TW201035283A - Organic electroluminescent element - Google Patents

Abstract

This invention provides an organic electroluminescent element which is obtained by forming a laminate of an anode, a luminescent layer and a cathode and processing the laminate by applying a voltage of 10v or higher in between the anode and the cathode to cause an electric current to flow from the anode to the cathode, wherein the luminescent layer contains an ion-pair and a polymeric luminescent member, the ion-pair containing a negative ion represented by formula (1a), formula (1b), formula (2) or formula (3), wherein Y1 represents an atom of 13 family, Ar1 represents aryl group etc., having an electron-absorbing group, Q1 represents an oxygen atom, X1 represents a halogen atom, a represents an intega of 1 to 3, K represents an intega of 1 to 4, V1 represents an atom of 16 family, b represents an intega of 2 to 6, Z1 represents -C ≡ N- etc. C represents an intega of 1 to 6.

Description

201035283 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an organic electric field light-emitting element. [Prior Art] [Background Art] An organic electroluminescent device using a high molecular weight luminescent material is different from an organic electroluminescent device using a low molecular weight luminescent material, and in order to form a luminescent layer of an organic electroluminescent device by a coating method, Conduct a variety of reviews. For example, an organic electric field light-emitting element having a light-emitting layer of a polyfluorene containing a total of a polymer compound (Advanced Materials Vol. 12 1737-1750 (2000)) is known. In order to extend the luminance half life of an organic electroluminescence device, an organic electroluminescence device having a light-emitting layer containing a polymer phosphor and an ion pair is known (International Publication No. 2004/99340). [Disclosure of the Invention] However, in the state where the luminance of the organic electroluminescence device described above is 100 when the driving is started, the lifetime until the luminance becomes 80 is not necessarily sufficient. An object of the present invention is to provide an organic electroluminescence device which has a long life until the luminance becomes 80 in a state where the luminance at the start of driving is 100. The present invention provides an organic electric field light-emitting element, which is formed by a laminate having the following steps: an anode comprising the formula (la), the formula (lb), the formula 4 321711 201035283 (2) or the formula (3) The ion pair of the anion and the light-emitting layer of the polymer light-emitting body and the cathode are electrically connected to the cathode by applying a voltage of 10 V or more between the anode and the cathode. Organic electric field light-emitting element. r (Q1-Ar1): Z1" - v1 into i X (3-a) L ^ > b (1a)

(lb) (wherein Y1 represents a group 13 atom, Ar1 represents an aryl group having an electron attracting group or a monovalent heterocyclic group having an electron attracting group, and Q1 represents an oxygen atom or a direct bond, and the X1 system Represents a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylsulfanyl group, a dilute group, a block group, and an aromatic group. Base group, aryl block group, substituted chopped oxy group, substituted sulphur group, substituted alkyl group, substituted amine group, aryl amine group, anthracene group, decyloxy group, monovalent heterocyclic group , heteroaryloxy, heteroarylthio, cyano or nitro, a represents an integer from 1 to 3, k represents an integer from 1 to 4, and V1 represents a group 16 atom, a divalent aliphatic hydrocarbon group, 2 Avalent aromatic fe group, 2-denty heterocyclic group, -〇ξΝ_, or direct bond, b represents an integer from 2 to 6, and Z1 represents -M'(=0)p- (wherein M' represents 3, 4, 5, 6, 6, 7, 8, 9, 10, 11, 12, 13, 14, and 15 , group 16 or group 17 atom, p system represents an integer from 0 to 2.), 5 3 21711 201035283 Or a b-valent aliphatic hydrocarbon group, a b-valent aromatic hydrocarbon group, a b-heterocyclic heterocyclic group, a phase, -N=N=N_, _., Qin, Qin or a direct bond.: Yes: at Z1 is - In the state of M, ( = 0) P-, -CeN-, -Mu, n or one H-, 13=2 41 is different from V1, in the state where Yl, Ql, Arl and ^ are plural These systems may be the same or different, and the plural a and V1 systems may be the same or different, and represent an integer from 1 to 6. (Ar2^2^^ X2 (2-d) 丫^(〇2-Αγ\· VX (2-d') e- (2) (wherein Υ2 represents a group 13 atom, and Ar2 represents an aryl group having an electron attracting group or an electron attracting group I-valent heterocyclic group, _ represents an oxygen atom or a direct bond, X2 is a halogen atom, a silk, an alkoxy group, a sulfur-containing group, an aryl group, a green group, a base group, a aryl group, an aryloxy group, an aryl group Sulfur-based, county, fast-group 'arylalkenyl' arylalkynyl, substituted alkaloxy, substituted Weithio, substituted, secreted, substituted amine, ruthenium, fluorenyl , a monovalent heterocyclic group, a heteroaryloxy group, a heteroarylthio group, a chaotic group or a nitro group, d and d, which is the same or different, represents 丨 or 2, and f represents a f 16 group material, a divalent aliphatic (tetra) aryl group, a divalent aromatic hydrocarbon group, a 2 dentate heterocyclic quinone (5), or a singular" Y2, Ai· 2. The Q2 and r systems can be the same 'may be different'. χ2 is a plurality of X2 states. The systems can be the same 'may be different, and the e system is an integer from 1 to 6.) 321711 6 201035283

Ar3-Q3- γ^Λ/^γ Χν3^ Q3-Ar3f (3) Ο 〇 (wherein, 3 is a group of a Group 3 atom, an aryl group of an fluorenyl group or an electron attracting group having an electron attracting group An atom or a direct bond, indicating a group 16 atom: a dibasic system representing a valence aromatic atom group, a 2-dentyl heterocyclic group, a hepta group, Y, Ar3, Q3, and v3 俜 barium-Γ | ^ The integer river of 6 is the same 'may be different, f is represented by :::: provides an organic electric field light-emitting element == sub-luminescence Zhao and ion pair light-emitting layer, :=): formula (10), formula (2) or (3) The subroutine is obtained by energizing the anode to the galvanic current by the electric current of '= νν or more between the anode and the hum. Electric field illuminating element. [Embodiment] [Embodiment of the Invention] Hereinafter, the present invention will be described in detail. The organic electric field light-emitting element of the present invention has:

An ion pair of an anion represented by Ua), (lb), formula (2) or (3) and a light-emitting layer of a high molecular illuminant. The Y1 of the formula (la) and the formula (lb) represents a Group 13 atom, preferably a boron atom, an aluminum atom, a gallium atom, and more preferably a boron atom. 321711 7 201035283 The Ar1 of the formula (1) and the formula (lb) represents an aryl group having an electron attracting group or a monovalent heterocyclic group having an electron attracting group. The electron-attracting group is an atom or a group of atoms which adsorbs electrons by a resonance effect or an excitation effect, and examples thereof include a halogen atom, a stone-based group, a sub-wall group, a cyano group, a aryl group, a carboxy group, and an alkoxy group. A group, an aryloxycarbonyl group, an arylalkoxycarbonyl group, a heteroaryloxycarbonyl group, a perfluoroalkyl group or the like. The electron-attracting group is exemplified by a fluorine atom, a gas atom, a bromine atom or a ruthenium atom, and a fluorine atom. The carbon number of the fluorenyl group is usually from 2 to 20, and as an example thereof, it is a series of ethyl fluorenyl, propyl fluorenyl, butyl fluorenyl, isobutyl fluorenyl, trimethyl acetyl sulfonyl, benzhydryl, trifluoroethenyl, pentafluorobenzene.醯基等. The alkoxycarbonyl group has a carbon number of usually from 2 to 20, and examples thereof include an oxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, and an isobutoxycarbonyl group. , a second butoxycarbonyl group, a third butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a cyclohexyloxycarbonyl group, a heptoxy group, an octyloxy group, a 2-ethylhexyloxy group Alkyl, anthracenyloxy, decyloxycarbonyl, 3,7-dimethyloctyloxycarbonyl, dodecyloxycarbonyl, trifluoromethoxyphenyl, pentafluoroethoxy group, all A fluorobutoxy group, a perfluorohexyloxycarbonyl group, a perfluorooctyloxycarbonyl group or the like. The aryloxycarbonyl group has a carbon number of usually about 7 to 60, and as an example thereof, a phenoxycarbonyl group or a fluorene to C12 alkoxyphenoxycarbonyl group ((^ to C12 represents a carbon number of 1 to 12. The same applies hereinafter). Octa to C12 alkylphenoxycarbonyl, 1-naphthyloxycarbonyl, 2-naphthyloxycarbonyl, pentafluorophenoxycarbonyl, etc. The arylalkoxycarbonyl group usually has a carbon number of about 8 to 60. As an example thereof, 8321711 201035283 h subunits are exemplified by phenyl-fluorene to C12 alkoxycarbonyl, (:! to C12 alkoxyphenyl-C! to C12 alkoxycarbonyl, oxime to C12 alkylphenyl- 0 to c12 alkoxycarbonyl, 1-naphthyl-(^ to C12 alkoxycarbonyl, 2-naphthyl-Ci to c12 alkoxycarbonyl- and the like. Heteroaryloxycarbonyl (by Q4-0 (C) = 0) - the group shown; Q4 represents a monovalent heterocyclic group.) The carbon number is usually from about 2 to about 60, and as an example thereof, a thienyloxycarbonyl group, a fluorene to a C12 alkylthiophenyloxycarbonyl group, or a C Oxycarbonyl, 吱α南oxydyl, ° σ oxy group, Cl to Cl 2 alkyl 0 σ oxy group, quinazolyloxycarbonyl, pyrazolyloxycarbonyl, triazole oxygen Carbocarbonyl, oxazoloxycarbonyl, thiazole oxygen A carbonyl group, a thiadiazolyloxycarbonyl group, etc. The monovalent heterocyclic group is preferably a monovalent aromatic heterocyclic group. The perfluoroalkyl group means a straight chain, a branched alkyl group or a cycloalkyl group. The atom is a group substituted by a fluorine atom, and the carbon number is usually about 1 to 20, and as an example thereof, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a hepta-isopropyl group, a perfluorobutyl group, Nonafluoro-isobutyl, 1,1-bis-trifluoromethyl-2, 2, 2-trifluoroethyl, perfluoropentyl, perfluorohexyl, perfluorocyclohexyl, perfluoroheptyl, perfluoro An aryl group having an electron-attracting group and an electron-attracting group represented by Ar1 represented by the formula (1) and the formula (lb), and an aryl group, a perfluoroindenyl group, a perfluoroindolyl group, a perfluorolauric group, and the like. The aryl group having an electron attracting group is usually about 6 to 60 carbon atoms, and as an example thereof, the phenyl group and the C! to C12 alkoxy group are substituted by the above electron attracting group. a group of one or more hydrogen atoms contained in a phenyl group, a C! to C12 alkylphenyl group, a naphthyl group, a 2-naphthyl group or the like. The monovalent heterocyclic group having an electron attracting group has a carbon number of usually -2 To 6 0 9 321711 201035283 or so, as a specific example thereof, the electron attracting group is replaced by the above-mentioned electron-attracting group, the Cii C12-based phenyl group, the π-pyrrolyl group, the fluorene group, and the bite group. C! to C, a 2-alkyl pyridyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a carbazolyl group, a sessile wire, a ruthenium wire, or the like, which is one or more hydrogen atoms. The ring-based system is preferably an anthracene aromatic heterocyclic group. The following is a group of the following (^ to ^) in the Ar1 series. In the formula (la) and the formula (ib), Ar! is in a plurality of states, and these systems are Can be the same or different. (I) An aryl group having an electron attracting group: ~^3~ci ~^3~Br ~~^3~n〇2 ,1 N〇2 CN c -6 ^i 17

NC

Cl ct

Br Br

N02 A

CN

Co2h

N〇2 CN co2h ~0~0~n〇2 -〇-〇-cn -〇-^co2h-q>Br -q> (11) Monovalent heterocyclic group having an electron attracting group: 10 321711 201035283 - ^3"°* ~丨^^-n〇2 ~^=3~cc^h -〇~& -O^1 ~0~指~1=^ -C^° -〇-' -〇kc〇 Zh

-^•<3 —^-Br -^r~N〇2-^-CN —^«CQzH -^-° ~^ό~& ~^}~l -^jr^-^jr-^ - ^)-°0^ o

Me Me Me Me Me-{y° -{y^ -^V1 -<ycN Me Me Me Me Me Me

Me Me Me Me Me -^ya -^_>-i -Qmn^-^^cn -^^-c〇2 Me, Me Me, Me Me Me, Me Yan Me Me ^y·' -^- N〇2-〇-cn

H H H (III) aryl group having a fluorine atom or a trifluoromethyl group as an electron attracting group: -〇~F heart % -〇F J i %

F CFS Cl Br I CF3 N〇2 -0-0-0 ^ -0 -0 F CF3 F F F F F

11 321711 201035283 valence heterocycle Ον) has a ruthenium atom or a trifluoromethyl group as the base of the electron attracting group:

