CN110520427A - Novel heterocyclic compounds and the organic illuminating element for utilizing it - Google Patents

Novel heterocyclic compounds and the organic illuminating element for utilizing it Download PDF

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CN110520427A
CN110520427A CN201880021113.6A CN201880021113A CN110520427A CN 110520427 A CN110520427 A CN 110520427A CN 201880021113 A CN201880021113 A CN 201880021113A CN 110520427 A CN110520427 A CN 110520427A
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chemical formula
compound
layer
mentioned
illuminating element
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CN110520427B (en
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车龙范
许瀞午
金渊焕
全相映
李成宰
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LG Chem Ltd
LG Corp
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    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
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    • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
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Abstract

The present invention provides novel heterocyclic compounds and the organic illuminating element using it.

Description

Novel heterocyclic compounds and the organic illuminating element for utilizing it
Technical field
With the mutual reference of related application
This application claims South Korea patent application No. 10-2017-0083851 and 2018 5 based on June 30th, 2017 Months 25 days South Korea patent application the 10-2018-0059816th priority, it is public in the document comprising the South Korea patent application The full content as part of this specification opened.
The present invention relates to novel heterocyclic compounds and include its organic illuminating element.
Background technique
Under normal conditions, organic light emission phenomenon refers to the phenomenon that making electric energy be converted to luminous energy using organic substance.Using having The organic illuminating element of machine luminescence phenomenon have wide viewing angle, excellent contrast, fast response time, brightness, driving voltage and Response speed excellent, to largely be studied.
Organic illuminating element usually has the organic matter layer comprising anode and cathode and between anode and cathode Structure.In order to improve the efficiency and stability of organic illuminating element, above-mentioned organic matter layer is in most cases by being utilized respectively difference Substance constitute multilayered structure formed, for example, can by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, The formation such as electron injecting layer.For the structure of such organic illuminating element, if applying voltage between electrodes, Hole is injected into organic matter layer from anode, and electronics is injected into organic matter layer from cathode, when institute's injected holes and electronics meet It will form exciton (exciton), and light will be issued when the exciton transits to ground state again.
It is lasting to require exploitation new material for the organic matter for organic illuminating element as described above.
Existing technical literature
Patent document
(patent document 0001) Korean Patent Publication No. the 10-2013-073537th
Summary of the invention
The project for needing to solve
The present invention relates to novel heterocyclic compounds compound and include its organic illuminating element.
The solution of project
The present invention provides the compound indicated by following chemical formula 1.
[chemical formula 1]
In above-mentioned chemical formula 1,
X1For O, S or NR1,
R1For substituted or unsubstituted unsubstituted C1-60Alkyl,
X2、X3And X4Be each independently N or CR', wherein one of which the above are N,
R ' is hydrogen or substituted or unsubstituted C1-60Alkyl,
Ar1And Ar2It is each independently substituted or unsubstituted C6-60Aryl or comprising more than one in N, O and S Substituted or unsubstituted C5-60Heteroaryl.
In addition, the present invention a kind of organic illuminating element is provided comprising: it is first electrode, opposed with above-mentioned first electrode And the second electrode that has and has one layer or more of organic matter between above-mentioned first electrode and above-mentioned second electrode Layer, one layer or more in above-mentioned organic matter layer includes above-mentioned the compound of the present invention.
Invention effect
The above-mentioned compound indicated by chemical formula 1 can be used as the material of the organic matter layer of organic illuminating element, organic It can be realized the raising of efficiency, the raising of lower driving voltage and/or life characteristic in light-emitting component.In particular, by above-mentioned Chemical formula 1 indicate compound can be used as electron injection, hole transport, hole injection and transmission, shine, electron-transport or Electron injection material.
Detailed description of the invention
Fig. 1 illustrates the examples for the organic illuminating element being made of substrate 1, anode 2, luminescent layer 3, cathode 4.
Fig. 2 illustrate by substrate 1, anode 2, hole injection layer 5, hole transmission layer 6, luminescent layer 7, electron transfer layer 8, with And the example of the organic illuminating element of the composition of cathode 4.
Specific embodiment
In the following, being illustrated in more details to help to understand the present invention.
The present invention provides the compound indicated by following chemical formula 1.
[chemical formula 1]
In above-mentioned chemical formula 1,
X1For O, S or NR1,
R1For substituted or unsubstituted unsubstituted C1-60Alkyl,
X2、X3And X4It is each independently N or CR ', but one of which is the above are N,
R ' is hydrogen or substituted or unsubstituted C1-60Alkyl,
Ar1And Ar2It is each independently substituted or unsubstituted C6-60Aryl or comprising more than one in N, O and S Substituted or unsubstituted C5-60Heteroaryl.
In this specification,Refer to the key connecting with other substituent groups.
