-N, N′-bis (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine>

Under an inert atmosphere, 36 ml of degassed dehydrated toluene was placed in a 100 ml three-necked flask, and 0.63 g of tri (t-butyl) phosphine was added. Subsequently, 0.41 g of tris (dibenzylideneacetone) dipalladium, 9.6 g of the above-mentioned 4-t-butyl-2,6-dimethylbromobenzene, 5.2 g of sodium t-butoxy, N, N′-diphenyl-1, After adding 4.7 g of 4-phenylenediamine, the mixture was reacted at 100 ° C. for 3 hours.
The reaction solution was added to 300 ml of saturated brine and extracted with 300 ml of chloroform warmed to about 50 ° C. After the solvent was distilled off, 100 ml of toluene was added, and the mixture was heated and allowed to cool until the solid was dissolved, and then the precipitate was filtered to obtain 9.9 g of a white solid.

不活性雰囲気下で、１０００ｍｌの３つ口フラスコに脱水Ｎ，Ｎ−ジメチルホルムアミド３５０ｍｌを入れ、上記のＮ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（４−ｔ−ブチル−２，６−ジメチルフェニル）−１，４−フェニレンジアミン５．２ｇを溶解した後、氷浴下でＮ−ブロモスクシンイミド３．５ｇ／Ｎ，Ｎ−ジメチルホルムアミド溶液を滴下し、一昼夜反応させた。
反応液に水１５０ｍｌを加え、析出した沈殿をろ過し、メタノール５０ｍｌで２回洗浄し白色の固体４．４ｇを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＴＨＦ−ｄ８）：
δ(ｐｐｍ) ＝ １．３〔ｓ，１８Ｈ〕、２．０〔ｓ，１２Ｈ〕、６．６〜６．７〔ｄ，４Ｈ〕、６．８〜６．９〔ｂｒ，４Ｈ〕、７．１〔ｓ，４Ｈ〕、７．２〜７．３〔ｄ，４Ｈ〕
ＭＳ（ＦＤ⁺）Ｍ⁺ ７３８ Synthesis Example 8
<Synthesis of N, N′-bis (4-bromophenyl) -N, N′-bis (4-tert-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine>

Under an inert atmosphere, 350 ml of dehydrated N, N-dimethylformamide was placed in a 1000 ml three-necked flask and the above N, N′-diphenyl-N, N′-bis (4-t-butyl-2,6- After dissolving 5.2 g of (dimethylphenyl) -1,4-phenylenediamine, a 3.5 g / N, N-dimethylformamide solution of N-bromosuccinimide was added dropwise in an ice bath and allowed to react overnight.
150 ml of water was added to the reaction solution, and the deposited precipitate was filtered and washed twice with 50 ml of methanol to obtain 4.4 g of a white solid.
¹ H-NMR (300 MHz / THF-d8):
δ (ppm) = 1.3 [s, 18H], 2.0 [s, 12H], 6.6 to 6.7 [d, 4H], 6.8 to 6.9 [br, 4H], 7 .1 [s, 4H], 7.2 to 7.3 [d, 4H]
MS (FD ⁺ ) M ⁺ 738

上記２，７−ジブロモ−３，６−ジオクチルオキシジベンゾチオフェン（特開２００４−００２７０３に従い合成、５．４ｇ、９ｍｍｏｌ）、上記Ｎ，Ｎ’−ビス（４−ブロモフェニル）−Ｎ，Ｎ’−ビス（４−ｔ−ブチル−２，６−ジメチルフェニル）−１，４−フェニレンジアミン（４．５ｇ、６ｍｍｏｌ）および２，２’−ビピリジル（５．１ｇ、３３ｍｍｏｌ）を脱水したテトラヒドロフラン４２０ｍＬに溶解した後、窒素でバブリングして系内を窒素置換した。窒素雰囲気下において、この溶液に、ビス（１、５−シクロオクタジエン）ニッケル（０）｛Ｎｉ（ＣＯＤ）₂｝（９．０ｇ、３３ｍｍｏｌ）加え、６０℃まで昇温し、攪拌しながら３時間反応させた。反応後、この反応液を室温（約２５℃）まで冷却し、２５％アンモニア水１５０ｍＬ／メタノール１５００ｍＬ／イオン交換水６００ｍＬ混合溶液中に滴下して１時間攪拌した後、析出した沈殿をろ過して２時間減圧乾燥し、トルエン４５０ｍＬに溶解させた。その後、１Ｎ塩酸４５０ｍＬを加えて１時間攪拌し、水層を除去し、有機層に４％アンモニア水４５０ｍＬを加え、1時間攪拌した後に水層を除去した。有機層はメタノール１３５０ｍＬに滴下して１時間攪拌し、析出した沈殿をろ過して２時間減圧乾燥し、トルエン４００ｍＬに溶解させた。その後、アルミナカラム（アルミナ量１００ｇ）を通して精製を行い、回収したトルエン溶液をメタノール１３５０ｍＬに滴下して１時間攪拌し、析出した沈殿をろ過して２時間減圧乾燥させた。得られた共重合体（以後、高分子化合物２と呼ぶ）の収量は５．５ｇであった。ポリスチレン換算の平均分子量および重量平均分子量は、それぞれＭｎ＝３．０×１０⁴、Ｍｗ＝１．８×１０⁵であった（移動相：クロロホルム）。 Synthesis Example 9
<Synthesis of Polymer Compound 2>