Ν-Ν 廿F order->

Me〆, Me

Me -\〇 Ap

Me I M〆, Me

Me (V) perfluoroaryl: Examples of perfluoroaryl groups such as pentafluorophenyl, heptafluoro-naphthyl, heptafluoro-2-naphthyl, nonafluoro-1-biphenyl 'nonafluorobiphenyl Base, nonafluoro-1~fluorenyl, nonafluoro-2-indenyl, nonafluoro-9-fluorenyl. The aryl group having an electron attracting group and the monovalent heterocyclic group having an electron attracting group are preferably an aryl group having a fluorine atom or a trifluoromethyl group, and a fluorene hetero ring having a fluorine atom or a trifluoromethyl group. More preferably, the perfluoroaryl group (formula (m), (IV) and (V)) is a perfluoroaryl group (formula (ν)). Q1 of the formula (la) and the formula (lb) represents an oxygen atom or a direct bond. In the case where Ql is plural, the systems may be the same or different. X is a dentate atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an ene 321711 12 201035283 u · Alkyl, alkynyl, arylalkenyl, arylalkynyl, substituted decyloxy, substituted decylthio, substituted decylamino, substituted amine, decylamino, quinone, methoxy, 1 A heterocyclic group, a heteroaryloxy group, a heteroarylthio group, a cyano group or a nitro group. - The halogen atom of X1 is exemplified by a fluorine atom, a chlorine atom, a bromine atom, or an argon atom. The alkyl group may be either a straight chain or a branched chain, or may be a cycloalkyl group. The alkyl group may have a substituent, and the carbon number is usually from about 1 to about 20, and examples thereof include a mercapto group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutylene group, a second butyl group, and a Tributyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, decyl, decyl, 3,7-dimethyloctyl, lauryl, trifluoromethyl, pentafluoro Ethyl, perfluorobutyl, perfluorohexyl, perfluorooctyl and the like. The alkoxy group may be either a straight chain or a branched chain, or may be a cycloalkoxy group. The alkoxy group may have a substituent, and the carbon number is usually from about 1 to about 20, and as an example thereof, an oxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, an isobutoxy group. , a second butoxy group, a third butoxy group, a pentyloxy group, a hexyloxy group, a cyclohexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a decyloxy group, a decyloxy group, 3,7-Dimethyloctyloxy, dodecyloxy, trifluoromethoxy, pentafluoroethoxy, perfluorobutoxy, perfluorohexyl, perfluorooctyl, decyloxyoxy , 2-methoxyethoxy, and the like. The alkylthio group may be either a straight chain or a branched chain, or may be a cycloalkylthio group. The alkylthio group may have a substituent, and the carbon number is usually from about 1 to about 20, and as an example thereof, a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, Second butylthio, tert-butylthio, pentane 13 321711 201035283 thio, hexylthio, cyclohexylthio, heptylthio, octylthio, 2-ethylhexylthio, sulfonylthio, sulfonium sulfide A '3,7-dimethyloctylthio group, a thiol group, a trifluoromethylthio group, and the like. The aryl group may have a substituent, and the carbon number is usually about 6 to 6 Å, as an example thereof (4), the Gl to Cl2 filament group, [to (5) alkylphenyl group, 1-naphthyl group, 2-naphthyl group, etc. . The aryloxy group may have a substituent on the aromatic ring, and the number of hindrance is usually from about 6 to 60, and as an example thereof, a phenoxy group or a fluorene group is given. Alkoxyphenoxy' d C12 alkylphenoxy, bnaphthyloxy, 2-naphthyloxy, pentafluorophenoxy, and the like. The arylthio group may have a substituent on the aromatic ring, and the carbon number is usually from about 6 to 60, and examples thereof include a phenylthio group. To G2 alkoxyphenylthio, (^ to C1Z alkyl thiol, naphthylthio, 2-naphthylthio, pentafluorophenylthio, etc. The aralkyl group may have a substituent, and the carbon number is usually 7 to 6 ,, as a series of examples, phenyl-(^ to Cn alkyl, (:! to C12 alkoxyphenyl seven to Cu alkyl, (^ to C! 2 alkyl styl-Ce C12) An alkyl group, a naphthyl-G to C! 2 alkyl group, a 2-naphthyl-anthracene group to a C12 alkyl group, etc. The aryl alkoxy group may have a substituent, and the carbon number is usually about 7 to 6 Å as an example thereof. a series of phenyl-Ci to Ci2 alkoxy, hydrazine to Ci2 alkoxyphenyl-Gi Cu alkoxy, hydrazine to C12 alkylphenyl-fluorene to 匕2 alkoxy, 1-naphthyl-d C !2 alkoxy group, 2-naphthyl-anthracene to C12 alkoxy group, etc. The aryl group thio group may have a substituent, and the carbon number is usually from about 7 to 60. ' As a series of examples, phenyl _Cl is used. Cl2 alkylthio, hydrazine to Ci2 alkoxy 14 321711 201035283 phenyl phenyl- to Cu alkylthio, (^ to clz alkylphenyl-(^ to C12 alkylthio, bnaphthyl-(:! to Ck alkane) a base, a 2-naphthyl group to a Cl2 alkylthio group, etc. The alkenyl group usually has a carbon number of from 2 to 20, as an example thereof. Examples of vinyl, 1-propenyl, 2-propenyl, 3-propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, cyclohexenyl. Alkenyl also contains hydrazine, a hydrocarbon dienyl group such as a butadienyl group. The 丞 咴 丞 书 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 a pentynyl group, a hexynyl group, a heptynyl group, an octyl group, a cyclohexyl group. The silk also contains a hydrocarbon dienyl group such as an anthracene or a 3-dibutyl group. The aryl group has a carbon number of usually 8 to 5G or so, the meaning of the aryl (tetra)yl-f-alkenyl group, examples are the same as the above examples of the aryl group, the rare group. As an example of the arylalkenyl group, the aryl group, 2 ^ ethyl group, 1 - aryl + propyl, 2 aryl + propenyl, 2 aryl f 2: propenyl, 3' aryl I propyl, etc. The arylalkenyl system also contains 4. An aryl hydrocarbon dienyl group such as a butadienyl group. The base number is usually from about 8 to 50, and the aryl alkyne (tetra) and the two L examples are the same as the above-mentioned aryl group, alkynyl group + propyl group. Listed as an aryl b-block, a 3-aryl-1, a heart; an alkynyl group also an aryl group -=:=:=, aryl, one original one-one. In addition, 3211715 201035283::=:r has a substituent. As a monovalent heterocyclic group, it is preferable to replace the carbon-oxyl group with a carbon number of usually i. Up to 60, preferably carbon number 3 to 30-' as a series of examples thereof, trimethylweiloxy' triethyl oxalate alkoxyl tri-n-propyl decyloxy, tri-isopropyl decyloxy Base, tert-butyl-fluorenyloxy, triphenylpropoxy, tri-p-xylylene, oxyalkyloxy, dibenzylmethylalkoxy, diphenylmethyldecyloxy, third A benzylideneoxyalkyloxy group, a dinonylphenyl decyloxy group, or the like. Soil as a substituted decanethio group, a group consisting of an alkyl group, an aryl group, an aralkyl group and a heterocyclic group of a working group, selected from 2 or 3 groups to replace the decylthio group of the chlorine atom (HAiS- ). The alkyl group, aryl group, aralkyl group or oxime & heterocyclic group may have a substituent. The substituted decanethio group has a carbon number of usually about 1 to 6 Torr, preferably 3 to 30 carbon atoms, and as an example thereof, a trimethyl decyl thio group, a triethyl decyl thio group, and a tri-n-propyl decane. Sulfur, tri-isopropyldecanethio, tert-butyldimethylsulfanylthio, triphenyldecanethio, tris-p-dimethylphenylsulfanyl, tribenzylsulfonylthio, diphenyl The base is a decylthio group, a tributyl sulfonylthio group, a dimethylphenyldecanethio group or the like. The earth as a substituted decylamine series, one to six groups selected from the group consisting of an alkyl group, an aryl group, an aryl group and an i-valent heterocyclic group to substitute a nitrogen atom of a decylamine group (HdiNH- or (H3Si) 2N-). The alkyl group, the aryl group, the aryl group, and the monovalent heterocyclic group may have a substituent. The substituted decylamine group has a carbon number of usually about 1 to 120, preferably a carbon number of 3 to 60, and as an example thereof, a trimethyldecylamine group, a tricynene 321711 16 201035283, a hospital base, a second N-propyl sulphate, tris-isopropyl sulphonate, 1,4-butyl decyl decylamino, triphenyl decylamino, tri-p-quinone hydrazide alkylamine, three Benzyl decylamino, diphenyldecyl decylamino, tert-butyldiphenyl decylamino, dimethyl decylamino, bis(trimethyldecyl)amine, bis(triethyl) Alkylalkyl)amino, bis(tri-n-propyldecyl)amino, mono(di-isopropylmethyl)amino, bis(t-butyldimethyloxalinyl)amine , bis(triphenyldecyl)amino, bis(tri-p-xylylphthalenyl)amine, bis(tris-decylalkyl)amine, bis(diphenylmethyldecanedecyl)amine, A bis(t-butyldiphenylphosphonyl)amino group, a bis(didecylphenylphosphanyl)amino group or the like. As the substituted amine group, one or two groups selected from the group consisting of an alkyl group, an aryl group, an aralkyl group and an anthracene ring group are substituted for the amine group of the hydrogen atom. Further, the alkyl group, the aryl group, the aralkyl group or the anthracene heterocyclic group may have a substituent. The substituted amine group carbon number is usually from about 〇 to about 4 ,, and as an example thereof, a methylamine group, a diammonium group, an ethylamine group, a diethylamino group, a propylamine Q group, a dipropylamine group, an isopropylamine group, and a second Isopropylamine, butylamino, isobutylamino, second butylamino, tert-butylamino, pentylamino, hexylamino, cyclohexylamino, heptylamino, octylamino, 2-ethyl Hexylamino, decylamino, decylamino, 3,7-dimethyloctylamino, dodecylamino, cyclopentylamino, dicyclopentylamino, dicyclohexylamine, pyrrolidinyl, Piperidinyl, bistrifluoroamylamine, anilino, diphenylamine, (^ to Cu alkoxyanilide, bis(匕 to C12 alkoxyphenyl)amine, bis (Ci to Ci2 alkylbenzene) Amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidinylamino group, oxime amino group, triple call Amino group, phenyl-Cl to Cl2 amphoteric group, 匕321711 17 201035283 to Cl2 methoxy phenyl _Cl to Cl2 amphoteric group, Cl to Cl2 basic group-Cl to Cl2 acryl group, two (Cl To Cl2 alkoxyphenyl-Cl to Cl2 alkyl) amine, two (Cl to Cl2 burn phenyl-Cl to Cl2 alkyl) amine group, 1-caiyl-Cl to oxime 12 amine group, 2-naphthyl-Cl to Cl2 arunyl group, etc. The guanamine group carbon number is usually about 2 to 20 As a series of examples, it consists of amidoxime, acetamido, acrylamide, butylammonium, alum, amine, trifluoroacetamido, pentafluorobenzamide, diterpenes Amine, diethylamine, dipropylamine, dibutylammonium, benzoylamino, bistrifluoroacetamido, bispentafluorobenzamide, etc. > The imine series is a residue obtained by removing a nitrogen-hydrogen atom from a quinone imine. The carbon number of the quinone imine group is usually 2, and _ ' ^ is preferably as an example of a _ group.

321711 18 201035283 The carbon number of the oxime group is usually from 2 to 20, and as an example thereof, it is an ethoxy group, a propenyloxy group, a butoxy group, an isobutyloxy group, a trimethylacetoxy group. , benzhydryloxy, trifluoroacetoxy, pentafluorobenzyloxy, and the like. The monovalent heterocyclic group refers to an atomic group remaining by removing a hydrogen atom from a heterocyclic compound, and the carbon number is usually about 2 to 6 Å, and as an example thereof, a thienyl group, (^ to C, 2 alkylthiophene) a pyridyl group, a pyrenyl group, a pyridyl group, a fluorenyl group to a L alkyl pyridyl group, an imidazolyl group, a carbazolyl group, a triazolyl group, a carbazolyl group, a snail H group, etc. Aromatic heterocyclic group, a heteroaryloxy group (the group represented by Q5-0-; q5 means a monovalent heterocyclic group), and the pain carbon number is usually about 2 to 6 G, and as an example thereof, it is a listening group. , c to Cl2, thiophene oxy, quaternary oxy, t-N-oxyl, oxime oxy, c to C12, ketone, tetra(oxy), benzyl, (tetra)oxy, ^ dioxo: hetero; Oxyl group, first class, etc. as a monovalent heteroarylthio group (represented by Q6-S-. q6 to 矣 _ number is usually 2 篆βη 士 士 杂环 heterocyclic group). Carbon to C m \ ' as an example The series Q is preferably a monovalent formula (la), which is a monovalent formula (la), which is a monovalent formula (la). The Z system indicates ( = ^ ? family, 4th, 5th, 6 family ^, M' series means the 3rd brother 7 know, 8th, 9th, 321711 19 201035283 10th, 11th, 12th, 13th. Family, 16th or 17th Atom, p is shown in Table 8, Group 14, 15 or an integer representing a b-valent aliphatic nicotine dioxime to 2), a succinct, a thiol group, a b-heterocyclic group, and a -M at z1. ( = 0) p_, _CsN~H or direct key. However, in the state of the meal, b = 2 "(4)-,,,-,.- or the system has a positive charge alone, but the province is -and-oh -

Commun., 1999, 1533) ^. I have already loaded it. (Refer to Chem. No, Group 5, Section 矣, Section 3 of the 3rd, 4th (9), (4), (4), 14th);: Atomic, Family or Group 17 Collapse atom, carbon atom group, 16th atom, fluorine atom, atom, stone atom, phosphorus atom: ❹Nitrogen: oxo atom, titanium atom, 鈒原_, now', sub., 虱 atom , child, nickel atom, copper atom, zinc atom:: child, record, desert atom, helium atom, wrong atom, pin atom wrong,:, Shixiyuan crane atom, _ son, etc., preferably atomic quantum to atom In the case of removing the oxygen, the third group, the seventh group, the 坌s, "不天弟13方矢, the sixth group, the 13th family, the second first 〇, the U, the twelfth, the 14 No, 15th, 16th or 17th, for example, can be ρ==14Μ, in the state of the atom of the child, can be ρ=2. 'The seventh group of the domain as the ρ~ One of the states of 2, (==〇)ρ_ The example of the soil is _Ti (yu, ϋ) _, seven b d 321711 20 201035283 0) 2-, -zr (= = 0) _, _Mo ( =0)) Waiting for the hb price of the ship-country county silk (four) (four) frequency to the atomic 囷, can be Any = hydrogen, branched or cyclic substituent having a group of the original. The carbon number of the b-valent wax-based aliphatic base is usually;; U is an integer of 6 months, but the 5 series does not exceed the hydrogen number of the aliphatic hydrocarbon. Ding Xuan '2, 2 - 2 2 ^:: Wu Xuan, Hyun, " methyl propane, hexane, cyclohexane, heptane, octane, 2_ base pit, smelting, simmering, 3, 7_Dimethyl octane and the like. Examples of the divalent aliphatic hydrocarbon group (the state of b = 2) include methylene chloride, alkenyl group, propenyl group, trimethylene group, tetramethylene group, pentamethylene group, and 13-cyclopentadienyl group.丨, 4_cyclohexadienyl and the like. Examples of the aliphatic cigarette base (b is a state of 3 or more and 6 or less) are as follows. 321711 21 201035283

.c'h CH,

CH-C|^

H2

plVH3 义 Ά 、, TT XX X

/C'^ChAH-'CH 乂1H, i I h2

/CH2 "^Η2 Z b-valent aromatic (four) base table * b atomic group of helium atom, can have a substituent on the non-m 4 square to remove the P ring, the carbon number is 6 to 6 Hey around.氢 The number of hydrogens on the ring. The aromaticity of the aromatic hydrocarbon is not more than 1 to 12, as the aryl-form, and the (10)-oxybenzene (1) 2 is not a carbon number of 1 to 12. In the following, the same is true. ), burnt benzene, naphthalene, onion, phenanthrene, Ding province, pu province, etc. The ^2 f-valent aromatic hydrocarbon group (the state of b == 2) means an atomic oxime in which two hydrogen atoms are removed by an aromatic hydrocarbon, and the carbon number is usually 6 to 60, preferably 6 to 20, as an example thereof. A series of extended phenyl groups (such as formulas 1 to 3 in the following figure), fluorenyl groups (forms 4 to 13 of the lower ring), thiol groups (formulas 14 to 19 in the following figure), and extensions 321711 22 201035283 * biphenyl (Formula 20 to 25 in the following figure), triphenylene (formulas 26 to 28 in the following figures), fused ring compound groups (formulas 29 to 38 in the following figures) and the like. The carbon number of the divalent aromatic hydrocarbon group does not include the carbon number of the substituent R' ''.