In this specification, " substituted or unsubstituted " this term is meant by selected from deuterium, halogen group, itrile group, nitre Base, hydroxyl, carbonyl, ester group, imide, amino, oxidation phosphino-, alkoxy, aryloxy group, alkyl sulfenyl (Alkyl thioxy), artyl sulfo (Aryl thioxy), alkyl sulfonyl Base (Alkyl sulfoxy), aryl sulfonyl (Aryl sulfoxy)、 Silicyl, boryl, alkyl, naphthenic base, alkenyl, aryl, aralkyl, arylalkenyl, alkylaryl, alkyl amine group, aralkylamine Base, heteroaryl amido, arylamine group, aryl phosphino- include one in the more than one heterocycle in N, O and S atom The above substituent group is substituted or unsubstituted, or is taken by what 2 or more substituent groups in foregoing illustrative substituent group were formed by connecting It is substituted or unsubstituted for base.For example, " substituent group that 2 or more substituent groups are formed by connecting " can be xenyl.That is, xenyl It can be aryl, can also be interpreted the substituent group that 2 phenyl are formed by connecting.
In this specification, the carbon atom number of carbonyl is not particularly limited, but preferably carbon atom number is 1 to 40.Specifically, It can be the compound of following structure, but not limited to this.
In this specification, in ester group, the oxygen atom of ester group can be by the straight chain of carbon atom number 1 to 25, branch or cyclic annular alkane Base or the aryl of carbon atom number 6 to 25 replace.Specifically, can be the compound of following structural formula, but not limited to this.
In this specification, the carbon atom number of imide is not particularly limited, but preferably carbon atom number is 1 to 25.Specifically For, it can be the compound of following structure, but not limited to this.
In this specification, silicyl specifically has trimethyl silyl, triethylsilyl, tertbutyldimethylsilyl chloride Silylation, vinyldimethylsilyl, propyl-dimethyl silicyl, triphenyl-silyl, diphenylsilyl group, Phenyl silyl groups etc., but not limited to this.
In this specification, boryl specifically has trimethyl boryl, triethyl group boryl, fert-butyidimethylsilyl boryl, triphenyl borine Base, phenyl boryl etc., but not limited to this.
In this specification, as the example of halogen group, there are fluorine, chlorine, bromine or iodine.
In this specification, abovementioned alkyl can be linear chain or branched chain, and carbon atom number is not particularly limited, but preferably 1 to 40.According to an embodiment, the carbon atom number of abovementioned alkyl is 1 to 20.According to another embodiment, the carbon atom of abovementioned alkyl Number is 1 to 10.According to another embodiment, the carbon atom number of abovementioned alkyl is 1 to 6.As the specific example of alkyl, there is first Base, ethyl, propyl, n-propyl, isopropyl, butyl, normal-butyl, isobutyl group, tert-butyl, sec-butyl, 1- methyl-butvl, 1- second Base-butyl, amyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, n-hexyl, 1- methyl amyl, 2- methyl amyl, 4- Methyl -2- amyl, 3,3- dimethylbutyl, 2- ethyl-butyl, heptyl, n-heptyl, 1- methylhexyl, cyclopentyl-methyl, hexamethylene Ylmethyl, octyl, n-octyl, t-octyl, 1- methylheptyl, 2- ethylhexyl, 2- propylpentyl, n-nonyl, 2,2- dimethyl Heptyl, 1- Ethyl-propyl, 1,1- Dimethyl-propyl, isohesyl, 2- methyl amyl, 4- methylhexyl, 5- methylhexyl etc., but It's not limited to that.
In this specification, above-mentioned alkenyl can be linear chain or branched chain, and carbon atom number is not particularly limited, but preferably 2 to 40.According to an embodiment, the carbon atom number of above-mentioned alkenyl is 2 to 20.According to another embodiment, the carbon atom of above-mentioned alkenyl Number is 2 to 10.According to another embodiment, the carbon atom number of above-mentioned alkenyl is 2 to 6.As concrete example, there are vinyl, 1- third Alkenyl, isopropenyl, 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 1- pentenyl, 2- pentenyl, 3- pentenyl, 3- methyl-1- Cyclobutenyl, 1,3- butadienyl, allyl, 1- phenylethylene -1- base, 2- phenylethylene -1- base, 2,2- benzhydryl ethylene - 1- base, 2- phenyl -2- (naphthalene -1- base) ethylene -1- base, 2,2- bis- (hexichol -1- base) ethylene -1- base, Stilbene base, styryls etc., But not limited to this.