2,7-dibromo-3,6-dioctyloxydibenzothiophene (synthesized according to JP 2004-002703, 5.4 g, 9 mmol), N, N′-bis (4-bromophenyl) -N, N′- Dissolve bis (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine (4.5 g, 6 mmol) and 2,2′-bipyridyl (5.1 g, 33 mmol) in 420 mL of dehydrated tetrahydrofuran. Then, the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (9.0 g, 33 mmol) was added to this solution, and the temperature was raised to 60 ° C. Reacted for hours. After the reaction, this reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 150 mL / methanol 1500 mL / ion exchanged water 600 mL and stirred for 1 hour, and then the deposited precipitate was filtered. It was dried under reduced pressure for 2 hours and dissolved in 450 mL of toluene. Thereafter, 450 mL of 1N hydrochloric acid was added and stirred for 1 hour, the aqueous layer was removed, 450 mL of 4% aqueous ammonia was added to the organic layer, and the aqueous layer was removed after stirring for 1 hour. The organic layer was dropped into 1350 mL of methanol and stirred for 1 hour, the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 400 mL of toluene. Then, it refine | purified through the alumina column (alumina amount 100g), and the collect | recovered toluene solution was dripped at methanol 1350mL, it stirred for 1 hour, the depositing precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained copolymer (hereinafter referred to as polymer compound 2) was 5.5 g. The average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 3.0 × 10 ⁴ and Mw = 1.8 × 10 ⁵ (mobile phase: chloroform), respectively.

化合物Ｐ
不活性雰囲気下、３００ｍｌ三つ口フラスコに１‐ナフタレンボロン酸５．００ｇ（２９ｍｍｏｌ）、２−ブロモベンズアルデヒド６．４６ｇ（３５ｍｍｏｌ）、炭酸カリウム１０.０ｇ（７３ｍｍｏｌ）、トルエン３６ｍｌ、イオン交換水３６ｍｌを入れ、室温で撹拌しつつ２０分間アルゴンバブリングした。続いてテトラキス（トリフェニルホスフィン）パラジウム１６．８ｍｇ（０.１５ｍｍｏｌ）を入れ、さらに室温で撹拌しつつ１０分間アルゴンバブリングした。１００℃に昇温し、２５時間反応させた。室温まで冷却後、トルエンで有機層を抽出、硫酸ナトリウムで乾燥後、溶媒を留去した。トルエン：シクロヘキサン＝１：２混合溶媒を展開溶媒としたシリカゲルカラムで生成することにより、化合物Ｐ５.１８ｇ（収率８６％）を白色結晶として得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ７．３９〜７．６２（ｍ、５Ｈ）、７．７０（ｍ、２Ｈ）、７．９４（ｄ、２Ｈ）、８．１２（ｄｄ、２Ｈ）、９．６３（ｓ、１Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ２３３ Synthesis Example 10
(Synthesis of Compound P)

Compound P
Under an inert atmosphere, in a 300 ml three-necked flask, 5.00 g (29 mmol) of 1-naphthaleneboronic acid, 6.46 g (35 mmol) of 2-bromobenzaldehyde, 10.0 g (73 mmol) of potassium carbonate, 36 ml of toluene, 36 ml of ion-exchanged water And argon bubbling was performed for 20 minutes with stirring at room temperature. Subsequently, 16.8 mg (0.15 mmol) of tetrakis (triphenylphosphine) palladium was added, and argon was bubbled for 10 minutes while stirring at room temperature. The temperature was raised to 100 ° C. and reacted for 25 hours. After cooling to room temperature, the organic layer was extracted with toluene, dried over sodium sulfate, and the solvent was distilled off. By producing on a silica gel column using a mixed solvent of toluene: cyclohexane = 1: 2 as a developing solvent, 5.18 g of Compound P (yield 86%) was obtained as white crystals.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 7.39-7.62 (m, 5H), 7.70 (m, 2H), 7.94 (d, 2H), 8.12 (dd, 2H), 9.63 (s, 1H)
MS (APCI (+)): (M + H) ^<+> 233

化合物Ｑ
不活性雰囲気下で３００ｍｌの三つ口フラスコに化合物Ｐ８．００ｇ（３４.４ｍｍｏｌ）と脱水ＴＨＦ４６ｍｌを入れ、−７８℃まで冷却した。続いてｎ−オクチルマグネシウムブロミド（１.０ｍｏｌ／ｌＴＨＦ溶液）５２ｍｌを３０分かけて滴下した。滴下終了後０℃まで昇温し、１時間撹拌後、室温まで昇温して４５分間撹拌した。氷浴して１Ｎ塩酸２０ｍｌを加えて反応を終了させ、酢酸エチルで有機層を抽出、硫酸ナトリウムで乾燥した。溶媒を留去した後トルエン：ヘキサン＝１０：１混合溶媒を展開溶媒とするシリカゲルカラムで精製することにより、化合物Ｑ７．６４ｇ（収率６４％）を淡黄色のオイルとして得た。ＨＰＬＣ測定では２本のピークが見られたが、ＬＣ−ＭＳ測定では同一の質量数であることから、異性体の混合物であると判断した。 (Synthesis of Compound Q)