23 321711 201035283

R"' Rm

Ru‘ R.« Rrn R-

24 321711 201035283 Ο

R- R,

R··· r^CTr-rm,

32

Rm R'" Rw Ru, 33 R,, 3l R- rm, R".

Ο alkyl, alkoxy, thiol, aryl, aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio, alkenyl, alkynyl, aryl dilute, Arylalkynyl, substituted nonyloxy, substituted nonylthio 'substituted decylamino, 321711 25 201035283 substituted amine, decyl, quinone, decyl, monovalent heterocyclic, heteroaryloxy The definitions, examples, and the like of the heteroarylthio group are the same as those of the above X1, definitions, examples, and the like. The definitions, examples, and the like of the halogen atom, the alkoxycarbonyl group, the aryloxycarbonyl group, the arylalkoxycarbonyl group, and the heteroaryloxycarbonyl group are the same as those in the above electron attracting group. The term "imine residue" is derived from an imine compound (refers to an organic compound having -N = C- in the molecule. As an example thereof, a series of hydrogen atoms on N, such as an imine, a ketimine, and the like A compound substituted with an alkyl group or the like.) A residue of one hydrogen atom is removed. The imine residue is usually from about 2 to about 60 carbon atoms, preferably from 2 to 20 carbon atoms. Specific examples of the imine residue include the basis of the following structural formula.

(In the formula, the wavy line is not bonded.) The substituted chopping group means a decyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, a aryl group and a monovalent heterocyclic group. The substituted alkylene group is usually a carbon number of from 1 to 60, preferably from 3 to 30 carbon atoms. The alkyl group, the aromatic 26 321711 201035283 group, the aralkyl group or the monovalent heterocyclic group may have a substituent. The alkyl group is a trimethyl decyl group, a triethyl decyl group, a tri-n-n-substituted fluorenyl group, a tri-isopropyl decyl group, a tert-butyl decyl decyl decyl decane phenyl decane. A group, a tri-p-nonylphenyl fluorenyl group, a tribenzyl fluorenyl group, a triyl fluorenyl group, a tert-butyl diphenyl sulphate group, a smectite group, a diphenyl group, and the like. Methylphenyl decane The residue of (b-2) R,, in the example of the aromatic ❹ 〇 _ ̄ & _ _ (tetra) divalent aromatic hydrocarbon group in the state where b is from 3 to 6. The main Qiu) is further removed. The heterocyclic group of the Z-dental ring refers to the group of the heterocyclic compound and the σ D moiety. As a series of binding sites: a site having b adjacent atoms bonded by a 4 bond and a site (coordination bonding moiety only) u site) is bonded by a coordinate bond as a b-heterocyclic heterocyclic group having a heterocyclic ring Go to - the atom, the atomic group with only the teeth. At least 1 substitution: as:::! Usually 2...right, joint (1) Jiazai:=(state of b=2) series with 2 covalent knot lengths I), and with 1 covalent knot The position-binding site (1) and the following series are as follows. Examples of the divalent heterocyclic group include a divalent heterocyclic group containing a nitrogen as a hetero atom; formulas 39 to 44) and a group (the following figure) Base (the following formula 49^ extends phenyl (formula 45 to 4δ in the figure below), 喧琳二十定二基 (pictured below, ?, Shiwulin two bases (the following figure & to (8), Formula 69 to 72), bipyridyldiyl group (Formula 73 321711 27 201035283 to 75 = phenanthrene-based dibasic group (Formula 76 in the following figure contains a ruthenium, a base as a hetero atom system (Formula 79 below) For the purpose of deuterium, sulfur, selenium, etc., it is preferable to have an aromatic atom containing a nitrogen atom I's a triphenyl t group or the like from the aspect of luminous efficiency. Examples of the hetero atomic dream, nitrogen, oxygen, sulfur, code, and the like are as follows: (Formula 94 to 98 in the following figure). The clothing coat contains as a hetero atom, a nitrogen, a miscellaneous 瑷, a 丨 丨 丨, a melon 5 members of the ring, such as 砸 稠: base: enumeration (The following formula 99 to _, benzothiazide, 7-yl or benzo-pyridazol _4, 7-diyl, etc. s contains as a hetero atom, Shi Xi, nitrogen, oxygen, sulfur, antimony The group which is a 5-membered ring heteropoly group and which is bonded to the α-position of the hetero atom to form a dimer or an oligomer is exemplified by the formula (110 to 111 in the following figure). Examples of the 5-membered ring heteropoly group of oxygen, sulfur, selenium, etc., and the phenyl group at the α-position of the hetero atom thereof are as follows: (Formulas 112 to 118 in the following figure).

321711 28 201035283

29 321711 201035283

30 321711 201035283

31 321711 201035283

(wherein Me is a fluorenyl group.) R is the same or different and represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, Arylalkoxy, arylalkylthio, alkenyl, alkynyl, arylalkenyl, arylalkynyl, substituted nonyloxy, substituted nonylthio, substituted nonylamino, substituted amine, amidino , fluorenylene, decyloxy, monovalent heterocyclic, heteroaryloxy, heteroarylthio, fluorenyl, imine residue, substituted alkylene, alkoxycarbonyl, aryloxycarbonyl, aryl Alkoxycarbonyl, heteroaryloxycarbonyl, carboxyl, cyano or nitro. Affiliation, alkoxy, thiol, aryl, aryloxy, arylthio, arylalkyl, aryl alkoxy, arylsulfanyl, dilute, alkynyl, aryl, aryl a radical group, a substituted calcined oxy group, a substituted calcined thio group, a substituted calcined amine group, a substituted amine group, a decylamino group, a quinone imine group, a decyloxy group, a monovalent heterocyclic group, a heteroaryloxy group, The definitions, examples, and the like of the heteroarylthio group are the same as those in the above X1, definitions, examples, and the like. The definitions, examples, etc. of a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryl alkoxycarbonyl group, a heteroaryloxycarbonyl group are the same as those of the aforementioned electron attraction 32 321 711 201035283. . The definitions, examples, and the like of the imine residue and the substituted alkylene group are the same as those of the above-mentioned seven, such as definitions, examples, and the like. Examples of the monovalent 2-dentate heterocyclic group include a group in which one of the above-mentioned 39 to 118 exemplified divalent heterocyclic groups is bonded with r, and a group having a coordinate bond at a hetero atom, the following group, or the like.

R i R R R rVvr N,rVR / \ /,, /N-N, Jn-N R

As a heterocyclic group in the state where b is 3 to 6 (having b)

The St moiety is a residue of (b-2) fluorene atoms removed by the example of the divalent heterocyclic group shown above.严-ίϋ V # denotes the 16th atom, the 2nd month of the aliphatic group, ^ =, 2 teeth heterocyclic group, -. ·,,, There are several V1 systems that can be the same, and the same is not the same. It’s different from the other. Z1 and V1 are exemplified as the 16th atomic group of V1, and the oxygen atom and the halogen atom are preferably an oxygen atom or a sulfur atom. ^,, Shi Xiyuan's definition, examples are the same as the aforementioned π. The definitions and examples of the scented fragrant domain are the same as those of the above-mentioned Z, 321711 33 201035283. The definition and examples of the 2-toothed heterocyclic group of Shanghai are the same as the above 2>. s is an integer of 3 or more and 3 or less in the formula (1U, a is a table *), preferably 疋 2 or 3 ' a is preferably 3. The plural a system may be the same or different. 'k is an integer of 丨 or more and 4 or less. From the viewpoint of long life when used in an organic electric field light-emitting element, k is preferably 3 or more, and more preferably k is 4. a), b is 2 or more, "乂下^ integer. However, in the state of -C = NN = N==N- or direct bond, b is 2. In the formula (la), c is expressed above 丨An integer of 6 or less. An example of the anion represented by the formula (5) is an anion represented by the following v VII. 321711 34 201035283 (Ar1). (χΛ<2: (Ar1). (Χ)3-β ( Ar1)«

%!>SS:>gWj 2· ^>-Λ-γ^ι·(Ar\XX,1)| (X)3·, ,Wh 2- o (Ar1)as W/(Ar1), LP〇3·,丫Y,(X)3·(Ar1)e 2- ^(Ar1)al 2· (Ar )a, Y_〇_必.OC (Χ)^γ Λ (--Y-( Ar1), -(Ar1)av Y,(Ar\- 闪3·'^ PN,"(A<\ N〇l (Ari)a -^Y v^a

4- (VI) (In the formula, Ar1 and a are the same as those described above. Ο Same as X. Y is the same as γ1.: (Ar1)a 夕|二才目

(XW (Ar1)a, Y, P〇3·〆 (where Ar1, a

I N-Y<(Ar’)” (ΑιΊγ υ/(Αγ\ί2- you〆' y/, P^a Pd Ν'

The V and a systems are the same as those described above. The χ system shows the phase 35 321711 201035283 is the same as the meaning of X1. The Y system represents the same meaning as γΐ. In the anions of the formula (VI) and the formula (VII), a substituent may be contained in the aromatic tobacco product, the heterocyclic ring or the hydrocarbon chain. Even if it is an anion represented by the formula (la), it is preferable that AjJ is a perfluoroaryl group from the viewpoint of the long life of the organic electroluminescent device, and it is more preferable that a is 2 or 3. State. The anion represented by the formula (la) is more preferably in the state of zl or shovel. Specifically, an anion represented by the formula VII is exemplified. More preferably, it is an anion system of the formula (la) or an anion of the formula. [(CeF5&gt;3B-CsN-B(C6F5)3 j (5-1) |M 十 CEN-B(C6F5)3y 2- (5-2) (wherein the lanthanide represents a nickel atom or a palladium atom.) Even in the case of the anion represented by the formula (lb), from the viewpoint of the long life of the organic electroluminescent device, it is preferable that A〆 is a state of all-air aryl, and more desirably, Ar1 is a perfluoroaryl group. In the case of the anion of the formula (lb), it is preferable that the state of the butterfly atom is 'the state of the butterfly atom', which is more desirable from the viewpoint of the long life of the organic electric field hairpin. The state of the anion represented by the formula (lb-ι). (ArV+x)4-k (1b-1) (wherein Ar, X and k are the same as those described above.) More desirable is the formula ( The anion state of 321711 36 201035283 represented by the anionic formula (lb_2) shown in lb-1). [B(Ar4)4]·(lb-2) (wherein Ar4 is represented by a fluorine group and a trifluoroantimony The phenyl group of the hydrogen atom is replaced by two or more substituents selected from the group consisting of a group. The plurality of Ar4 systems present may be the same or different.) In the formula (lb-2), 'the plural exists. The Ar4 system is best all With the anion. Examples of the anion series cited formula (12), formula (13), and preferably to the formula (12) shown in the anion.

The other preferred form of the anion represented by the formula (lb-1) is an anion represented by the formula (lb-3). (eighty seventy) four batches (11 &gt; 3) (wherein X represents the same meaning as described above. Arle represents a perfluoroaryl group, and kc represents an integer of 3 or 4.) The examples of the anions shown are the following anions. 37 321711 201035283

(In the formula, 'Me means a methyl group.) The ion used in the present invention is represented by the formula (2) or the formula (3).

The anion is an anion system of the formula (la), the formula (lb), wherein the formula (2)

(Ar^2)d>2^/^丫2((〇2 is xVd)〆, x2(2_d_) (2) (wherein Y2 represents a group 13 atom, and Ar2 represents an electron attracting group) An aryl group or a fluorenyl group having an electron attracting group, f is an oxygen atom, a direct bond, X2 wire is a 4-atom atom, a wire, an alkoxy group, a sulfur-burning group, a base group, a pure group, and a material H wire. , silk alkoxy, aryl sulphur-based, county, silk, silk county, silk, substituted oxy, substituted Wei thio, substituted residue, substituted silk, amide, sulfhydryl, oxime a heterocyclic group, a heteroaryloxy group, a heteroarylthio group, a cyano group or a deterministic group 'd and d, which are the same or different, or a 21 series, which means a group 16 or a divalent aliphatic hydrocarbon group. , a divalent aromatic hydrocarbon group, a 2-dental heterocyclic group, a -C or N-, a plurality of γ2, red 2, q2&amp; v2 are respectively the same 'may be different, and X2 is a plural existence state Hereinafter, the systems may be the same or different, and the e system represents an integer from 1 to 6.) 321711 38 201035283 The example of the 13th atom of Y is the same as the example of the 13th atom of the above γ1, and the electron of Ar2 Attractive basis The definitions, examples, and the like of the aryl group and the monovalent heterocyclic group having an electron-withdrawing group are the same as those described above, and the halogen atom, the alkyl group, the alkoxy group, the thiol group, the aryl group, the aryl group; , aryl f-based, aryl-based, aryl-alkoxy, aryl-thiol, dilute, • block, arylalkenyl, arylalkynyl, substituted oxalate alkoxy, substituted Shi Xiyuan sulfur Definitions, examples, etc. of the group, the substituted anthracene amine group, the substituted amine group, the decylamino group, the aryl iodide group, the aryloxy group, the monovalent heterocyclic group, the heteroaryloxy group and the heteroarylthio group With respect to the above-mentioned χ1, the definition, examples, etc. of the group ia atom of v2, the divalent valence hydrocarbon of the divalent month, the divalent heterocyclic hydrocarbon group, and the two-heterocyclic heterocyclic group are the same as those of the above-mentioned V1. An example of an anion which is not represented by the formula (2) is a 2-inch represented by the formula V(1).