In this specification, naphthenic base is not particularly limited, but the naphthenic base of preferably carbon atom number 3 to 60, real according to one Mode is applied, the carbon atom number of above-mentioned naphthenic base is 3 to 30.According to another embodiment, the carbon atom number of above-mentioned naphthenic base be 3 to 20.According to another embodiment, the carbon atom number of above-mentioned naphthenic base is 3 to 6.Specifically, having cyclopropyl, cyclobutyl, ring penta Base, 3- methylcyclopentyl, 2,3- dimethylcyclopentyl, cyclohexyl, 3- methylcyclohexyl, 4- methylcyclohexyl, 2,3- dimethyl Cyclohexyl, 3,4,5- trimethylcyclohexyls, 4- tert-butylcyclohexyl, suberyl, cyclooctyl etc., but not limited to this.
In this specification, aryl is not particularly limited, but the aryl of preferably carbon atom number 6 to 60, can be monocycle virtue Base or polyaromatic.According to an embodiment, the carbon atom number of above-mentioned aryl is 6 to 30.According to an embodiment, above-mentioned aryl Carbon atom number be 6 to 20.It can be phenyl, xenyl, terphenyl etc. as monocyclic aryl, but simultaneously about above-mentioned aryl It is not limited to this.As above-mentioned polyaromatic, can for naphthalene, anthryl, phenanthryl, pyrenyl, base,Base, fluorenyl etc., but simultaneously It is not limited to this.
In this specification, fluorenyl can be substituted, and 2 substituent groups can be bonded to each other and form spiro structure.In above-mentioned fluorenes In the substituted situation of base, it can become Deng but not limited to this.
In this specification, heterocycle is comprising more than one in O, N, Si and S as heteroatomic heterocycle, carbon atom Number is not particularly limited, but preferably carbon atom number is 2 to 60.As the example of heterocycle, have thienyl, furyl, pyrrole radicals, Imidazole radicals, thiazolyl,Oxazolyl,Di azoly, triazolyl, pyridyl group, bipyridyl, pyrimidine radicals, triazine radical, triazolyl, Acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolyl, quinoxalinyl, phthalazinyl, Pyridopyrimidine base, pyrido-pyrazine Base, pyrazine and pyrazinyl, isoquinolyl, indyl, carbazyl, benzoOxazolyl, benzimidazolyl, benzothiazolyl, benzo It is carbazyl, benzothienyl, dibenzothiophene, benzofuranyl, phenanthroline (phenanthroline), thiazolyl, differentOxazolyl,Di azoly, thiadiazolyl group, benzothiazolyl, phenothiazinyl and dibenzofuran group etc., but it is not limited only to this.
In this specification, the example phase of aralkyl, arylalkenyl, alkylaryl, aryl and above-mentioned aryl in arylamine group Together.In this specification, aralkyl, alkylaryl, the alkyl in alkyl amine group are identical as the example of abovementioned alkyl.This specification In, the heteroaryl in heteroaryl amine can be applicable in the above-mentioned explanation about heterocycle.In this specification, alkenyl in arylalkenyl with The example of above-mentioned alkenyl is identical.In this specification, arlydene is that divalent group can be applicable in above-mentioned about aryl in addition to this Explanation.In this specification, heteroarylidene is that divalent group can be applicable in the above-mentioned explanation about heterocycle in addition to this.This In specification, hydrocarbon ring not instead of 1 valence group, 2 substituent groups are combined into, and in addition to this, can be applicable in above-mentioned about aryl Or the explanation of naphthenic base.In this specification, heterocycle not instead of 1 valence group, 2 substituent groups are combined into, in addition to this, can be with It is applicable in the above-mentioned explanation about heterocycle.
Preferably, the compound indicated by above-mentioned chemical formula 1 can be for by any of following chemical formula 1-1 to 1-4 table The compound shown.
[chemical formula 1-1]
[chemical formula 1-2]
[chemical formula 1-3]
[chemical formula 1-4]
Above-mentioned chemical formula 1-1 into 1-4,
X1、X2、X3、X4、Ar1And Ar2It is as defined above.
Preferably, the compound of above-mentioned chemical formula 1-1 can be the compound indicated by following chemical formula 1-la to 1-lc Any of.
[chemical formula 1-la]
[chemical formula 1-1b]
[chemical formula 1-1c]
Above-mentioned chemical formula 1-la into 1-lc,
X1、X2、X3、X4、Ar1And Ar2It is as defined above.
Preferably, the compound of above-mentioned chemical formula 1-2 can be the compound indicated by following chemical formula 1-2a or 1-2b.
[chemical formula 1-2a]
[chemical formula 1-2b]
In above-mentioned chemical formula 1-2a or l-2b,
X1、X2、X3、X4、Ar1And Ar2It is as defined above.
Preferably, the compound of above-mentioned chemical formula 1-3 can be the compound indicated by following chemical formula 1-3a to 1-3c Any of.