Compound Q
Under an inert atmosphere, 8.00 g (34.4 mmol) of Compound P and 46 ml of dehydrated THF were placed in a 300 ml three-necked flask and cooled to -78 ° C. Subsequently, 52 ml of n-octylmagnesium bromide (1.0 mol / l THF solution) was added dropwise over 30 minutes. After completion of dropping, the temperature was raised to 0 ° C., stirred for 1 hour, then warmed to room temperature and stirred for 45 minutes. The reaction was terminated by adding 20 ml of 1N hydrochloric acid in an ice bath, and the organic layer was extracted with ethyl acetate and dried over sodium sulfate. After distilling off the solvent, the residue was purified by a silica gel column using a mixed solvent of toluene: hexane = 10: 1 as a developing solvent to obtain 7.64 g (yield: 64%) of Compound Q as a pale yellow oil. Although two peaks were observed in the HPLC measurement, they were determined to be a mixture of isomers because they were the same mass number in the LC-MS measurement.

化合物Ｒ
不活性雰囲気下、５００ｍｌ三つ口フラスコに化合物Ｑ（異性体の混合物）５.００ｇ（１４.４ｍｍｏｌ）と脱水ジクロロメタン７４ｍｌを入れ、室温で撹拌、溶解させた。続いて、三フッ化ホウ素のエーテラート錯体を室温で１時間かけて滴下し、的か終了後室温で４時間撹拌した。撹拌しながらエタノール１２５ｍｌをゆっくりと加え、発熱がおさまったらクロロホルムで有機層を抽出、２回水洗し、硫酸マグネシウムで乾燥した。溶媒を留去後、ヘキサンを展開溶媒とするシリカゲルカラムで精製することにより、化合物Ｒ３．２２ｇ（収率６８％）を無色のオイルとして得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９０（ｔ、３Ｈ）、１．０３〜１．２６（ｍ、１４Ｈ）、２．１３（ｍ、２Ｈ）、４．０５（ｔ、１Ｈ）、７．３５（ｄｄ、１Ｈ）、７．４６〜７．５０（ｍ、２Ｈ）、７．５９〜７．６５（ｍ、３Ｈ）、７．８２（ｄ、１Ｈ）、７．９４（ｄ、１Ｈ）、８．３５（ｄ、１Ｈ）、８．７５（ｄ、１Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ３２９ (Synthesis of Compound R)

Compound R
Under an inert atmosphere, 5.00 g (14.4 mmol) of Compound Q (mixture of isomers) and 74 ml of dehydrated dichloromethane were placed in a 500 ml three-necked flask, and dissolved by stirring at room temperature. Subsequently, boron ether trifluoride etherate complex was added dropwise at room temperature over 1 hour, and after completion, the mixture was stirred at room temperature for 4 hours. While stirring, 125 ml of ethanol was slowly added. When the exotherm subsided, the organic layer was extracted with chloroform, washed twice with water, and dried over magnesium sulfate. After distilling off the solvent, the residue was purified with a silica gel column using hexane as a developing solvent to obtain 3.22 g (yield 68%) of Compound R as a colorless oil.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 3H), 1.03-1.26 (m, 14H), 2.13 (m, 2H), 4.05 (t, 1H), 7.35 (dd, 1H), 7 .46-7.50 (m, 2H), 7.59-7.65 (m, 3H), 7.82 (d, 1H), 7.94 (d, 1H), 8.35 (d, 1H) ), 8.75 (d, 1H)
MS (APCI (+)): (M + H) ^<+> 329

化合物Ｓ
不活性雰囲気下２００ｍｌ三つ口フラスコにイオン交換水２０ｍｌをいれ、撹拌しながら水酸化ナトリウム１８．９ｇ（０.４７ｍｏｌ）を少量ずつ加え、溶解させた。水溶液が室温まで冷却した後、トルエン２０ｍｌ、化合物Ｒ５.１７ｇ（１５.７ｍｍｏｌ）、臭化トリブチルアンモニウム１．５２ｇ（４.７２ｍｍｏｌ）を加え、５０℃に昇温した。臭化ｎ−オクチルを滴下し、滴下終了後５０℃で９時間反応させた。反応終了後トルエンで有機層を抽出し、２回水洗し、硫酸ナトリウムで乾燥した。ヘキサンを展開溶媒とするシリカゲルカラムで精製することにより、化合物Ｓ５．１３ｇ（収率７４％）を黄色のオイルとして得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．５２（ｍ、２Ｈ）、０．７９（ｔ、６Ｈ）、１．００〜１．２０（ｍ、２２Ｈ）、２．０５（ｔ、４Ｈ）、７．３４（ｄ、１Ｈ）、７．４０〜７．５３（ｍ、２Ｈ）、７．６３（ｍ、３Ｈ）、７．８３（ｄ、１Ｈ）、７．９４（ｄ、１Ｈ）、８．３１（ｄ、１Ｈ）、８．７５（ｄ、１Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ４４１ (Synthesis of Compound S)