(Q?-Ar1)d $,(Q1-a~ to 1)2-d〆, (long 1)2-min

2- (wherein, Ar1, X1, Y1, q2, d, d are the same as described above. 321711 39 1

2-cT 201035283 Righteousness. The anion in the formula (nil) may have a substituent on the chain. It is preferable that the square ring, the heterocyclic ring or the hydrocarbon is in the form of an organic electric field (four) element state, and more preferably, the Ar2 is all 7^r, even if it is based on the long life of the anion shown in the formula (2). In the form of a perfluoroaryl group, the ion = d in the present invention is in a state of 2. Expressed by formula (2) or formula (3). Subsystem (5), formula (lb), wherein the anion system represented by formula (3)

(3) indicates that the group '3 atom' 'red 3' means an anthracene heterocyclic group having an electron two or an electron attracting group: a valent aromatic hydrocarbon group, a 2 dentium: a divalent waxy aliphatic hydrocarbon group , 2 Υ 3, Α ~ and ^ can be two _, a plurality of integers up to 6. ) Don't use the same 'can be different, f system means! Examples of the atom of the US 13 group are the same as those of the former W, and the aryl group of the heterocyclic Lr-inducing group and the monovalent "electron attracting group" having the electron attracting group are the same as those described above. The V3 shell = atom, the divalent waxy aliphatic hydrocarbon group, the divalent aromatic hydrocarbon group, the 2-dentate aromatic group, the examples, etc. are the same as those of the above V1. The earth 321711 40 201035283 is an anion represented by the formula (3) An example of this is an anion shown in Formula IV.

(K) (In the formula, Ar3, Q3, and Y3 are the same as those described above.) The anion of the formula (IV) may have a substituent on an aromatic hydrocarbon ring, a heterocyclic ring or a hydrocarbon chain. In the anion of the formula (3), it is preferable that Ar3 is a perfluoroaryl group from the viewpoint of extending the life of the organic electroluminescent device. Q is used in the ion pair of the present invention, and among the anions represented by the formula (la), the formula (lb), the formula (2) and the formula (3), an ion pair containing an anion represented by the formula (la) is preferred. The cations of the ion pair used in the present invention will be described. The cation series is a rust of an element selected from a carbocation, a hydrogen ion or a metal cation, or an element selected from a nitrogen atom, an oxygen atom, a filling atom, a sulfur atom, a chlorine atom, a ruthenium atom, an amphoteric atom, a monumental atom, and a moth atom. The carbocation system may be monovalent or higher than valence, and is exemplified by n-methyl scale, n-ethyl ion, n-pentyl ion, n-cyclopropene ion, 41 321711 201035283 n-phenyl ion, orthoquinone Base ion, n-triphenylphosphonium ion, and the like. The rust system as a nitrogen atom may be a monovalent or a valence of two or more valences, and is exemplified by an aliphatic ammonium salt of the following formula: CH3 C2Hs CjHy 〇4Hfi h3c ten ch3 c2h5-n-c2h5 C3H7-N^C3H7 CiHe- N^Ha C2H5 〇4H9 ^6^13 CgH^7 ^10^21 ^12^*25 〇βΗΐ3-Νρ〇6Ηΐ3 CflH17-t\/±-C8H17 〇1〇Η21*-^^1〇Η21 C12H25-Ni -Cl2H25 ^6H13 0βΗ17 6i〇H2i Η2Η25

A cyclic aliphatic ammonium salt of the formula: X ^ , 3⁄4 H3i 〇 03⁄4 03⁄4 is shown in the following formula. Aromatic ammonium salt, 0 0 0 〇-ί〇 Οτ°Η3Ο 0

H3G—Ν ^ΌΗ3 ch3 CH,

a rust salt of a heterocyclic ring containing a nitrogen atom, which is shown in the following formula,

(wherein η' represents a natural number.) 42 321711 201035283 A cation or the like represented by the following formula (6). (R5). (^· (6) r3-+o~kV-r4 where π and R4 are the same or different and represent alkyl, alkoxy, aryl, • aryloxy, aralkyl, aromatic Alkoxy, fluorenyl, decyloxy, monovalent heterocyclic oxime or heteroaryloxy. 1 and R6 are the same or different and represent a halogen atom, an alkane, an alkoxy group, an alkylthio group, or an aromatic group. , aryloxy, arylthio, aralkyl, arylalkoxy, arylalkylthio, alkenyl, alkynyl, arylalkenyl, arylalkynyl f, substituted decyloxy, substituted decane sulphur Substituted, substituted decylamino, substituted amine, arylamino, flavonimide, decyloxy, fluorenyl heterocyclyl, heteroaryl = aryl arylthio, decyl, imine residue, substituted decyl , alkoxy group oxy group, aryloxysilyl group, heteroaryloxysilyl group, hydrazine: cyano group or nitro group. Τ system means direct bond, divalent aliphatic hydrocarbon group, divalent bar scent (tetra) group, a dilute base, an alkynyl group or a divalent heterocyclic group. i and the [] phase, = the same 'is an integer from G to 4. In the presence of a plurality of hearts, the lines may be the same or different.] —r atom, silk, alkoxy, sulfur-burning, aromatic oxygen Aryl group, aralkyl group, aryl alkoxy furnace base, alkenyl group, alkynyl group, aromatic 抡 抡 坌 ^ ^ 沉 沉 沉 沉 沉 沉 沉 沉 沉 沉 沉 沉 沉 沉 沉 芙 芙 芙 芙 芙 芙 芙 芙 芙 芙 芙 芙 芙 芙The substituted amine group, the substituted amine group, the decylamino group, the oxime group, the ethoxylated hetero-valent heterocyclic group, the heteroaryloxy group and the heteroaryl group are the same as those described in Yu, f γ1, + #ingot soil.疋疋 勤 勤 甘 甘 述 XX XX 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The base group is set to be the same as the definition of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group in the T of the electron attracting formula (6) of the above-mentioned Ar^Ar2 and Ar3, and the same is true for the divalent aromatic hydrocarbon group. The divalent heterocyclic group described in the electron attracting groups of the above V1 and VI v3 means that two hydrogen atoms are removed from the heterocyclic compound, and the carbon number is usually about 2 to 6 Å, preferably 2 to 2. Further, the number of substituents may be limited to the divalent heterocyclic group, and the carbon number of the substituent may not be contained. ^ As an example of the divalent heterocyclic group, the beauty exemplified in the above zl is given. Usually, it is about 2 to 2G, and it is exemplified by stretching and stretching of the ground, and in the case of extending an alkenyl group, it also contains a 1,3-aliphatic dialkyl group such as a 1,3-butyl dibasic group. The number is usually about 2 to 2 G, fresh ethynyl group, etc. Diacetylene/isoblock group also contains a group having two triple bonds, and examples thereof include, for example, I 3-butyl as a non-cation of the formula (6). cation

From the viewpoint of light intensity, it is preferable that the cation of the ion pair is separated from the system and the state of the divalent cation represented by (6). The lanthanide of the oxygen atom may be a monovalent atom y 疋 M shell or a multivalent valence of 2 mussels or more. As an example of the preparation of oxygen 7 三 三 三 三 三 三 三 三 三 三 三 三 三 心 心 心 心 心 心 心 心 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 321 Chromenylium) ' 咕 咕 rust and so on. The rust system of the phosphorus atom may be a monovalent or a valence of two or more. As an example of a scorpion atom, a series of tetramethyl hydrazine, tetraethyl sulphate, tetrapropyl sulphate, tetrabutyl sulphate, tetrahexyl squama, tetraphenyl squaring, trisyl fluorenyl sulphate, methyl triphenyl Scales and so on. The lanthanide of the sulfur atom may be a monovalent or higher valence. Examples of sulfonium atoms include trimethyl sulfonium, triethyl hydrazine, tripropyl hydrazine, butyl mirror, dihexyl hydrazine and the like, an aliphatic mirror, a triphenyl mirror, and a tris(4-methylphenyl group). Mirror, tris(4-tert-butylphenyl)fluorene or the like, anthracene diphenyl mirror, dimethylphenyl hydrazine, or the like shown in the following formula.

The rust of the propyl chloride atom may be a monovalent or higher valence. As a series of examples of chlorine and bismuth, dimethyl chlorohydrazine, diethyl chlorohydrazine, xenon surface, dibutyl chloro rust, diphenyl chlorohydrazine, methyl stupyl chlorohydrazine, etc. 321711 45 201035283 selenium atom The rust system may be a monovalent or a valence of two or more. As a series of examples of selenium atoms, triterpene selenium rust, triethyl selenium quinone, tripropyl selenium rust 'tributyl selenium quinone, trihexyl selenium rust, triphenyl selenium rust, tris(4-mercapto) Phenyl) lithite, tris(4-tributylphenyl) lithite, fluorenyl diphenyl sulphate, tridecyl phenyl ruthenium, and the like. The rust of the bromine atom may be a monovalent or a valence of two or more. Examples of the rust of the bromine atom include bismuthyl bromide, diethyl bromide, dipropyl bromide, dibutyl bromide, diphenyl bromide, nonylphenyl bromide and the like. The enthalpy of the cesium atom may be a valence of one or more valences. As an example of the rust of bismuth atoms, it is a series of ruthenium ruthenium, triethyl sulfonium, tripropyl ruthenium, tributyl ruthenium, trihexyl ruthenium, triphenylsulfonium rust, and tris(4-mercapto Stupid base, iron, tris(4-tert-butylphenyl) shoe, thiol diphenyl hoof, dimercaptophenyl hoof, etc. The oxime of the iodine atom may be a monovalent or higher valence. As an example of the rust of iodine atoms, it is a series of bismuth iodine rust, diethyl iodonium, dipropyl iodine rust, dibutyl iodine rust, diphenyl iodine rust, and bis (tert-butylphenyl) iodine rust. , 4-methylphenyl-4-(1-mercaptoethyl)phenyl moth iron, nonylphenyl iron, or rust as shown by the following formula.

As the metal cation series, a cation of an alkali metal, an alkaline earth metal 46 321711 201035283, a cation, a rare cation, a transitional gold cation, and the like. The gold cation system may be a monovalent or a valence of two or more. There is a narration state due to the effect of the heavy atom, and therefore, it is preferably a cation of a metal having an atomic weight of less than 50. The cation series of the alkali metal is a lithium ion, a sodium ion, a potassium ion, a cesium ion, a planing ion, or a cerium ion. Examples of the cation series of the alkaline earth metal include cerium ions, magnesium ions, calcium ◎ ions, ionic ions, cerium ions, (_)+, (MgBr), (MgI)+, and the like. Examples of the cation series of rare earths include ruthenium ions and ruthenium ions. As a series of cations of transition metals, titanium ions, cerium ions, ion ions, ions, chromium ions, [double U5-benzene) Cr]+, manganese ions, iron ions, [(: _ pentadienyl ▽ 6_) Benzene)Fe] +, [( π 5-cyclopentadienyl)(π toluene 5)Fe], ["5-cyclopentaphthyl" (?? 6-1-methylnaphthalene)Fe]+, [ (β-cyclopentadienyl) "6-cumene" Fe]+, [bis("5-mesitylene)

Fe]+, cobalt ion, nickel ion, copper ion, reciprocal ion, and the like. 〇 The following ion pairs are listed as an example of the ion pair used in the present invention. The ion pairs in which the cation is a carbocation are the following ion pairs. 321711 47 201035283

Examples of the ion pair in which the cation is a nitrogen atom include an aromatic ammonium salt system, an aliphatic ammonium salt system, an aromatic amine salt system, and an aromatic diazonium salt system. A series of ion pairs in which the cation is an aromatic ammonium salt system, for example, 1-benzyl 48 321711 201035283 -2-cyano quinone 镔 镔 tetra (pentafluorophenyl) ru

Salt, 1_(naphthylmethyl)_2-cyano0, bite-missing tetrakis(pentafluorophenyl)folate,]M ▲ 'I dimethylaniline tetrakis(pentafluorophenyl)borate, 1-butyl Benzyl-3-methylimidate in the king's tetrakis(pentafluorophenyl)borate, 1-ethyl-3-indolyl sulphate, sputum, tetrakis(pentafluoro, violent), citrate, 1 - Octyl-3-mercaptoimidazole tetrakis(pentafluorophenyl)borate, :::~bromophenyl)ammonium tetrakis(pentafluorophenyl)borate. The cation is an aliphatic ammonium salt-based hybrid 2, and the genomic pair is a tetrabutylammonium tetrakis(penta-phenyl) shed acid salt or a tetraethyl-tetrakis(pentafluorophenyl)borate. The ion system in which the cation is an aliphatic ammonium salt system is exemplified by the following ion pair in addition to the ion pair described above. n-BuN+/n-Bu n-BU', BU [(〇6Ρ5)3Β-^ί-Β(ΟβΡ5)3 ] I (C6F5)3B-3N-B(CeF5)3"I (CeF^B-eN -BiCeFsJa" ,rvBu n-Bu 2 Vn· n-Βυ^ n-Bu [&gt;u 1 2- n-Bu γ&gt;·Βιι 2 ^ -(CeFs)3B, k,B(CeFfi)3_\ ^ (CeFsJsB-fVBiCeFBJs N! n-Bu \.Bu N〆\| • ”, B(CeFs)3· (CeFs)3B. Pd PN* N 〆.B(C6F5)3· 2-

Me + Me 2- Ο n-Bu n-Bu> v n-Bu n-Bu n-8u&gt; η·Β〆

(CeFshB

BpeF^ +/ivBu I (CeFsJaB-N^N-N-BfCeF^j -n-Bu, 2-n-Bux n-Bu ! N n-Bk/ n-Bu (CeFs) (CeFs):

Ws) , n-Bu n-Bu (CeF^bB-N two N-B(CeF5)3

2- (wherein Me is a fluorenyl group, and Bu is a butyl 321711 49 201035283 cation is an aromatic amine sulfonium salt ion series of tris(4-bromophenyl)amine 镔tetrakis(pentafluorophenyl) Borate, hydrazine, hydrazine, hydrazine, Ν'-tetraphenyl-4,4'-extended biphenylenediamine bis(tetrakis(pentafluorophenyl)borate), etc. The cation is an aromatic amine rust salt system. The ion pair is exemplified by the following ion pair in addition to the aforementioned ion pair.