[chemical formula 1-3a]
[chemical formula l-3b]
[chemical formula 1-3c]
Above-mentioned chemical formula l-3a into 1-3c,
X1、X2、X3、X4、Ar1And Ar2It is as defined above.
Preferably, the compound of above-mentioned chemical formula 1-4 can be the compound indicated by following chemical formula l-4a or 1-4b.
[chemical formula l-4a]
[chemical formula 1-4b]
In above-mentioned chemical formula l-4a or l-4b,
X1、X2、X3、X4、Ar1And Ar2It is as defined above.
Preferably, Ar1And Ar2It is each independently selected from any of following radicals.
In addition, it is highly preferred that Ar1And Ar2It is each independently
Preferably, the compound indicated by above-mentioned chemical formula 1 can be for selected from any of following compounds.
The compound indicated by above-mentioned chemical formula 1 can be manufactured by the manufacturing method of such as following reaction equations 1.It is above-mentioned Manufacturing method can further embody in aftermentioned Production Example.
[reaction equation 1]
In above-mentioned reaction equation 1, X1、X2、X3、X4、Ar1And Ar2It is as defined above, X indicate halogen atom F, Cl, Br, I.Reactant for above-mentioned reaction equationIt can suitably be selected with catalyst type.Above-mentioned manufacturing method can be It is more specific in aftermentioned Production Example.
In addition, the present invention provides the organic illuminating element of the compound comprising being indicated by above-mentioned chemical formula 1.As an example Son, the present invention a kind of organic illuminating element is provided comprising: first electrode, it is opposed with above-mentioned first electrode and have Two electrodes and have one layer or more of organic matter layer between above-mentioned first electrode and above-mentioned second electrode, it is above-mentioned organic One layer or more the compound comprising being indicated by above-mentioned chemical formula 1 in nitride layer.
The organic matter layer of organic illuminating element of the invention can be formed by single layer structure, can also by be laminated with two layers with On the multilayered structure of organic matter layer formed.For example, organic illuminating element of the invention can have comprising hole injection layer, sky The structure as organic matter layer such as cave transport layer, luminescent layer, electron transfer layer, electron injecting layer.But organic illuminating element It's not limited to that for structure, may include lesser amount of organic layer.
In addition, above-mentioned organic matter layer may include hole injection layer, hole transmission layer or carry out hole injection and biography simultaneously Defeated layer, above-mentioned hole injection layer, hole transmission layer or to carry out the layer of hole injection and transmission simultaneously include by above-mentioned chemical formula 1 compound indicated.
In addition, above-mentioned organic matter layer may include luminescent layer, above-mentioned luminescent layer includes the chemical combination indicated by above-mentioned chemical formula 1 Object.
In addition, above-mentioned organic matter layer may include electron transfer layer or electron injecting layer, above-mentioned electron transfer layer or electronics Implanted layer includes the compound indicated by above-mentioned chemical formula 1.
In addition, above-mentioned electron transfer layer, electron injecting layer or carry out simultaneously electron injection and electron-transport layer include by The compound that above-mentioned chemical formula 1 indicates.In particular, the thermal stability of the compound according to the present invention indicated by chemical formula 1 is excellent It is different, and deep HOMO energy level, high triplet energy level (ET) and hole stability with 6.0eV or more.In addition, will be by above-mentionedization It, can be with the field when compound that formula 1 indicates for that can carry out the organic matter layer of electron injection and electron-transport simultaneously Used in n-type dopant be used in mixed way.
In addition, above-mentioned organic matter layer includes luminescent layer and electron transfer layer, above-mentioned electron transfer layer be may include by above-mentioned The compound that chemical formula 1 indicates.
In addition, organic illuminating element according to the present invention can be to be sequentially laminated with anode, one layer or more on substrate The organic illuminating element of the structure (standard type (normal type)) of organic matter layer and cathode.In addition, according to the present invention organic Light-emitting component (can be inverted for the reverse structure of the organic matter layer and anode that are sequentially laminated with cathode, one layer or more on substrate Type (inverted type)) organic illuminating element.For example, the knot of the organic illuminating element of an embodiment according to the present invention Structure is illustrated in Fig. 1 and 2.
Fig. 1 illustrates the examples for the organic illuminating element being made of substrate 1, anode 2, luminescent layer 3, cathode 4.In institute as above In the structure stated, it may be embodied in above-mentioned luminescent layer by the compound that above-mentioned chemical formula 1 indicates.
Fig. 2 illustrate by substrate 1, anode 2, hole injection layer 5, hole transmission layer 6, luminescent layer 7, electron transfer layer 8 with And the example of the organic illuminating element of the composition of cathode 4.In structure as described above, the compound that is indicated by above-mentioned chemical formula 1 It may be embodied in one layer or more in above-mentioned hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.