Compound S
Under an inert atmosphere, 20 ml of ion-exchanged water was placed in a 200 ml three-necked flask, and 18.9 g (0.47 mol) of sodium hydroxide was added little by little with stirring to dissolve. After the aqueous solution was cooled to room temperature, 20 ml of toluene, 5.17 g (15.7 mmol) of Compound R and 1.52 g (4.72 mmol) of tributylammonium bromide were added, and the temperature was raised to 50 ° C. N-Octyl bromide was added dropwise, and after completion of the addition, the mixture was reacted at 50 ° C. for 9 hours. After completion of the reaction, the organic layer was extracted with toluene, washed twice with water, and dried over sodium sulfate. Purification by a silica gel column using hexane as a developing solvent gave 5.13 g (yield 74%) of compound S as a yellow oil.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.52 (m, 2H), 0.79 (t, 6H), 1.00-1.20 (m, 22H), 2.05 (t, 4H), 7.34 (d, 1H), 7 40 to 7.53 (m, 2H), 7.63 (m, 3H), 7.83 (d, 1H), 7.94 (d, 1H), 8.31 (d, 1H), 8. 75 (d, 1H)
MS (APCI (+)): (M + H) ^<+> 441

化合物Ｔ
空気雰囲気下、５０ｍｌの三つ口フラスコに化合物Ｓ４．００ｇ（９．０８ｍｍｏｌ）と酢酸：ジクロロメタン＝１：１混合溶媒５７ｍｌを入れ、室温で撹拌、溶解させた。続いて三臭化ベンジルトリメチルアンモニウム７．７９ｇ（２０．０ｍｍｏｌ）を加えて撹拌しつつ、塩化亜鉛を三臭化ベンジルトリメチルアンモニウムが完溶するまで加えた。室温で２０時間撹拌後、５％亜硫酸水素ナトリウム水溶液１０ｍｌを加えて反応を停止し、クロロホルムで有機層を抽出、炭酸カリウム水溶液で２回洗浄し、硫酸ナトリウムで乾燥した。ヘキサンを展開溶媒とするフラッシュカラムで２回精製した後、エタノール：ヘキサン＝１：１、続いて１０：１混合溶媒で再結晶することにより、化合物Ｔ４．１３ｇ（収率７６％）を白色結晶として得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．６０（ｍ、２Ｈ）、０．９１（ｔ、６Ｈ）、１．０１〜１．３８（ｍ、２２Ｈ）、２．０９（ｔ、４Ｈ）、７．６２〜７．７５（ｍ、３Ｈ）、７．８９（ｓ、１Ｈ）、８．２０（ｄ、１Ｈ）、８．４７（ｄ、１Ｈ）、８．７２（ｄ、１Ｈ）
ＭＳ（ＡＰＰＩ（＋））：（Ｍ＋Ｈ）⁺ ５９８ (Synthesis of Compound T)

Compound T
Under an air atmosphere, 4.00 g (9.08 mmol) of Compound S and 57 ml of a mixed solvent of acetic acid: dichloromethane = 1: 1 were placed in a 50 ml three-necked flask and stirred and dissolved at room temperature. Subsequently, 7.79 g (20.0 mmol) of benzyltrimethylammonium tribromide was added and stirred, and zinc chloride was added until benzyltribromide tribromide was completely dissolved. After stirring at room temperature for 20 hours, the reaction was stopped by adding 10 ml of 5% aqueous sodium bisulfite solution, and the organic layer was extracted with chloroform, washed twice with aqueous potassium carbonate solution, and dried over sodium sulfate. After purification twice with a flash column using hexane as a developing solvent, 4.13 g of Compound T (yield 76%) was obtained as white crystals by recrystallization with ethanol: hexane = 1: 1, followed by a 10: 1 mixed solvent. Got as.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.60 (m, 2H), 0.91 (t, 6H), 1.01-1.38 (m, 22H), 2.09 (t, 4H), 7.62-7.75 (m, 3H), 7.89 (s, 1H), 8.20 (d, 1H), 8.47 (d, 1H), 8.72 (d, 1H)
MS (APPI (+)): (M + H) ^<+> 598