Br

i (C6FS>3BSN&quot;^(C6FS)3"{ (CeF Hawthorn-B (CeF6h" 2 { {〇6&amp;)38 Butterfly-5(〇6戸5)3 J

"(CSFS&gt;3B, .B(CfiF5)3 2-Dh (〇6"5 ννα μ Ni / \ rn 2 &gt; Ph \pn \^N Pd / j 1-(c6f5)3b B(CeF5)3 j L(c6f5)3b B(C6F5)3 J

(Ce^aB (wherein, Ph represents a phenyl group). The ion pair used in the present invention is also an ion pair of an aromatic diazonium salt system, and a series of examples thereof are phenyldiazonium tetrazide Pentafluorophenyl)borate, etc. The ion pair of the cation as the aromatic diazonium salt system is exemplified by the following ion pair in addition to the ion pair described above. ph ph, Ph

2 Ph

Ph

—B(C6Fs)3 P〆 ^ [(CeF6)3B-Hv〇M- •B(CGFS)3

50 321711 2· 201035283

[(CeFgJsB-^l-BCCeFsJsf 2 Q-N

^nI

F

(C^Fs^B (CeFs)3 2- !〇-n=n (CeFs)3B. /B(CeF6)3 N. M \ λ Ni (〇eF5)3By -8(0^5)3 2- (CeFs) 3B, \家Pd〆》N, {C^shB B(CeF5)3 ^^-N=n[ (〇6Ρ5)3Β-Ν=Ν=Ν—Β(0^5)3| ^^ 4j=fvj I (CeFgJsB-N^N —B(CeF5)3

O W/'R. (CeFs) ^ -

F

(CeFs) (CeFs) 2-

-, the 2-cation is an aromatic ammonium salt-based ion pair, and the ion pair shown in the formula (10) is equivalent.

(R^i (R6)j 2B| Μ (1〇) 〇

Vf r /4 (wherein R3, R4, R5, R6 and lanthanide are the same as those described above. The ion pair series shown in the formula (10) are exemplified by the following ion pairs. 51 321711 201035283

2 2 C3HT-N^-Q+-C3H7

2 BTMr^JV*F j H^C-CHs 2 B · H^C —(CHjJa —~CH5

The ion pair represented by the formula (10) can be produced, for example, by reacting a compound represented by the formula (11) with Li[B(C6F5)4]·n(Et2〇). 52 321711 (11)201035283 χ3' (R5)i (R6)j χ4'

[In the formula, R3, R4, R5, R6, ·|, i, and τ are not the same as those described above in the main _J ^ 3_ 4_ 1 factory 1 series. X and X4 are the same or different and represent a halide ion, an alkylsulfonate ion, or an aryl sulfonate ion. The bromide ion ions are exemplified by fluoride ions, chloride ions, cesium ions, and iodide ions. The burnt radix ion ❹彳 甲 甲 甲 纠 纠 纠 纠 纠 纠 纠 纠 纠 纠 纠 纠 纠 纠 纠 纠 纠 纠 纠 。 。 。 。 The arylsulfonate ion is exemplified by a benzenesulfonate ion and a p-toluenesulfonate ion. The ion pair in which the cation is an aromatic ammonium salt system is exemplified by the following ion pair in addition to the ion pair described above. 321 321711 53 201035283

Me^2N^ MeJ〇^CN+_Me {(C^fihB-asW-BiCftFs^ j* 2 [(CeFftJsB-esN-fiiCeFehj 2 1(〇Λ)ϊΒ, 一Β{^ΡώΓ

Ph (CgF^B-

2-

1(ΡΛ}αΒ-«Ν·**Β(〇Λ)&gt; I (four) secret, 2- W6&gt;jB, n ν/Β(〇Λ)» - _MJ &gt;NV «Τ, N, \l ( CeW, «BtCjFs)* (CeF^feB 'BfCeFs)!. 2- (wherein Me is a sulfhydryl group and Ph is a phenyl group.) The cation is a phosphorus atom rust ion pair series of tetraphenyl scales (Pentafluorophenyl)borate, etc. The ion pair in which the cation is a rust of a phosphorus atom is exemplified by the following ion pair, etc. 54 321711 2[(CeF^B-NeN^N-BiCfiFeJa { Ph-^N^^—^^N-Ph 2 (CeF^B-l'i^N-BtCfiF^s

201035283

QOGO

2 P+GO {0^5) 3 days

z r*T GO 2, p WsbB VI B{C6F5)3

(CeW,

(C^5)3B S(C6Fs)3 ί 2- V / Pd / \l B^CeFsb j

QD

(^aB-N^N^BiCeFsb

(CeFs)3B-N-N=N-B{C6F5}3

OO

QO 2 P+

The OO cation is an ion pair of a sulfur atom, and a series of aromatic sulfonium salts, as an example thereof, is a series of bis[4-(diphenylscale)phenyl]thioether tetrakis(pentafluorophenyl)borate, diphenyl. 4-(phenylthio)phenyl scale, tetrakis(pentafluorophenyl)borate Q acid, triphenylscale tetrakis(pentafluorophenyl)borate, bis[4-(di(4-(2) -Hydroxyethoxy))phenylphenyl)phenyl]thioether tetrakis(pentafluorophenyl)borate. The ion pair in which the cation is a sulfur atom is exemplified by the following ion pair in addition to the ion pair described above. 55 321711 201035283

b 〇 Ο * 2 |&lt;〇Λ)38·βΝ -BiCePe&gt;5j

&gt; WCeFsh / V (〇Λ)3Β〆

X 12- (ΟΛ〆, 8{c*F6)»

The ion pair of the iodine atom is an ion pair of an aromatic iodonium salt series, and as an example thereof, diphenyl iodine tetra(pentafluorophenyl) borate, bis(dodecylphenyl) Essence of tetrakis(pentafluorophenyl)borate, 4-indolyl~4-(1-methylethyl)phenyl iodide tetrakis(pentafluorophenyl)borate [by Rh〇DIA) RH0D0RSIL) The name of photopolymerization initiator PI-2074" is sold on the market. ]Wait. The ion pair in which the cation is an iodine atom is exemplified by the following ion pair in addition to the aforementioned ion pair. 56 321711 201035283 〇 卜 ο m κχ [(CeFg^B-sN-BiCeFsbf |(CeF6)3B-BW~8(C6Fs)3 Factory 1(〇^&gt;38— Η-F (CeFdaS^y-BiCeFsh

(C«Fs) 3B

N 2-

_ (Cfif §)sB (CeF^B. ^CeFeJs &quot;BtCeFsJa ^BiCeFgJa ' 2-

^€h+^Ch\ - Bu CeFB^BN»tvMs}~B(CeFs&gt;3"-〇+-CK ❹ \/. Pd N〆\ (C6Fs)3B/ Β(〇βΡ5)3 J ~0~i+ -〇~(

2-ionion is a metal cation ion pair series (2, 4-cyclopentadienyl-1-yl)[(1-mercaptoethyl)benzene]-Fe(II) tetrakis(pentafluorophenyl)borate Hey. The ion pair in which the cation is a metal cation is exemplified by the following ion pair in addition to the ion pair described above. 57 321711 201035283 {(CeFshB-^-BfCeFsh j' K+[ (CeFs}3B-«N-B(CeF5h]

Na+1 {C6F5)3B-«N-B(CeF6b | * MgBr4 [ (CeF-O^B-eN-BiCeFshj

‘ ‘Umbrella· h -12- F- F (CeFs) sy\ACifd bowl,) “&lt; Ws).

The anion of a certain form of the ion pair included in the present invention is represented by the formula (5-1), and the cation is σ pyridine rust cation, scaly cation or iodonium cation. 1(C6F5)3B-CB(C6F5)3] (5-1) An example of the ion pair is shown below. The ion pair with a cation ratio of σ to the iron cation is exemplified by the following ion pairing. 58 321711 201035283

^N-CHS[ (CeFs)3B-CiN-B(CeFs)s | I &lt;C#Fe)i0-C5N-«CeFs)s |

(CeFsJaB-Cai-eiCifsh I (CePshB-CaJ-8((3⁄43⁄43⁄4 j ΐ-c^h [ (CeFsJsB-CsN-atCeFeh j*

〇^-〇 1 Yang Ming*, CeFfth I Ο^Ο'ξΟ+Ό

2 I (CeFs^-CsN-SiCeFsH I

Γ~〇&gt; j (C^5b6-CSN-B(CeF5h Ο

HjC-N, 2 [ {CePsbB-CSN-BtCeFds | 2 I (CeFs^-CsN-BlCeFda | 2 [ (CeFsjsB-cai-fiiCeFyo 2 [ (CeFfiWB-C^-BiCeFeb 聊一+r〇-O^~CiN7 I 2 [ (Ce^aB-ca^-BiCeFeh 1'

2 I &lt;G^=e)sB-CSN-BCCefBh I

\ / ^ 2 I (C^PsisB-^ 2 I (CeFB)jB-C2N-B(CeFs)9 | 2 | (C«Fs)sB-05^-8(0^ |

Ms 〇 59 321711 201035283

》·~(CH2)2 —^ ^N~~CH3 H3C—^(CH2>3. -~CH3 2| (C#5 shout~C3^~B(GsF5)3 I 2l (CsF5)3B~C= N-B(C6F5)3 | H3C-i

~ch3

N~—CH3 21 (C^3B-C5N-B(CeF5)3 j · 21 &lt;CeF5)3B-CSN-Β(0#5&gt;3

H3〇—Ni \—^ N~~CH3

+ CH3

2( (〇6p5}3B-C=N-B{C6F5}3 )

O^D^(CH2fe^N+HQ 2[ (C6F5)3B~CHN-~S(C6F5)3 ] 21 (C5F5)38--C3N-B{CeF5}3 | 1 B&lt;CsF5)3 j 2[ (〇βΡδ)3Β -8(0^5)3 ] (.6 corpse 5) 3曰1.荆一3{C0F5)3

z[ {〇6Ρ5)3Β-〇5Ν-~Β(〇6Ρ6)3

2[(C6F5)3B-C5N-8^0^5)3 I The cation is an example of an ion pair of scaly cations. The following series of ions are equivalent. 60 321711 201035283

[(C6F5)3B-^N-B(C6F5)3" [ (CsF5&gt;3B-^M-B(C6F5)3j

Examples of ion pairs in which the cation is an iodine rust cation are given by the following ion pairing.

{(C6F5)3B~((C#5&gt;3B *^(&lt;^6^5)3] [(〇6尸5&gt; 3rd] The above-mentioned β-rust salt, scale salt and sputum salt system It can be produced by reacting a compound represented by the formula (7-1) with K[(C6F5)3B-C三NB(C6F5)3]. Ο E1+ X5' (4) (wherein E1+ represents an acridine cation, a squamous cation or an iodonium cation. X51 represents a halide ion, an alkyl sulfonate ion, or an aryl sulfonate ion.) As an example of a ii compound ion, a fluoride ion, a chloride ion, a desert ion, a fragment ion Examples of the alkylsulfonate ion are a decanesulfonate ion, an ethanesulfonate ion, a trifluorosulfonate ion. The arylsulfonate ion series is a benzenesulfonate ion, p-toluenesulfonate 61 321711 201035283 The other forms of anion used in the ion pair of the present invention are of the formula (-, represented by a cation system, a cation, a cation, a cation, a cation, or an iodine cation). Ten CiN-B(CeF5)3y 2· (wherein M represents a nickel atom or a palladium atom.) An example of the ion pair is shown below. Ion $ "Example of ion pair of iron cations (5-2) List the following 321711 62 »2*· 201035283 2- 2 &quot;*CH3| μ-jC --B(CbF&)3 IJ 2 〇 2Η$|μ-jC =N —B(CgF$)3 J | 2 }/2 i4. fo 2 chs 卜 inch (10)一取0^ Q^jM^.N-BiCeF^ ) j2* ^-+NDO- C^ »3^: &gt;~Ci H-CH, ,2- h2

C3H7-N |M-fCSN—Β(0«Ρδ)3 jJ inch C5N—BiCeFA 丨p [M-|-C5N—B(C6F6)3 j NC^H,HaC -N *C&amp;H7 H3C- 2- 2*· ^ |Mj^5N-S(CeF5)3 II Bu (5)-Qiu Mail I Factory k2-

. Miscellaneous

[w -|-C5N-j 63 321711 201035283 ^30 (CK2)3 CH3 jM-j-CsN-BCC^J ^-jC^I-B(C6F5)3] 4J 41

-4f\ \25aZ "Τ_________ , , 2-

H^C

N-CH3 2&gt; [M-^ChN-8^5) 3(^]

N+ 1/2[W*fC£N-B&lt;C6F5)3j j CH3 4 2- |M*|〇5N&quot;-B(CeF5)31

(4)·〇Ό|Μ·^χΝ -*&amp;(〇£^5&gt;3 «2- '4*

卜寸 C —-B (CsFsh

^M*|cafsi—β(〇0Ρ§&gt;3 J 4j |M&quot;j-C=N-6 (0^5)31 j

1/2 [M-fCsN-8(CsF5)3( »2* cation is a four-level cation, and her series of ion pairs is the same as the ion pair. 64 321711 201035283 I J2' 2 QjHs- Ni-CsHis [Mj-CsN-BCCeFs)» | | I——C^Hii ,—I 4:3⁄4 13⁄4 2 Meaning 2