For organic illuminating element according to the present invention, one layer or more in above-mentioned organic matter layer includes by above-mentioned chemistry The compound that formula 1 indicates can be manufactured in addition to this by material well known to the technical field and method.In addition, when upper When stating organic illuminating element comprising multiple organic matter layers, above-mentioned organic matter layer can be by identical substance or different substance shapes At.
For example, organic illuminating element according to the present invention can be by stacking gradually first electrode, organic matter on substrate Layer and second electrode and manufacture.At this moment, it can manufacture as follows: utilize sputtering method (sputtering) or electron beam evaporation method (e- Beam evaporation) etc PVD (physical Vapor Deposition: physical vapour deposition (PVD)) method, in substrate Upper evaporation metal or conductive metal oxide or their alloy and form anode, then on the anode formed packet Organic matter layer containing hole injection layer, hole transmission layer, luminescent layer and electron transfer layer, vapor deposition can on the organic matter layer later Substance as cathode and manufacture.Other than this method, can also on substrate successively evaporation cathode substance, organic matter Layer, anode material and manufacture organic illuminating element.
In addition, the compound indicated by above-mentioned chemical formula 1 not only can use vacuum steaming when manufacturing organic illuminating element Plating method can also form organic matter layer using solution coating method.Herein, so-called solution coating method refers to, spin-coating method, dip-coating Method, knife coating, ink jet printing method, silk screen print method, spray-on process, rolling method etc., but it is not limited only to this.
In addition to these methods, can also on substrate successively evaporation cathode substance, organic matter layer, anode material and make Make organic illuminating element (WO2003/012890).But it's not limited to that for manufacturing method.
As an example, above-mentioned first electrode is anode, and above-mentioned second electrode is cathode or above-mentioned first electrode is Cathode, above-mentioned second electrode are anode.
As above-mentioned anode material, generally for enabling hole to be smoothly injecting into organic matter layer, preferably work function Big substance.As the concrete example of above-mentioned anode material, just like the metals such as vanadium, chromium, copper, zinc, gold or their alloy；Such as oxidation The metal oxides such as zinc, indium oxide, tin indium oxide (ITO), indium zinc oxide (IZO)；Such as ZnO:Al or SNO2: the metals such as Sb and oxygen The combination of compound；Such as poly- (3 methyl thiophene), poly- [3,4- (ethylidene -1,2- dioxy) thiophene] (PEDOT), polypyrrole and polyphenyl Electroconductive polymers such as amine etc., but it is not limited to this.
As above-mentioned cathode substance, generally for enabling electronics to be easily injected into organic matter layer, preferably work function Small substance.As the concrete example of above-mentioned cathode substance, just like magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminium, silver, tin and lead Equal metals or their alloy；Such as LiF/Al or LiO2Multilayered structures substance such as/Al etc., but it is not limited only to this.
Above-mentioned hole injection layer is the layer in the hole that injection carrys out self-electrode, as hole injecting material, preferably followingization Close object: the ability with transporting holes has hole injection effect from anode, for the excellent of luminescent layer or luminescent material Hole inject effect, prevent the exciton generated in luminescent layer from migrating to electron injecting layer or electron injection material, and film Forming ability is excellent.It is preferred that HOMO (highest occupied molecular orbital(HOMO), the highest occupied of hole injecting material Molecular orbital) between the work function of anode material and the HOMO of surrounding organic matter layer.As hole infusion The concrete example of matter has metalloporphyrin (porphyrin), Oligopoly thiophene, aryl amine system organic matter, six nitriles, six azepine benzophenanthrene system to have It is organic matter, anthraquinone and polyaniline and polythiophene that machine object, quinacridone (quinacridone), which are organic matter, (perylene), It is electroconductive polymer etc., but is not limited only to this.
Above-mentioned hole transmission layer is to receive the hole from hole injection layer and by the layer of hole transport to luminescent layer, as Hole transporting material is the substance that can be received the hole from anode or hole injection layer and transfer them to luminescent layer, empty Mobility big substance in cave is suitable.As concrete example, there are aryl amine system organic matter, electroconductive polymer and deposit simultaneously In conjugate moiety and the block copolymer of non-conjugated portion etc., but it is not limited only to this.
It is that can receive hole and electronics from hole transmission layer and electron transfer layer respectively as above-mentioned luminescent substance And make they in conjunction with and issue the substance of the light of visible light region, object preferably high for the quantum efficiency of fluorescence or phosphorescence Matter.As a specific example, there is 8-hydroxyquinoline aluminum complex (Alq3)；Carbazole based compound；Two is polystyrene-based (dimerized styryl) compound；BAlq；10- hydroxy benzo quinoline metal compound；BenzoAzoles, benzothiazole and Benzimidazole based compound；Poly- (to phenyleneethenyl) (PPV) is macromolecule；Loop coil (spiro) compound；It is polyfluorene, red glimmering Alkene etc., but it is not limited only to this.