Synthesis Example 11
<Synthesis of Polymer Compound 3>
Compound T (8.0 g) and 2,2′-bipyridyl (5.9 g) were dissolved in 300 mL of dehydrated tetrahydrofuran and then bubbled with nitrogen to replace the system with nitrogen. In a nitrogen atmosphere, the temperature of the solution was raised to 60 ° C., bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (10.4 g, 0.038 mol) was added, and the reaction was performed for 5 hours. I let you. After the reaction, this reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 40 mL / methanol 300 mL / ion exchanged water 300 mL and stirred for 30 minutes, and then the deposited precipitate was filtered. Air dried. Then, after dissolving in 400 mL of toluene, filtration is performed, the filtrate is purified through an alumina column, about 300 mL of 1N hydrochloric acid is added and stirred for 3 hours, the aqueous layer is removed, and about 300 mL of 4% aqueous ammonia is added to the organic layer. In addition, the aqueous layer was removed after stirring for 2 hours. About 300 mL of ion exchange water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. About 100 mL of methanol was added dropwise to the organic layer, stirred for 1 hour, and allowed to stand, and then the supernatant was removed by decantation. The obtained precipitate was dissolved in 100 mL of toluene, dropped into about 200 mL of methanol, stirred for 1 hour, filtered and dried under reduced pressure for 2 hours. The yield of the obtained copolymer was 4.1 g (hereinafter referred to as polymer compound 3). The average molecular weight and weight average molecular weight in terms of polystyrene of the polymer compound 3 were Mn = 1.5 × 10 ⁵ and Mw = 2.7 × 10 ⁵ (mobile phase: tetrahydrofuran), respectively.

Synthesis Example 12
<Synthesis of Polymer Compound 4>
Compound T (0.65 g), N, N′-bis (4-bromophenyl) -N, N′-bis (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine (0 .34 g) and 2,2′-bipyridyl (0.58 g) were dissolved in 100 mL of dehydrated tetrahydrofuran, and the inside of the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (1.0 g) was added to this solution, the temperature was raised to 60 ° C., and the reaction was continued for 3 hours with stirring. I let you. After the reaction, this reaction solution is cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 10 mL / methanol about 100 mL / ion exchange water about 100 mL, and stirred for 1 hour, and then the deposited precipitate is filtered. The solution was dried under reduced pressure for 3 hours, and then dissolved in 50 mL of toluene, followed by filtration. The filtrate was purified through an alumina column, added with about 50 mL of 4% aqueous ammonia, stirred for 2 hours, and then the aqueous layer was removed. About 50 mL of ion exchange water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. The organic layer was dropped into about 100 mL of methanol, stirred for 1 hour, and allowed to stand, and then the supernatant was removed by decantation. The obtained precipitate was dissolved in 50 mL of toluene, dropped into about 200 mL of methanol, stirred for 1 hour, filtered and dried under reduced pressure for 2 hours. The yield of the obtained copolymer was 390 mg (hereinafter referred to as polymer compound 4). The average molecular weight and weight average molecular weight in terms of polystyrene of the polymer compound 4 were Mn = 1.6 × 10 ⁴ and Mw = 7.4 × 10 ⁴ (mobile phase: tetrahydrofuran), respectively.

Synthesis Example 13 (Synthesis of Compound E)
The 200 ml four-necked flask was purged with nitrogen, and 0.486 g of tri (4-t-butylphenylsulfonium) trifluoromethanesulfonate, 0.873 g of Compound A, 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 at room temperature and then dried to a constant weight with a vacuum pump at 70-75 ° C. 1.19 g of compound E was obtained.
¹ H-NMR (300 MHz, DMSO-D ₆ )
δ 7.78 (12H, m), 1.32 (27H, s)

Example 4 (Synthesis of Compound F)
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 A, 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 compound F 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

Synthesis Example 14 (Synthesis of Compound G)
Synthesis of Potassium Salt A 200 ml four-necked flask was purged with nitrogen and charged with 3.01 g of K2 [Ni (CN) 4], 25.5 g of tris (pentafluorophenyl) borane, and 100 ml of diethyl ether. After attaching a stir bar, thermometer and condenser, the reaction was carried out at 21-23 ° C. for 16 hours. The precipitated crystals were filtered and the cake was washed with 100 ml of ethyl acetate. Residual K2 [Ni (CN) 4] on the filter was treated with 5% sodium hypochlorite. The filtrate was transferred to a 500 ml separatory funnel and washed three times with 100 ml of ion exchange water. The organic layer was transferred to a 500 ml Erlenmeyer flask and dehydrated by adding anhydrous sodium sulfate, and then anhydrous sodium sulfate was filtered off. The solvent was concentrated with an evaporator to obtain 31.4 g of a crude cake. To the crude cake, 60 ml of diethyl ether and 120 ml of n-hexane were added and stirred at room temperature for 1 hour, followed by filtration. The cake was washed with 50 ml of n-hexane. It dried at 70-75 degreeC until it became constant weight with the vacuum dryer. 24.4 g of potassium salt was obtained.