2 HaC Ο 03⁄4 &quot;2' |M-|C Cut -3⁄43⁄43⁄4 CHj 2 I U O &quot;[M-tCHN-BC^lf* )^^3}) 2q 4σο : (MfcsN-fiiCiFe)»} J2'

itCHajM-fCSN-BtCeF^ J | ' 2

MfCSN-BiCeF^j ] 2-

I2-

OQh03'1,8^/ (Μ-^δΝ^ΟβΡδ)»! Γ ,

CHj &lt; CH3 (

I2* JSN-^CeFsJs} γ CH3 CHj 4 2[W'fCSN-BtCeFsJs | J2 2 [MfCsN-ejCeFrfa | J2 cation is an example of an ion pair of scaly cations. The following ion 〇 is equivalent. 65 321711 201035283

2

[M-jOEN-B(C6F5}3 ] , 2- 41

M-j-C=N-^B(CsF5)3 J 2-

4J 2 o 2

M ~|c ΞΝ —BfCgFgJg 2-

l4J {M 十 C ΞΝ —S(Cgp5)3 ,2-

The 4J cation is an ionic cation cation ion pair series with the following ion pairing.

|m-{-C=N—B(CeF5}3 j J2 2 \/ |m-|-C5N—B (CeFg?3

The H3CO cation is an example of an ion pair of a ruthenium cation. The following series of ions are equivalent. 66 321711 201035283 Λ Ά ‘,: qi to’

ΓΓ5!3 ιΓ^Ι [MiC5N~B(CeF5)s 11 I I 2/3 *' * 4

[M-jC^-B^^jJ 2 s^-H^-^-jMjC^N-BtCeFfiisJ j2' ^ [MfCSNHBtCeF^jJ2*

O

Ο OH 4 Ο 4

O-^^St^ -/( ό 2〇io! [M-jCsN-BiCeF^ I J2* [MfCSN-aiCeF^ | J2 1/2 ] | Ο The cation is a series of ion pairs of rusting cations. Ion pair. 'ΟτΆjM-fCsN-BfCeFsJj j J2*

p-fCsN-BjCeF^JJ Bu C C||&gt;B(C6Fs)5j j2-41 The aforementioned pyridine salt, scale salt and iodonium salt can be obtained, for example, by hydrazine (7-2) And K2_ when B ((5) mountain] reacts. "Working E2+ X6· (7-2) (wherein, E2+ is a table (4) pin cation, a fourth-order yoke, an oxonium, a mirror cation, or a cation ion , alkyl sulfonate + tyrosine is very different from thousands, sulfonate ion.) As a halide ion, sputum alkyl acidate ion, aryl sulfonate ion ion, scale cations 311711 67 201035283 example The ion to be used in the present invention may be one type or two or more types. The polymer light-emitting body used in the present invention will be described. The average molecular weight of the light-emitting system in terms of polystyrene is usually 1〇3 straight 108. Among the polymer light-emitting materials used in the present invention, a conjugated polymer compound is preferred. a main chain skeleton of a molecular compound and a polymer compound having a non-localized 7-electron pair. #定域电子系有有相相的手手或孤电子对对对反应的反应以及以及双键的之间。 <lt>Co-roll polymer compound&gt; The conjugated polymer compound used in the present invention means (1) substantially a polymer compound formed by alternately arranging a structure of a double bond and a single bond, (2) a polymer compound substantially composed of a structure in which a double bond and a single bond are arranged by a nitrogen atom, and (3) substantially interacting a structure in which a double bond and a single bond are arranged, and a polymer compound or the like in which a double bond and a single bond are arranged by a nitrogen atom. Examples of the conjugated polymer compound are, for example, an unsubstituted or substituted geminal group. Unsubstituted or substituted stupid and anthranyl, unsubstituted or substituted dibenzoxanthene-N-diyl, unsubstituted or substituted di- and di-substituted thiophene diyl, unsubstituted or substituted carbazolediyl, unsubstituted Substituted or substituted thiophenediyl, unsubstituted or substituted furandiyl, unsubstituted or substituted pyrrolidinyl, unsubstituted or substituted benzofluorene H, unsubstituted or substituted phenylene Substituted or substituted thiophene Unsubstituted or substituted three 68 321711 201035283 one or more selected from the group consisting of phenylamine dimers as a repeating unit, a polymer compound which is directly or through a lotus group bonded between the repeating units In the state in which the above-mentioned compound polymer compound is bonded to the above-mentioned repeating unit-transfering group, as a series of the linking group, for example, a phenyl group, a phenylene group, a naphthyl group, and a fluorene group are mentioned. In view of the charge transport property, the conjugated polymer compound used in the present invention is preferably one selected from the group consisting of the group consisting of formulas (8) and (9). The above repeating unit.

(8) (9) q [In the formula, R8, R9, R1. And R11, R12, R13, R14, R15, R16 and R17 are the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group or an aromatic group. Alkoxy or arylalkylthio. In the formulae (8) and (9), the alkyl group, the aryl group, the alkoxy group, the sulfur-burning group, the aryloxy group, the arylthio group, the aryl group, the aryl alkoxy group represented by R8 to R17. Specific examples of the arylalkylthio group are the same as those defined in the above X1, examples, and the like. From the viewpoints of film formation energy and solubility in a solvent, the number average molecular weight of the conjugated polymer compound in terms of polystyrene is preferably 69 321 711 201035283 is lxl Ο 3 to lxl Ο 7, more preferably lxl Ο 3 to lxl Ο 6. The conjugated polymer compound contained in the organic layer of the organic electroluminescent device of the present invention may be one type or two or more types. The above-mentioned compound-based polymer compound can be synthesized by mixing a monomer having a functional group suitable for the polymerization reaction to be used, and if necessary, dissolved in an organic solvent, for example, by using an alkali or a suitable catalyst. The polymerization is carried out by a polymerization method such as a conventional aryl coupling. &lt;Light-emitting layer&gt; The light-emitting layer of the organic electroluminescence device of the present invention includes an ion pair represented by the formula (1), the formula (1b), the formula (2) or the formula (3), and a polymer light-emitting body. The weight of the ion pair represented by the formula (1), the formula (1b), the formula (2) or the formula (3) in the light-emitting layer is preferably 0.001 to 10 parts by weight based on 100 parts by weight of the polymer light-emitting body. More preferably, it is 0.01 to 1 part by weight. The light-emitting layer of the organic electroluminescence device of the present invention may include the formula (la), the formula (lb), the formula (2) or the formula (3) without impairing the charge transport property and the charge injection property. A component other than the ion pair. <Organic electric field light-emitting element> The organic electroluminescent element of the present invention has a pair of electrodes and a polymer-containing light-emitting body and a formula (1a), a formula (1b), a formula (2) or a formula (between the electrodes) 3) The luminescent layer of the ion pair shown. One of the pair of electrodes is an anode and the other is a cathode. At least one of the pair of electrodes is transparent or translucent.

The series of organic electroluminescent elements of the present invention (a) forms a light-emitting layer comprising a polymer light-emitting body and an ion pair on the anode, and then, on the light-emitting layer, a cathode is formed between the anode and the cathode. An organic electroluminescence element obtained by energization treatment of the anode to the cathode current is applied by applying a voltage of 10 V 70 321711 201035283 or more.

The organic electroluminescent device of the present invention is characterized in that (b) forming an illuminating layer comprising a polymer illuminant and an ion pair on the cathode, and then forming an anode on the luminescent layer, at the anode and the cathode An organic electric field light-emitting element obtained by energization treatment of the anode to the cathode flowing current was applied with a voltage of 10 V or more. The light-emitting layer may be formed directly on the anode or through the electron injection layer and/or the hole transport layer. The cathode system may be formed directly on the light-emitting layer or may be formed by an electron injection layer and/or an electron transport layer. The light-emitting layer included in the organic electroluminescence device of the present invention may be a composition comprising an ion pair represented by the formula (1), the formula (1b), the formula (2) or the formula (3), and the polymer light-emitting body. Manufacturing. The weight of the 0 ion pair compound represented by the formula (1), the formula (1b), the formula (2) or the formula (3) in the above composition is 100 parts by weight relative to the polymer illuminant (preferably a conjugated polymer compound). 01至第一重量份。 By weight, preferably from 0.001 to 10 parts by weight, more preferably from 0.01 to 1 part by weight. The method for producing the light-emitting layer is not particularly limited, and for example, a film formed by a solution containing the above-mentioned composition and a solvent may be used, and a film may be formed by a vacuum deposition method. The solvent used for film formation from the solution is capable of dissolving the ion pair and the polymer illuminant (preferably the conjugated polymer compound) represented by the formula (la), the formula (lb), the formula (2) or the formula (3). There is no special restriction. 71 321711 201035283 As the solvent series, for example, benzene, xylene, mesitylene, tetralin, decalin, dicyclohexyl, n-butylbenzene, t-butylbenzene, t-butylbenzene, etc. Saturated hydrocarbon solvent, four gasified carbon, chloroform, dichloromethane, dichloroethane, butane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromine A saturated hydrocarbon solvent such as cyclohexane, an unsaturated hydrocarbon solvent such as benzene, dichlorobenzene or trichlorobenzene, or an ether solvent such as tetrahydrofuran or tetrahydropyran. The composition of the ion pair and the polymer illuminant of the formula (1), the formula (1), the formula (2) or the formula (3) is usually dissolved in the solvent 0.1. More than weight%. In the film formation from the solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a pressure coating method, a wire coating method, or the like can be used. Coating methods such as dip coating method, spray coating method, screen printing method, flexographic printing method, lithography method, inkjet printing method, dispersion printing method, nozzle coating method, capillary coating method, etc. It is a spin coating method, a flexographic printing method, an inkjet printing method, and a dispersion printing method. Examples of the method for forming the cathode include a vacuum deposition method, a sputtering method, an ion implantation method, and a plating method. The organic electroluminescent device of the present invention is obtained by performing an energization treatment between an anode and a cathode to obtain an organic electroluminescent device. The voltage applied to the energization treatment is preferably 10 V or more and 100 V or less, more preferably 10 V or more and 50 V or less. The application of the voltage can apply a certain voltage, and the voltage applied in stages can also be increased and/or decreased. The total power-on time is preferably from 0.01 to 1 hour, more preferably from 0.1 second to 30 minutes. It is considered that the organic light-emitting element can be aligned by the ion pair of the light-emitting layer towel by the voltage of 10 321 711 and 2010 35 283 at a voltage of 10 V or more. 〃 ^ The temperature at the time of energization treatment is preferably about room temperature. The atmosphere at the time of energization treatment is preferably an inert atmosphere free from moisture or oxygen. For example, it is preferable to seal the laminate including the anode, the light-emitting layer and the cathode in an inert gas, and conduct electricity between the anode and the cathode of the laminate.有机 有机 The organic electroluminescent device of the present invention is (1) an organic electroluminescent device in which an electron transporting layer is provided between a cathode and an illuminating layer 2, and (2) an organic electroluminescent device in which a hole transporting layer is provided between an anode and a first layer, and (3) An organic electroluminescence element or the like in which an electron transport layer is provided between the two electrodes and the light-emitting layer, and a hole transport layer is interposed between the anode and the light-emitting layer. The organic electric field light-emitting element of Ming is usually formed on a substrate. The 2 series is best for the Wei, and it is not shaped in the shape of the money. The material of the substrate is, for example, lang, (4), a polymer film, a chip, or the like. As the substrate 彳H, it is good to use the state of the plate, and the opposite electrode (that is, the electrode away from the substrate) is transparent or translucent. The material film is made of an transparent or translucent electrode material _ a conductive metal oxide = a translucent metal film or the like. Specifically, a film made of a conductive material made of indium, tin, oxide, or a composite of a fresh composite of indium oxide and zinc oxynitride, and a thin composite of zinc (oxide) is used ( Nesa, etc.) i gold, silver, copper, etc., preferably 1τ°, indium·zinc·oxide, =. As a series of manufacturing methods of electrodes, the vacuum distillation method, the fiber, the inlet method, and the electric boat method are used. Further, as the electrode material, an organic transparent conductive film of 321711 201035283 polyaniline and its derivatives, polythiophene and its derivatives can be used. Further, as the electrode material, a metal, a conductive polymer or the like can be used, and it is preferable that one of the pair of electrodes has a material having a small work function. For example, the use of chain, nano, Shu, #Π, planing, magnesium, Ma, recorded, 钡, Ming '铳, 鈒, zinc, Ji, indium, Jin, Peng, 铕, test, 镱 and other metals, and these Two or more kinds of alloys, or one or more of these, and one or more alloys of gold, silver, platinum, copper, lanthanum, titanium, lanthanum, lanthanum, and tin, graphite or graphite intercalation compounds, and the like. Examples of alloys include magnesium-silver alloys, town-indium alloys, magnesium-alloys, indium-silver alloys, memant alloys, inner-alloys, chain indium alloys, calcium-aluminum alloys, and the like. As a series of materials used in the aforementioned electron transport layer, oxadiazole derivatives, quinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, hydrazine and its derivatives, tetracyano Dioxane and its derivatives, anthrone derivatives, diphenyldicyanoethylene and its derivatives, biphenyl hydrazine derivatives, metal sterols of 8-meridinium and its derivatives, polypyrene And its derivatives, polyphosphonium and its derivatives, polyfluorene and its derivatives. Further, as a material series used for the above-mentioned hole transport layer, a polyvinylcarbazole and a derivative thereof, a polydecane and a derivative thereof, a polyoxyalkylene derivative, a polymer compound having an aromatic amine residue, and a poly Aniline and its derivatives, polythiophene and its derivatives, poly(p-phenylene vinyl) and its derivatives, poly(2,5-threquivalent vinyl) and its derivatives. The organic electroluminescent device of the present invention may further comprise a buffer layer, and a series of materials used as a buffer layer may be used as a buffer layer of an alkali metal such as lithium fluoride or an oxide or an oxide of an alkaline earth metal. Further, fine particles of an inorganic semiconductor such as titanium oxide may be used in the buffer layer. The film thickness of the light-emitting layer is usually from Inm to l〇〇/zm, preferably to 100 nm, more preferably from 5 nm to 500 nm, even more preferably from 2 to 20 Grim. &lt;Use of the device&gt; The organic electric field light-emitting element described above can be suitably used for a curved or planar illumination device, for example, a planar aperture source as a scanning light source and a display device. Examples of the display device including the organic electroluminescence element include a segment display device, a dot matrix display device, and the like. In the dot matrix display device, there are an active matrix display device and a passive matrix display device. The organic electric field generating element is used as an active matrix display device and a passive matrix display device, and is used as a light-emitting element constituting each element. Further, the organic EL element is used as a light-emitting element constituting each segment in a segment display device, and is used as a backlight in a liquid crystal display device. Further, the present invention will be described in more detail below, but the present invention is not limited thereto. —Measurement Method 1 of Molecular Weight In the examples, the number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of polystyrene were determined by gel permeation chromatography (GPC). Specifically, the TSKgel SuperHM-H (manufactured by T0S0H Co., Ltd.), which is made of GPC (manufactured by Tosoh Corporation, trade name: HLC-8220GPC), is connected in series with 321711 75 201035283 in series, and is expanded with tetrahydrofuran. The solvent was flowed at a flow rate of 0.5 mL/min, and the measurement was carried out at 40 °C. The detector uses a differential refractive index detector. &lt;Synthesis Example 1&gt; (Synthesis of Polymer Compound 1) Into a 500-ml 4-necked flask, a trimethyl sulfonyl ammonium hydride (Triscaprylyl methylammoniuinchloride 'product name: A1 iquat 336 "registered trademark", manufactured by Aldrich Co., Ltd.) was placed. , the following formula:

〇8Ηΐ7〇δΗ17

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

CaHi7 CeH-iy

The compound B represented by the compound B is 0. 5G85g, the following formula:

The compound C represented by the compound C is 6.225 g, and the following formula: 76 321711 201035283

0. 5487g of the compound D is represented by nitrogen substitution. 6 曱 ml of toluene was added, and hexahydrate (triphenylphosphine) Ι ε (11) 7.6 mg and 24 ml of an aqueous sodium carbonate solution were added, and the mixture was stirred under reflux for 3 hours. Then, 0. 40 g of phenylboric acid was added and stirred overnight. Then, an aqueous solution of sodium N,N-diethyldithiocarbamate was added, and the mixture was stirred under reflux for 3 hours. The obtained reaction liquid was subjected to liquid separation, and the organic phase was washed with an aqueous acetic acid solution and water, and then dropped into methanol to cause precipitation. The obtained precipitate was filtered and dried under reduced pressure, and then dissolved in toluene, and washed with phthalic acid through a silica gel-alumina column. When the obtained toluene solution was dropped into methanol, precipitation occurred. The obtained precipitate was filtered, dried under reduced pressure, dissolved in toluene, and dropped to methanol to give a precipitate. The obtained precipitate was filtered and dried under reduced pressure to give 7.72 g of polymer compound 1 as a conjugated polymer compound. 2x105。 The weight average molecular weight Mw of the polystyrene conversion is 1. 9x105. &lt;Synthesis Example 2&gt; (Synthesis of Polymer Compound 2) In a 5 L separable flask, Triscaprylylmethylaimnoniuinchloride (trade name: 77 321711 201035283) was placed.

Aliquat 336 "registered trademark", made by Aldrich) 40. 18g, the following formula:

234. 06g of the compound E represented by the formula:

172.06g of the compound F represented, and the following formula:

5528g of the compound G represented by gas replacement. 2620 g of toluene which was bubbled with argon was added at 78 321 711 201035283 to carry out the ageing, and at the same time, foaming and treatment were carried out for 3 minutes. After adding acetic acid, 99. lmg^(〇_甲笨基) scale 937·〇 was washed with 158 g of benzene to heat to the mosquito. After dripping 855 g of 175% by weight aqueous sodium carbonate solution, the temperature of the bath was raised to U (rc, after stirring for 5 ° 5 -hour, 5.39 g of phenylboric acid was added and dissolved in 96 ml of toluene, and stirred for 14 hours. The toluene' reaction solution was liquid-separated, and several phases were treated with 8 times by weight of a 3 wt% aqueous acetic acid solution of 85 〇ml, and 85 〇mi of water and sodium N,N-diethyldithioamine citrate were also added. 19.89g, stirred for 4 hours. After liquid separation, it was washed with toluene through a silica-alumina column. When the obtained toluene solution was dropped to 5 〇L of sterol, a precipitate was formed, which was washed with decyl alcohol. The precipitate was dried under reduced pressure, and dissolved in toluene of UL, and the obtained toluene solution was dropped to 50 L of decyl alcohol to cause precipitation. The obtained precipitate was filtered and dried under reduced pressure to give 278·39 g of polymer compound 2. The number average molecular weight of the molecular compound 2 in terms of polystyrene is Mn. 7. ^ ίο4 'The weight average molecular weight in terms of polystyrene - is 3 8x1 〇 5. q <Synthesis Example 3> (Synthesis of ion pair (H)) Do not replace the Oml eggplant flask with nitrogen, tris(pentafluorophenyl)borane 5. 00g was dissolved in 200ml of diethyl ether, and 31g of potassium cyanide was added. After refluxing at 3 hours%, the solvent was distilled off to obtain & "Ion pair (ugly). MS (ESI-negative) m/z 1049. 8([MK]') k[(〇6F5)3B—=NB(C6F5)3]' (H) 321711 79 201035283 &lt;Synthesis Example 4&gt;(Synthesis of ion pair (I)) For a 4-ml flask of 200 ml Nitrogen replacement was carried out, and tris(4-t-butylphenylhydrazine)trifluoromethanesulfonate 〇.486 g, ion pair (H) 0.873 g, ion-exchanged water 20 ml, and diethyl ether 60 ml were charged. After the reaction, the thermometer and the condenser were reacted for 16 hours at 21 to 23 ° C. 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 three times with 30 ml of ion-exchanged water. The ether layer was transferred to a 200 ml Erlenmeyer flask and dehydrated by adding anhydrous sodium sulfate, and the anhydrous sodium sulfate was filtered off. The ether layer was concentrated by an evaporator, followed by drying at 70 to 75 ° C by a vacuum pump until a constant amount was obtained. 1. Ig-I (I) is obtained. IH-NMR (300 MHz, DMS〇-D6) δ 7. 7 8 (12Η, m), 1. 3 2 (2 7Η, s)

(CeF5)3B-〇=N-B{C6F5)3

合成 &lt;Synthesis Example 5&gt; (Synthesis of ion pair (J)) A 200 ml 4-neck flask was replaced with nitrogen, and 1, Γ-dibenzyl-4,4'-bipyridyl rust dichloride was added. 205 g Compound Η 1. 089 g, 20 ml of ion-exchanged water and 60 ml of diethyl ether. After installing a stir bar, a thermometer and a condenser of 80 321 711 201035283, the reaction was carried out for 18 hours at 21 to 23 °C. After the reaction, the grains in the flask were transferred to a 2 ml ml separatory funnel, and the aqueous layer was separated. Next, the ether layer was washed three times with 30 ml of water by the ion father. The ether layer was transferred to a 200 ml triangular flask and dehydrated by adding anhydrous sodium sulfate, and anhydrous sodium sulfate was filtered off. The ether layer was concentrated by an evaporator. Further, at 80 to 851:, it is dried by a vacuum pump until it becomes a constant amount. 1. 21 g of ion pair J was obtained. 1 H-NMR (2 7 0MHz, DMS〇-D6) δ 9· 50 1 (4H, d), 8· 7 3 3 (4H, d), 7. 6〇6 (4H, m) 〇, 7· 4 7 9 (6H, m)

[{CeF^BC^N-BiCeFsJs]® &lt;Synthesis Example 6&gt;(Synthesis of ion pair (k)) q Nitrogen replacement was carried out on a 5-inch flask of 5 〇ml, and charged into poly(i_正丁j -4) - Vinyl acridine rust trifluoromethanesulfonimide) 0.3 〇 9 g, 1.088 g of the compound hydrazine and 30 ml of decyl decylamine. After installing the condenser, at 21 to 23. 〇, Reaction 16 = Select the stick, thermometer and 8 contents to transfer to the 2_1 separatory funnel. After the reaction, 50 ml of exchange water was burned to extract the beach. With water 5 〇 πι 1 xylene _, transfer from the layer to the 2_Triangle flask and add 8 no layers of stupid 3 times. Hyperthyroidism except for the anhydrous sulfur axis. After dehydration of 7 () to diacid dihydrate by an evaporator, drying was carried out by means of a vacuum pump until the concentration of the toluene layer was reduced. The ion pair κ of LOh 321711 81 201035283 was obtained. 1 H-NMR (300 MHz, DMSO~D6) δ 5. 8, 7. 4, 9. 1 1 9 F-NMR (300 MHz, DMS 〇-D6) 5 - 1 3 2. 7, 133. 6 , 134. 8, 157. 7, 159. 8, -162. 5,-164. 0,-165. 2,-166. 0

&lt;Synthesis Example 7&gt; (Synthesis of ion pair (L)) A 200 ml 4-neck flask was replaced with nitrogen, and 1.89 g of the compound H, 20 ml of ion-exchanged water, and 50 ml of diethyl ether were charged. After installing a stir bar, a thermometer and a condenser, 1% hydrochloric acid llg was dropped at 21 to 23 ° C for 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 three times with 30 ml of ion-exchanged water. The ether layer was transferred to a 200 ml Erlenmeyer flask and dehydrated with anhydrous sodium sulfate, and anhydrous sodium sulfate was filtered off. The organic layer was concentrated by an evaporator. Further, it was dried at 80 to 85 ° C by a vacuum pump until it became a constant amount. Obtained 1.06g of ion pair L. 82 321711 201035283 1 9 F_NMR (3 〇〇MH z, DMS〇—) δ-132. 7,- 1 33 7,-134. 3,-154. 8,-i57&gt; g -159. 2. “161. 〇, one 162.9, -164. 3, -165 4 __ 165.8, a 166.5

H 〇 [(c6f5) 3b-c valence B (C6F5) 3] G (L) <Preparation of coating solution A> O The polymer compound 1 is dissolved in xylene at a concentration of 重量.0% by weight and then 'relative' The weight of the polymer compound i is a mixed ion pair (I) of a bath of 〇. 2%. Next, the solution was filtered through a Teflon (registered trademark) filter having a pore size of 〇. 2 # m to prepare a coating solution A. &lt;Preparation of Coating Solution B&gt; The polymer compound 1 was dissolved in diphenylbenzene at a concentration of 1.0% by weight, and then passed through a Teflon (registered trademark) filter having a pore size of 22/im. Solution solution B was prepared. 〇 <Preparation of coating solution C> The polymer compound i is dissolved in dioxane f at a concentration of 1.0% by weight, and then mixed with a solution of 2% by weight based on the weight of the polymer compound 1. The ion pair M (N,N-dimercaptophenyl rust tetrakis(pentafluorophenyl) borate (manufactured by STREM CHEMICALS)) represented by the following formula. The solution was filtered by a Teflon (registered trademark) transition vessel having a pore size of 22. to prepare a coating solution C. 321711 83 201035283

(Μ) &lt;Production of Coating Solution D&gt; The polymer compound 1 was dissolved in diterpene benzene at a concentration of 1.0% by weight and then mixed with a weight of the polymer compound 1 to a weight of 0.2%. An ion pair N(4-isopropyl-4,-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following formula. Next, the solution was filtered through a Teflon (registered trademark) filter of 0.20m to prepare a coating solution D.