Above-mentioned luminescent layer may include material of main part and dopant material.As material of main part, there is aromatic fused ring derivative Object or nitrogen-containing heterocgcies etc..Specifically, having anthracene derivant, pyrene derivatives, naphthalene derivative as aromatic fused ring derivative Object, pentacene derivative, phenanthrene compound, fluoranthene compound etc. have carbazole derivates, dibenzo furan as nitrogen-containing heterocgcies It mutters derivative, ladder type furan compoundAnd pyrimidine derivatives etc., but do not limit In this.
As above-mentioned dopant material, there are aromatic amine derivative, styrylamine compound, boron complexes, fluoranthene chemical combination Object, metal complex etc..Specifically, being the virtue with substituted or unsubstituted arylamino as aromatic amine derivative Fragrant race's fused-ring derivatives, have pyrene with arylamino, anthracene,Two indeno pyrenes (Periflanthene) etc., as styrene Ylamine compounds are to replace the compound for having at least one aryl vinyl on substituted or unsubstituted arylamine, are selected from Substituent group more than one or two of aryl, silicyl, alkyl, naphthenic base and arylamino is substituted or unsubstituted. Specifically, having styryl amine, styryl diamines, styryl triamine, styryl tetramine etc., but it is not limited to This.In addition, having complex of iridium, platinum complex etc., but not limited to this as metal complex.
Above-mentioned electron transfer layer is from electron injecting layer reception electronics and by the layer of electron-transport to luminescent layer, as electronics Transport materials are can to inject well electronics from cathode and transfer them to the substance of luminescent layer, the big object of electron mobility Matter is suitable.As concrete example, there is the Al complex of 8-hydroxyquinoline, comprising Alq3Complex, organic free radical chemical combination Object, flavonol-metal complex etc., but it is not limited only to this.Electron transfer layer can be as used in the prior art It is used together with the cathode substance of any desired.In particular, the example of suitable cathode substance be with low work function and with The common substance of aluminium layer or silver layer.Specially caesium, barium, calcium, ytterbium and samarium, with aluminium layer or silver layer in each situation.
Above-mentioned electron injecting layer is the layer for the electronics that injection carrys out self-electrode, preferably following compound: has transmission electronics Ability, there is electron injection effect from cathode, for the excellent electron injection effect of luminescent layer or luminescent material, prevent Only generated exciton is migrated to hole injection layer in luminescent layer, and film Forming ability is excellent.Specifically, have Fluorenone, Anthraquinone bismethane (Anthraquinodimethane), diphenoquinone, thiopyrandioxide,Azoles,Diazole, triazole, imidazoles, Tetrabasic carboxylic acid, fluorenylidene-methane, anthrone etc. and their derivative, metal complex and nitrogenous five-membered ring derivative Deng but not limited to this.
As above-mentioned metal complex, there are 8-hydroxyquinoline lithium, bis- (8-hydroxyquinoline) zinc, bis- (8-hydroxyquinolines) Copper, bis- (8-hydroxyquinoline) manganese, three (8-hydroxyquinoline) aluminium, three (2- methyl -8-hydroxyquinoline) aluminium, three (8-hydroxyquinolines) Gallium, bis- (10- hydroxy benzo [h] quinoline) berylliums, bis- (10- hydroxy benzo [h] quinoline) zinc, bis- (2- methyl -8- quinoline) gallium chlorides, Bis- (2- methyl -8- quinoline) (o-cresol) galliums, bis- (2- methyl -8- quinoline) (1- naphthols) aluminium, bis- (2- methyl -8- quinoline) (2- Naphthols) gallium etc., but not limited to this.
Organic illuminating element according to the present invention can be top emission type, bottom emission type or double according to the material used To light emitting-type.
In addition, the compound indicated by above-mentioned chemical formula 1 other than organic illuminating element, be further included in it is organic too In positive energy battery or organic transistor.
Manufacture to the compound and the organic illuminating element comprising it that are indicated by above-mentioned chemical formula 1 in the examples below It is concretely demonstrated.But following embodiments are for illustrating the present invention, it's not limited to that for the scope of the present invention.
<manufacture of midbody compound>
Production Example 1: the manufacture of midbody compound P-6
By the fluoro- 2- iodobenzene (1-bromo-3-fluoro-2-iodobenzene) (100g, 333.5mmol) of bromo- 3-, 5- Chloro- 2- methoxyphenylboronic acid ((5-chloro-2-methoxyphenyl) boronic acid) (62.2g, 333.5mmol) is molten Solution is in the tetrahydrofuran (THF) of 800ml.Sodium carbonate (Na is added thereto2CO3) 2M solution (500mL), tetrakis triphenylphosphine palladium (0)[Pd(PPh3)4] (7.7g, 6.7mmol), it flows back 12 hours.After reaction, it is cooled to room temperature, the mixture of generation is used Water and toluene extract 3 times.After separation of methylbenzene layer, it is dried with magnesium sulfate (magnesium sulfate), by the filtrate of filtering Vacuum distillation, obtained mixture utilizes chloroform, ethyl alcohol recrystallization 3 times, to obtain compound P-l (53.7g, yield 51%；MS:[M+H]+=314).