Synthesis of Compound G
The 200 ml four-necked flask was purged with nitrogen, and 3.0 g of potassium salt, 100 ml of diethyl ether and 20 ml of ion-exchanged water were squeezed, and a stir bar, thermometer and condenser were attached. While stirring at 21 to 23 ° C., 15 g of 1% hydrochloric acid was added dropwise over 10 minutes, followed by stirring for 1 hour. 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 with ion exchange water three times. 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 filtrate was concentrated with an evaporator at room temperature, and then dried at 70 to 75 ° C. with a vacuum pump until a constant weight was obtained. 81 g of compound G2 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

Example 5 (Synthesis of Compound H)
The 200 ml four-necked flask was purged with nitrogen and charged with 0.323 g of 1,1′-di-2-ethylhexyl-4,4′-bipyridinium diiodide, 1.223 g of compound A, 20 ml of ion-exchanged water, and 60 ml of diethyl ether. After attaching a stir bar, a thermometer and a condenser, the reaction was carried out at 21-23 ° C. for 22 hours. After the reaction, the contents of the flask were transferred to a 200 ml separatory funnel, the aqueous layer was separated, and the ether layer was washed 3 times with 40 ml of ion-exchanged 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. 50 ml of toluene was added and the mixture was stirred and washed at 60 to 65 ° C. for 0.5 hour, cooled to room temperature and filtered. This washing operation was performed three times, and then dried at 80 to 85 ° C. with a vacuum pump until a constant weight was obtained. 1.15 g of compound H was obtained.

¹ H-NMR (270 MHz, CD ₃ OD)
δ 9.258 (4H, m), 8.687 (4H, m), 4.665 (4H, d),
2.049 (2H, m), 1.387 (16H, m), 0.943 (12H, m)

Synthesis Example 15 (Synthesis of Compound I)
Synthesis of Quaternary Salt A 50 ml four-necked flask was purged with nitrogen, and 27.4 g of 1,8-dioazabicyclo [5,4,0] undec-7-ene and 11.6 g of n-octyl bromide were charged. After attaching a stir bar, thermometer and condenser, the reaction was carried out at 110 to 115 ° C. for 5.5 hours. After cooling to 80 ° C., 50 ml of toluene and 150 ml of hexane were added and cooled to 5 ° C. The mixture was stirred at 5 ° C. or lower for 1 hour and allowed to stand at the same temperature for 1 hour. The flask was charged with 50 ml of toluene and 150 ml of hexane, stirred at 60 to 65 ° C. for 1 hour, and then cooled to 5 ° C. The mixture was stirred at 5 ° C. or lower for 1 hour, allowed to stand at the same temperature for 1 hour, and the supernatant was removed by decantation. After this operation was performed again, the remaining solvent was distilled off with an evaporator. Next, it dried at 80-85 degreeC with the vacuum pump until it became constant weight, and obtained 19.5g of quaternary salts.

Quaternary salt ¹ H-NMR (270 MHz, CD ₃ OD)
δ 3.676 (2H, m), 3.545 (6H, m), 2.054 (2H, m),
1.722 (10H, m) 1.332 (10H, m), 0.798 (3H, m)

Synthesis of Compound I A 200 ml four-necked flask was purged with nitrogen, and 0.590 g of a quaternary salt, Compound A 1.240, ion exchange 20 ml, and diethyl ether 60 ml were charged. After attaching a stir bar, thermometer and condenser, the reaction was carried out at 21-23 ° C. for 24 hours. After the reaction, the contents of the flask were transferred to a 200 ml separatory funnel, the aqueous layer was separated, and the ether layer was washed 3 times with 40 ml of ion-exchanged 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. 1.53 g of compound I was obtained.


Compound I ¹ H-NMR (270 MHz, CD ₃ OD)
δ 3.660 (2H, m), 3.520 (6H, m), 2.064 (2H, m),
1.748 (10H, m) 1.296 (10H, m), 0.867 (3H, m)

Example 6 (Synthesis of Compound K)
A 200 ml four-necked flask was purged with nitrogen, 0.31 g of 1,1′-di-2-ethylhexyl-4,4′-bipyridinium diiodide, Synthesis Example 12 1.144 g of potassium salt obtained by the synthesis of Compound G, ion 20 ml of exchange 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 18 hours. After the reaction, the contents of the flask were transferred to a 200 ml separatory funnel, and 50 ml of ethyl acetate was added to separate the aqueous layer. Next, the organic layer was washed three times with 30 ml of ion exchange water. The organic layer was transferred to a 200 ml Erlenmeyer flask, 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. 1.18 g of compound K was obtained.

¹ H-NMR (270 MHz, DMSO-D ₆ )
δ 9.385 (4H, d), 8.805 (4H, d), 4.634 (4H, m),
2.073 (2H, m) 1.300 (16H, m), 0.870 (12H, m)

Example 7 (Synthesis of Compound L)
The 200 ml four-necked flask was purged with nitrogen, and 0.205 g of 1,1′-dibenzyl-4,4′-bipyridinium dichloride, 1.089 g of Compound A, 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 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 compound L 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)

Example 8 (Synthesis of Compound M)
The 200 ml four-necked flask was purged with nitrogen, 0.595 g of tri (4-t-butylphenylsulfonium) trifluoromethanesulfonate, 1.144 g of the potassium salt obtained by the synthesis of Compound G, 20 ml of ion-exchanged water, diethyl ether 60 ml was 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 50 ml of ethyl acetate was added to separate the aqueous layer. Next, the organic layer was washed three times with 30 ml of ion exchange water. The organic layer was transferred to a 200 ml Erlenmeyer flask, 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. 1.24 g of compound M was obtained.