<Preparation of coating solution> X (4) The concentration of 4% by weight causes the polymer compound 1 to be dissolved in the two's, and then it becomes 0.2% white weight relative to the polymerized 署 嗖汸 old man π 1 The second ion pair (8). Then, by the aperture oil 〇n ((4) riding) (4) _ return, f recording cloth 321711 84 201035283 breaking &lt; preparation of coating solution F &gt; Dissolving polymer compound 1 in the concentration of 1.0% by weight苯, Then, the ion pair (J) is mixed with a solution of 0.2% by weight with respect to the weight of the polymer compound 1. Next, the solution was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 m to prepare a coating solution F. The solution of the solution of the ruthenium weight of 0.2% by weight of the polymer compound 1 is dissolved in a concentration of 1.0% by weight. Ion pair (K). Next, the solution was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 / zm to prepare a coating solution G. The solution of the mixed ion pair in a solution of 0.2% by weight based on the weight of the polymer compound 1 is dissolved in a concentration of 1.0% by weight. (L). Next, the solution was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 m/z m to prepare a coating solution.实施 <Example 1> (Production and evaluation of organic electroluminescent element) On a glass substrate to which an indium tin oxide (IT0) film having an anode of 150 nm thickness was attached by sputtering, spin coating was used. The film injection layer solution (manufactured by HC Starck GmbH, trade name: CLEVIOS AI4083) was formed into a film, and dried in a hot plate at 200 ° C for 10 minutes in the atmosphere to prepare a hole injection layer (film thickness: 65nm). Next, the polymer compound 2 xylene solution was filtered through a Teflon (registered trademark) filter having a pore size of 22/zm, and then applied to the hole injection layer by spin coating, in the hand 85 321711 201035283 The hole transporting layer (film thickness: 20 nm) was prepared by baking at 180 ° C for 15 minutes in a nitrogen atmosphere in a box. Further, the coating solution A was applied onto the hole transport layer by spin coating to form a light-emitting layer. In the production of the light-emitting layer, the film thickness was adjusted to 80 nm. Then, after baking for 10 minutes under a nitrogen atmosphere on a hot plate at 130 ° C, NaF was distilled at a thickness of 4 nm, and then A1 was vapor-deposited to a thickness of 100 nm to form a cathode. The vacuum degree of the vapor deposition is in the range of lxlO_4Pa to 9x1 (T3Pa. The shape of the element is a regular square of 2 mm x 2 mm. The obtained component is applied periodically from -5 V to 15 V, and voltage is applied periodically at intervals of 0.2 V. An electric field treatment was performed to produce an organic electroluminescent device. The energization time was once for one second with each voltage. Then, the constant current driving life test was performed at an initial luminance of 5000 cd/m 2 until the initial luminance was 4000 cd/m 2 ( The time until the initial brightness is 80%) (referred to as LT80). The results are shown in Table 1. The voltage at the start of the drive of the constant current drive life test is about 7.5 V. &lt;Example 2&gt; Preparation and Evaluation of Organic Electric Field Light-Emitting Element) An organic electric field light-emitting element was produced by the same method as in Example 1 except that the applied voltage applied to the element was 15 V and the energization time was once every one second. The LT80 of the organic electroluminescent element is shown in Table 1. The voltage at the start of the driving of the constant current driving life test is about 7.6 V. &lt;Example 3 &gt; 86 321711 2 01035283 (Production and evaluation of organic electroluminescent element) An organic electroluminescent element was produced by the same method as in Example 1 except that the applied voltage applied to the element was 20 V and the energization time was once every 1 second. The LT80 of the organic electroluminescent device is obtained. The results of the measurement are shown in Table 1. In addition, the driving of the constant current driving life test is about 7.5 V. &lt;Example 4&gt; Manufacture and evaluation of the device) The organic electroluminescent device was fabricated in the same manner as in Example 1 except that the coating solution C was used instead of the coating solution A, and the LT80 of the organic electroluminescent device was obtained. Further, the voltage at the start of the driving of the constant current driving life test is about 9.8 V. &lt;Example 5&gt; (Production and evaluation of organic electroluminescent element) In addition to coating using coating solution D The organic electroluminescent device was produced by the same method as in Example 1 except for the solution A, and the LT80 of the organic electroluminescent device was obtained. Further, the voltage at the start of the driving of the constant current driving life test is about 6.6 V. <Example θ> (Production and evaluation of organic electric field light-emitting element) The coating solution was replaced with a coating solution. The OT80 of the organic electroluminescent device was obtained by the same method as in Example 1 except that the organic electroluminescent device was produced in the same manner as in Example 1. The measurement results are shown in Table 1. Further, the driving of the constant current driving life test was started. The voltage system is about 6.7 V. 87 321711 201035283 &lt;Example 7 &gt; (Production and evaluation of organic electroluminescent element) The same applies to Example 1 except that the coating solution F is used instead of the coating solution A. In the method, an organic electroluminescence element was produced, and LT80 of the organic electroluminescence element was obtained. The measurement results are shown in Table 1. The voltage at the start of the driving of the constant current drive life test is about 7.2V. &lt;Example 8&gt; (Production and evaluation of organic electroluminescent device) An organic electroluminescent device was produced by the same method as in Example 1 except that the coating solution G was used instead of the coating solution A. LT80 of electric field illuminating element. The measurement results are shown in Table 1. The voltage at the start of the drive of the constant current drive life test is approximately 7. IV. &lt;Example 9&gt; (Production and evaluation of organic electroluminescent device) An organic electroluminescent device was produced by the same method as in Example 1 except that the coating solution A was used instead of the coating solution A. LT80 of electric field illuminating element. The measurement results are shown in Table 1. The voltage at the start of the driving of the constant current drive life test is about 6.6 V. <Comparative Example 1 &gt; Wide - (Production and Evaluation of Organic Electric Field Light-Emitting Element) The same procedure as in Example 1 was carried out except that no voltage was applied to the element before the start of driving of the constant current driving life test. The organic electric field light-emitting element was obtained as the LT80 of the organic electric field light-emitting element. The results of the measurements are shown in Table 1. In addition, the drive of the constant current drive life test 88 321711 • 4 201035283 The voltage at the beginning is about 7. IV, and the voltage when the LT80 passes is about 8.8V. <Comparative Example 2> (Preparation and evaluation of organic electroluminescent device) In addition to the application of the coating solution B in place of the coating solution A, before the start of the driving of the constant current drive and the life test, the components are not energized. An organic electroluminescent device was produced in the same manner as in Example 1, and LT80 of the organic electroluminescent device was obtained. The results of the measurements are shown in Table 1. 5伏。 The voltage of the LT80 is about 4. 5V. &lt;Comparative Example 3 &gt; (Production and Evaluation of Organic Electric Field Light-Emitting Element) Except that the coating solution B was used instead of the coating solution A, the applied voltage applied to the element was 15 V, and the energization time was once every 1 second. An organic electroluminescent device was produced in the same manner as in Example 1 to obtain an LT80 of an organic electroluminescent device. The measurement results are shown in Table 1.

5伏。 The voltage is about 4. 4V when the drive of the LT80 is about 4. 9V. &lt;Comparative Example 4 &gt; (Production and Evaluation of Organic Electric Field Light-Emitting Element) Except that the coating solution B was used instead of the coating solution A, the applied voltage applied to the element was 20 V, and the energization time was once every 1 second. An organic electroluminescent device was produced in the same manner as in Example 1 to obtain an LT80 of the organic electroluminescent device. The measurement results are shown in Table 1. 89 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 &lt;Comparative Example 5 &gt; (Production and Evaluation of Organic Electric Field Light-Emitting Element) Except that the coating solution C was used instead of the coating solution A, the element was not subjected to the energization treatment before the start of the driving of the constant current driving life test. An organic electroluminescent device was produced in the same manner as in Example 1 to obtain an LT80 of the organic electroluminescent device. The measurement results are shown in Table 1. 2伏。 The voltage of the LT80 is about 10. 2V. &lt;Comparative Example 6 &gt; (Production and Evaluation of Organic Electric Field Light-Emitting Element) Except that the coating solution D was used instead of the coating solution A, the element was not subjected to the energization treatment until the element was driven before the start of the driving of the constant current driving life test. An organic electroluminescent device was produced in the same manner as in Example 1 to obtain an LT80 of the organic electroluminescent device. The measurement results are shown in Table 1. In addition, the voltage at the start of the drive of the constant current drive life test is about 6.7 V, and the voltage at the time of passage of the LT 80 is about 8. IV. &lt;Comparative Example 7 &gt; (Production and Evaluation of Organic Electric Field Light-Emitting Element) Except that the coating solution E was used instead of the coating solution A, the element was not subjected to the energization treatment before the start of the driving of the constant current driving life test. An organic electroluminescent device was produced in the same manner as in Example 1 to obtain an LT80 of the organic electroluminescent device. The measurement results are shown in 90 321711 201035283 w Table 1. The voltage is about 7.4V when the LT80 passes. The voltage is about 7.4V when the LT80 passes. &lt;Comparative Example 8 &gt; (Production and Evaluation of Organic Electric Field Light-Emitting Element) - Except that the coating solution F was used instead of the coating solution A, the current was driven, and before the start of the driving of the life test, the element was not energized. In the same manner, an organic electroluminescent device was produced in the same manner as in Example 1, and LT80 of the organic electroluminescent device was obtained. The results of the measurements are shown in Table 1. The voltage at the start of the LT80 is about 7.9 V. &lt;Comparative Example 9 &gt; (Production and Evaluation of Organic Electric Field Light-Emitting Element) Except that the coating solution G was used instead of the coating solution A, the element was not subjected to the energization treatment before the start of the driving of the constant current driving life test. An organic electroluminescent element q was fabricated in the same manner as in Example 1 to obtain LT80 of the organic electroluminescent device. The measurement results are shown in Table 1. The voltage at the start of the LT80 is about 7.9 V. <Comparative Example 10 &gt; (Production and Evaluation of Organic Electric Field Light-Emitting Element) The coating solution A was used instead of the coating solution A, and before the start of driving of the constant current driving life test, the components were not energized, and the others were borrowed. An organic electroluminescent device was produced in the same manner as in Example 1, and LT80 of the organic electroluminescent device was obtained. The measurement results are shown in Table 1 of 91 321711 201035283. In addition, the voltage at the start of the drive of the constant current drive life test is about 6.6 V, and the voltage at the passage of the LT 80 is about 7. π. Table 1 EXAMPLES EXAMPLES EXAMPLES EXAMPLES EXAMPLES EXAMPLE 6 EXAMPLES EXAMPLES Example 9 Comparative Example 1 Comparative Example Comparative Example 4 Comparative Example LT80 (hours) 15 hours 10 hours 11. 5 hours 11. 5 hours 8. 2 hours 11. 5 hours 15. 5 hours 13. 5 hours 13. 0 hours 7. 5 hours 0. 5 hours of ionization treatment of 10V or more 1 (coating solution A) K coating solution A) 1 (coating Solution A) Μ (coating solution c) --------- Ν (coating solution D) Η (coating solution Ε) J (coating solution F) Κ (coating solution G) L (coating Cloth solution Η) Coating solution Α) There are some or none of the comparative examples (coating solution Β) None (coating solution Β)

Comparative Example 8 ------- Comparative Example ------ 6. 0 hours J (coating solution F) Κ (coating solution G) No 5. 5 hours Comparative Example 10 No 4. 0 hours L (Coating solution η) No evaluation 1. It is known from Table 1 that luminescence is formed by using a composition containing a conjugated polymer compound (polymer 321711 92 201035283 compound 1) and an ion pair (Η) to (N). The organic electroluminescent device in which the voltage is applied to the layer and the energization treatment is performed is longer than the organic electroluminescence device that does not perform the energization treatment or the organic electroluminescence device that does not contain the ion pairs (H) to (N). - [Industrial Applicability] The organic electroluminescent device of the present invention has a long life until the brightness becomes 80 in a state where the luminance at the start of driving is 100. Therefore, the present invention is extremely useful industrially. . 〇 [Simple description of the diagram] None. [Main component symbol description] None 0 93 321711

Claims (1)

201035283 VII. Patent application scope: - An organic electric field light-emitting element, which is formed by forming a laminate 11 having the following steps: an anode comprising the formula (la), the formula (lb), the formula (2) or The ion pair of the anion represented by the formula (3) and the light-emitting layer of the polymer light-emitting body, and the cathode 'applying a voltage of 10 μm or more between the anode and the cathode, and energizing the current from the anode to the cathode Processed, and obtained; (1a) (lb) (wherein Y1 represents a quinone 13 atom, Arl represents an aryl group having an electron attracting group or an ivalent heterocyclic group having an electron attracting group, and q1 represents an oxygen oxime bond , ^ shirt from the material, burning base, ethoxy group, sulfur-based, aryl, aryloxy, arylthio, aryl, aryl alkoxy, aromatic silk, county, silk, aryl base , aryl block, substituted oxy, substituted Weis, substituted Wei, substituted amine, decyl, fluorene, decyl, monovalent heterocyclic, heteroaryloxy, heteroaromatic a group, a cyano group or a fluorene group, a is an integer representing the number of '^, and the group k represents an integer of 1 to 4, and v1 represents a group 16 valence aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a 2-dentyl heterocyclic group, —CsN. —, —N=N=N- or direct key, b is an integer from 2 to 6, zl is a table 321711 94 201035283 shows -M'( = 0)p- (where M is a family, 6th Atoms of Family, Group 7, Group 3, Group 4, Group 5, Group 12, Group r3,: Group 9, Group 10, Group or Group 17, ? Family, Group K, 16th means (4) (4) group hydrocarbon group, integer of 2), or Is -C ... ™,: = fun group, b teeth heterocyclyl group, that, in zm〇) t _, - CsnH2 '' or a direct bond; however. - In the state of brain- or -0H-, b=2, ~N=N=N_, -NH~, A!, '2 and v1 are different, and γ1, Q1, ... are in a plurality of states, The system can be the same, and the two are different. The plurals can be the same, or the 'c can be an integer from 1 to 6. (Ai^-Q^d X2 (2-d) :d/Y2( (Q2 is ▽ X2(2-d·) (2) G (wherein Υ2 represents a group 13 atom, and Ar2 represents an aryl group having an electron attracting group or an i-valent heterocyclic group having an electron attracting group; , 〇 2 represents an oxygen atom or a direct bond, and χ 2 represents a 4-atom atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an aryl alkoxy group, Arylalkylthio, alkenyl, alkynyl, arylalkenyl, arylalkynyl, substituted decyloxy, substituted decylthio, substituted decylamino, substituted amine, decyl, quinone, a methoxy group, a fluorene heterocyclic group, a heteroaryloxy group, a heteroarylthio group, a gas group or an exact group, d and d' are the same or different and represent 1 or 2, and f is a group 16 atom, 2 valence Aliphatic hydrocarbon group, divalent aromatic hydrocarbon group, 2-dentate heterocyclic group, -C eN- or -N==N-, plural 321711 95 201035283 Χ2Λ^ Ar q and ν2 systems can be the same or different, X is a plural existence state, (4) can be the same, e system means 1 to 6 Integer) Wherein Y+ is a group 13 atom, and red 3 is a monovalent heterocyclic group having an electron withdrawing group or an electron attracting group, Q3 is an oxygen atom or a direct bond, and v3 is a 16th. a group atom, a divalent aliphatic group, a divalent aromatic hydrocarbon group, a 2-dentate heterocyclic group, a -CeN_ or 2. '(four)-, a plurality of 丫3, 仏 (^ and &quot; respectively can be the same, It can be different, f is an integer from 丨 to 6). For example, apply for the organic electric field starting part of the first item, including the formula (la) and the formula (A1 of (8), the red of formula (2), and the Ar3 system of perfluoroantimony of formula (3). The organic electric field light-emitting element of the above-mentioned item (a), wherein the type is 2 or 3. The organic electroluminescent element of any one of claims 1 to 3 is in the formula (la) The organic electroluminescent device of any one of the first to fourth aspects of the invention, wherein the anion system (5-1) or the formula (5_2) of the formula (la) Anion shown; 321711 96 201035283 [(CeF5&gt;3B-CsN - B(C6F5)3 j J M-[~C=N-B(C6F5)3j^ J (wherein M represents a nickel atom or a palladium atom) (5-1) (5-2) ' 6. The organic electroluminescent device of claim 1 or 2, wherein in the formula (lb), k is 3 or more. 7. a sixth-order organic electroluminescent device, wherein an anion represented by the formula (lb) has an anion represented by the formula (lb-2); 0 [B(Ar4)4]·(lb-2) (wherein the Ar4 system represents 2 selected from the group consisting of a fluorine group and a trifluoromethyl group The phenyl group substituted by the above-mentioned group, the plurality of Ar4 systems may be the same or different, respectively. 8. The organic electroluminescent device according to any one of claims 1 to 7, wherein the ion pair a cationic hydrogen ion, a metal cation or a carbocation, or a group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, a ruthenium atom, a ruthenium atom, a desert atom, a hoof atom, and a broken atom. The 001 to 10 weight, when the amount of the ion pair is 100 parts by weight of the polymer illuminant, the weight of the element is from 0.001 to 10 parts by weight. 10. The organic electroluminescent device of any one of claims 1 to 9, wherein the voltage for energization treatment is 100 V or less. 97 321711 201035283 \ IV. Designated representative figure: There is no drawing in this case. The designated representative figure of this case is: ( ). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 3217Γ