After compound P-l (50.0g, 158.5mmol) is dissolved in methylene chloride (Dichlorometahne) (600ml), It is cooled to 0 DEG C.After Boron tribromide (boron tribromide) (15.8ml, 166.4mmol) slowly is added dropwise, stir 12 hours. After reaction, it is washed with water 3 times, it is dry with magnesium sulfate (magnesium sulfate), the filtrate decompression of filtering is distilled, With column chromatographic purifying, to obtain compound P-2 (47.4g, yield 99%；MS:[M+H]+=300).
Compound P-2 (40.0g, 132.7mmol) is dissolved in the dimethylformamide (DMF) (400ml) of distillation.By its It is cooled to 0 DEG C, sodium hydride (sodium hydride) (3.5g, 145.9mmol) slowly is added dropwise thereto.It stirs after twenty minutes, It is stirred 1 hour at 100 DEG C.After reaction, it is cooled to room temperature, is slowly added into the ethyl alcohol (Ethanol) of 100ml.It will be above-mentioned mixed Mixture chloroform, re-crystallizing in ethyl acetate obtained from object vacuum distillation are closed, (30.3g is received to obtain compound P-3 Rate 81%；MS:[M+H]+=280).
After compound P-3 (30.0g, 106.6mmol) is dissolved in tetrahydrofuran (300ml), -78 DEG C are cooled the temperature to, It is slowly added into 1.7M tert-butyl lithium (t-BuLi) (62.7ml, 106.6mmol).After mutually synthermal stirring one hour, boron is added Sour three isopropyl esters (B (OiPr)3) (28.3ml, 213.1mmol), temperature is slowly promoted to room temperature, while stirring 3 hours.In 2N aqueous hydrochloric acid solution (200ml) is added in reaction mixture, at stirring at normal temperature 1.5 hours.The sediment of generation is filtered, successively After being washed with water and ether (ethyl ether), vacuum drying.After drying, it is scattered in ether, after stirring two hours, filtering, It is dry, to manufacture compound P-4 (24.4g, yield 93%；MS:[M+H]+=247).
By the chloro- 4,6- diphenyl -1,3,5- triazine (2-chloro-4,6- of compound P-4 (20.0g, 81.2mmol) and 2- Diphenyl-1,3,5-triazine) after (21.8g, 81.2mmol) is scattered in tetrahydrofuran (250ml), 2M potassium carbonate is added Aqueous solution (aq.K2CO3) (33.6ml, 243.5mmol), tetrakis triphenylphosphine palladium [Pd (PPh is added3)4] (1.9g, 2mol%) Afterwards, it is stirred at reflux 4 hours.Room temperature is cooled the temperature to, the solid of generation is filtered.By the solid tetrahydrofuran and acetic acid of filtering Ethyl ester recrystallization, after filtering, is dried, to manufacture compound P-5 (32.4g, yield 92%；MS:[M+H]+= 434)。
By compound P-5 (30g, 69.2mmol), bis- (pinacol combined) two boron (Bis (pinacolato) diborone) (19.3g, 76.1mmol), potassium acetate (potassium acetate) (20.4g, 207.5mmol), tetrakis triphenylphosphine palladium (0) [Pd(PPh3)4] (1.6g, 2mol%) be added in tetrahydrofuran (300ml), it flows back 12 hours.After reaction, it is cooled to often Temperature, vacuum distillation removal solvent.It is dissolved in chloroform (Chloroform), after being washed with water 3 times, separates organic layer, use Magnesium sulfate (Magnesium sulfate) is dried.It is evaporated under reduced pressure, to manufacture compound P-6 (34.5g, yield 95%；MS:[M+H]+=526).
Production Example 2: the manufacture of midbody compound P-8
By compound P-4 (40.0g, 162.3mmol) and 2- ([1,1 '-biphenyl] -4- base) -4- chloro-6-phenyl -1,3,5- Triazine (2- ([1,1 '-biphenyl] -4-yl) -4-chloro-6-phenyl-1,3,5-triazine) (55.8g, After 162.3mmol) being scattered in tetrahydrofuran (500ml), 2M wet chemical (aq.K is added2CO3)(67.2ml, 486.9mmol), tetrakis triphenylphosphine palladium [Pd (PPh is added3)4] after (3.8g, 2mol%), be stirred at reflux 4 hours.Temperature is dropped To room temperature, the solid of generation is filtered.By the solid tetrahydrofuran and re-crystallizing in ethyl acetate of filtering, after filtering, done It is dry, to manufacture compound P-7 (73.7g, yield 89%；MS:[M+H]+=510).