¹ H-NMR (300 MHz, DMSO-D ₆ )
δ 7.774 (12H, m), 1.313 (27H, s)

Synthesis Example 17 (Synthesis of Compound N)
The 200 ml four-necked flask was purged with nitrogen and charged with 1.089 g of Compound A, 20 ml of ion-exchanged water, and 50 ml of diethyl ether. 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 compound N 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

<高分子化合物溶液組成物の調製１>
高分子化合物２と高分子化合物１の２５：７５（重量比）混合物をトルエン／酢酸エチル＝８０／２０（重量比）の混合溶媒に０．９ｗｔ％、さらに添加物としてイオン対を表１に示される添加量で混合し溶解させた。その後０．２ミクロン径のテフロン（登録商標）フィルターでろ過して塗布溶液を調整した。イオン対としては、合成例で合成したものを用いた。イオン対の添加量は、高分子化合物全体の重量１００重量部に対する重量部で表した。

<Preparation of polymer compound solution composition 1>
A 25:75 (weight ratio) mixture of polymer compound 2 and polymer compound 1 is 0.9 wt% in a mixed solvent of toluene / ethyl acetate = 80/20 (weight ratio), and ion pairs are listed in Table 1 as additives. Mix and dissolve in the indicated addition amount. Thereafter, the solution was filtered through a 0.2 micron diameter Teflon (registered trademark) filter to prepare a coating solution. As the ion pair, the one synthesized in the synthesis example was used. The addition amount of the ion pair was expressed in parts by weight with respect to 100 parts by weight of the whole polymer compound.

    <Element creation and evaluation 1>

A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is formed to a thickness of 70 nm by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Bayer, Baytron). Dried on plate for 10 minutes at 200 ° C. Next, a film having a thickness of about 85 nm was formed by spin coating at 1000 rpm using the prepared polymer compound coating solution. Further, this was dried at 90 ° C. under reduced pressure for 1 hour, and then, as a cathode buffer layer, lithium fluoride was deposited at 1 nm, calcium was deposited as a cathode at 5 nm, and then aluminum was deposited at 100 nm to produce a polymer LED. The degree of vacuum at the time of vapor deposition was 1 to 9 × 10 ⁻⁵ Torr. By applying voltage to the resulting device, EL light emission from the polymer compound was obtained. Table 1 shows the characteristics of the obtained element. In the life test, luminance was measured while driving at a constant current of 10 mA with an element having a light emitting portion of 2 mm × 2 mm (area 4 mm ² ). The converted lifetime is converted to the lifetime when the initial luminance is 2000 cd / m ² and assumes a relationship of half-life ∝ (initial luminance) ⁻¹ (Organic EL materials and displays, published by CMC (2001)) , Page 107).
Devices of Evaluation Examples 1 to 12 prepared using the polymer composition solution of the present invention containing ion pairs as a coating solution, compared to the device of Evaluation Comparative Example 1 prepared using a coating solution containing no ion pair There was a significant improvement in lifespan.

<高分子溶液組成物の調製２>
高分子化合物３と高分子化合物４の７０：３０（重量比）混合物をトルエン／酢酸エチル＝８０／２０（重量比）の混合溶媒に１．２ｗｔ％、さらに添加物としてイオン対を表２に示される添加量で混合し溶解させた。その後０．２ミクロン径のテフロン（登録商標）フィルターでろ過して高分子溶液組成物（塗布溶液）を調整した。イオン対としては、合成例で合成したものを用いた。イオン対の添加量は、高分子化合物全体の重量１００重量部に対する重量部で表した。

<Preparation of polymer solution composition 2>
A 70:30 (weight ratio) mixture of polymer compound 3 and polymer compound 4 is 1.2 wt% in a mixed solvent of toluene / ethyl acetate = 80/20 (weight ratio), and ion pairs are listed in Table 2 as additives. Mix and dissolve in the indicated addition amount. Thereafter, the mixture was filtered through a 0.2 micron diameter Teflon (registered trademark) filter to prepare a polymer solution composition (coating solution). As the ion pair, the one synthesized in the synthesis example was used. The addition amount of the ion pair was expressed in parts by weight with respect to 100 parts by weight of the whole polymer compound.

  <Element creation and evaluation 2>

A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is formed to a thickness of 70 nm by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Bayer, Baytron). Dried on plate for 10 minutes at 200 ° C. Next, a film having a thickness of about 85 nm was formed by spin coating at a rotational speed of 1000 rpm using the prepared polymer solution composition. Further, this was dried at 90 ° C. under reduced pressure for 1 hour, and then, as a cathode buffer layer, lithium fluoride was deposited at 1 nm, calcium was deposited as a cathode at 5 nm, and then aluminum was deposited at 100 nm to produce a polymer LED. The degree of vacuum at the time of vapor deposition was 1 to 9 × 10 ⁻⁵ Torr. By applying voltage to the resulting device, EL light emission from the polymer compound was obtained. Table 1 shows the characteristics of the obtained element. In the life test, luminance was measured while driving at a constant current of 10 mA with an element having a light emitting portion of 2 mm × 2 mm (area 4 mm ² ). The converted lifetime is converted to the lifetime when the initial luminance is 5000 cd / m ² and assumes a relationship of half-life ∝ (initial luminance) ⁻¹ (Organic EL materials and displays, published by CMC (2001)) , Page 107). Compared to the device of Evaluation Comparative Example 2 prepared using a coating solution containing no ion pair, the devices of Evaluation Examples 13 to 16 prepared using a polymer solution composition (coating solution) containing an ion pair were: A significant improvement in life was seen.

Claims (14)

A polymer composition comprising a conjugated polymer compound having luminescence and / or conductivity and an ion pair, wherein an anion of the ion pair is represented by the following formula (1), (2) or (3 ) indicated by the content of the ion pair, when the total weight of the conjugated polymer compound having a light emitting and / or electrically conductive and 100 parts by weight, 0.001 to 10 parts by weight of der Rukoto A polymer composition characterized by the above.

(Wherein Y ¹ represents a group 13 atom, Ar ¹ represents a perfluoroaryl group, 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 a direct bond, b represents an integer of 2 to 6, and Z ¹ represents M ′ (═O) p (wherein M 'Is a group 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 16, or 17 atoms. P represents an integer of 0 to 2), or a b-valent aliphatic hydrocarbon group, a b-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 ¹ is —C≡N—, —N═N═N—, —NH—, —NH ₂ In the case of-or -OH-, b = 2, Z ¹ and V ¹ In contrast, when a plurality of Ar ¹ are present, they may be the same or different, the plurality of V ¹ may be the same or different, and c represents an integer of 1 to 6. )

Wherein Y ² represents a Group 13 atom, Ar ² represents a perfluoroaryl group, V ² represents a Group 16 atom, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, Represents a bidentate heterocyclic group, —C≡N— or —N═N—, wherein a plurality of Y ² , Ar ² and V ² may be the same or different, and e represents an integer of 1 to 6; )

(In the formula, Y ³ represents a group 13 atom, Ar ³ represents a perfluoroaryl group, Q ³ represents a direct bond, V ³ represents a group 16 atom, a divalent aliphatic hydrocarbon group, 2 Represents a valent aromatic hydrocarbon group, a bidentate heterocyclic group, —C≡N— or —N═N—, and a plurality of Y ³ , Ar ³ , Q ³ and V ³ may be the same or different. And f represents an integer of 1 to 6.) 2. The polymer composition according to claim 1, wherein in the formula (1), Z ¹ or V ¹ is —C≡N—. The polymer composition according to claim 1 or 2, wherein the anion of the formula (1) is represented by the following formula (5-1) or (5-2).

(In the formula, M represents a nickel atom or a palladium atom.)   An element in which the cation of the ion pair is a hydrogen ion, a metal cation or a carbocation, or is selected from a nitrogen atom, oxygen atom, phosphorus atom, sulfur atom, chlorine atom, selenium atom, bromine atom, tellurium atom and iodine atom The polymer composition according to claim 1, wherein the polymer composition is an onium. The polymer composition according to any one of claims 1 to 4, wherein the conjugated polymer compound having luminescence and / or conductivity contains a repeating unit represented by the following formula (4).

(In the formula, A represents an atom or atomic group for completing a two 5- or 6-membered ring together with four carbon atoms on the benzene ring in the formula, R ^4a, R ^4b , R ^4c , R ^5a , R ^5b and R ^5c are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, aryl Alkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group Substituted silylthio group, substituted silylamino group, cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, heteroaryl Represents a thio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group or a carboxyl group, and R ^4b and R ^4c , and R ^5b and R ^5c are each taken together to form a ring May be formed.) The conjugated polymer compound having luminescence and / or conductivity is a polymer compound having luminescence or a conjugated polymer compound having luminescence and conductivity. 6. The polymer composition according to any one of 5 above. A polymer solution composition, wherein the polymer composition according to any one of claims 1 to 6 further contains a solvent. Between electrodes consisting of an anode and a cathode, a polymer light emitting device characterized by having a layer comprising a polymer composition according to any one of claims 1-6. The polymer light emitting device according to claim 8 , wherein the layer containing the polymer composition is a light emitting layer. A polymer light emitting device comprising a layer formed by using the polymer solution composition according to claim 7 between electrodes composed of an anode and a cathode. Polymer light-emitting device according to claim 1 0 layer formed using the polymer solution composition is a light emitting layer. The polymer light-emitting device according to any one of claims 8 to 11 , wherein the polymer light-emitting device is manufactured by heat treatment at a temperature of 50 ° C or higher when or after the layer containing the polymer composition is formed. An ion pair, wherein the anion is represented by the following formula (5-1), and the cation is a pyridinium cation, a phosphonium cation, or an iodonium cation.

An ion pair, wherein the anion is represented by the following 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.

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