By compound P-7 (70.5g, 138.3mmol), bis- (pinacol combined) two boron (Bis (pinacolato) Diborone) (38.6g, 152.13mmol), potassium acetate (potassium acetate) (40.7g, 414.9mmol), four (three Phenylphosphine) palladium (0) [Pd (PPh3)4] (3.2g, 2mol%) be added in tetrahydrofuran (600ml), it flows back 12 hours.Reaction knot Shu Hou, after being cooled to room temperature, vacuum distillation removal solvent.It is dissolved in chloroform (Chloroform), after being washed with water 3 times, Organic layer is separated, is dried with magnesium sulfate (Magnesium sulfate).It is evaporated under reduced pressure, to manufacture compound P-8 (75.7g, yield 91%；MS:[M+H]+=602).
Production Example 3: the manufacture of midbody compound P-10
By compound P-4 (40.0g, 162.3mmol) and 2- ([1,1 '-biphenyl] -3- base) -4- chloro-6-phenyl -1,3,5- Triazine (2- ([1,1 '-biphenyl] -3-yl) -4-chloro-6-phenyl-1,3,5-triazine) (55.8g, After 162.3mmol) being scattered in tetrahydrofuran (500ml), 2M wet chemical (aq.K is added2CO3)(67.2ml, 486.9mmol), tetrakis triphenylphosphine palladium [Pd (PPh is added3)4] after (3.8g, 2mol%), it is stirred at reflux 4 hours.By temperature It is down to room temperature, the solid of generation is filtered.By the solid tetrahydrofuran and re-crystallizing in ethyl acetate of filtering, after filtering, carry out It is dry, to manufacture compound P-9 (69.5g, yield 84%；MS:[M+H]+=510).
By compound P-9 (70.5g, 138.3mmol), bis- (pinacol combined) two boron (Bis (pinacolato) Diborone) (38.6g, 152.13mmol), potassium acetate (potassium acetate) (40.7g, 414.9mmol), four (three Phenylphosphine) palladium (0) [Pd (PPh3)4] (3.2g, 2mol%) be added in tetrahydrofuran (600ml), it flows back 12 hours.Reaction knot Shu Hou is cooled to room temperature, then vacuum distillation removal solvent.It is dissolved in chloroform (Chloroform), is washed with water 3 times Afterwards, organic layer is separated, is dried with magnesium sulfate (Magnesium sulfate).It is evaporated under reduced pressure, to manufacture chemical combination Object P-10 (73.5g, yield 88%；MS:[M+H]+=602).
Production Example 4: the manufacture of midbody compound Q-4
Use (2- methoxyphenyl) boric acid ((2-methoxypheny1) boronic acid) (50.7g, 333.5mmol) replace the chloro- 2- methoxyphenylboronic acid of 5- ((5-chloro-2-methoxyphenyl) boronicacid) (62.2g, 333.5mmol) has obtained compound Q -1 (81.6g, yield by method identical with Production Example 1 in addition to this 87%；MS:[M+H]+=280).
Using compound Q -1 (75.7g, 269.4mmol) replace compound P-1 (85.0g0,269.4mmol), except this with Outside, compound Q -2 (71.2g, yield 99% have been obtained by method identical with Production Example 1；MS:[M+H]+=266).
Using compound Q -2 (70.9g, 265.3mmol) replace compound P-2 (80.0g, 265.3mmol), except this with Outside, compound Q -3 (62.3g, yield 95% have been obtained by method identical with Production Example 1；MS:[M+H]+=246).
Compound Q -3 (40g, 161.9mmol) is dissolved in the acetic acid (acetic acid) of 200ml.Iodine is added thereto (4.16g, 81.0mmol), acid iodide (6.3g, 36.0mmol), sulfuric acid (10ml) stir 3 hours at 65 DEG C.After reaction, cold But to room temperature, water is added.The solid of generation is filtered, after being washed with water, is recrystallized with toluene and ethyl acetate, to obtain Compound Q -4 (50.1g, yield 83%；MS:[M+H]+=372).
Production Example 5: the manufacture of midbody compound Q-5
By compound Q -4 (15.3g, 41.1mmol), 2 '-(4,4,5,5- tetramethyl -1,3,2- dioxaborolanes - 2- yl) spiral shell [indoles simultaneously [3,2,1-de] acridine -8,9 '-xanthene] (2 '-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)spiro[indolo[3,2,1-de]acridine-8,9’-xanthene])(24.7g, It 45.1mmol) is dissolved in the tetrahydrofuran (THF) of 250ml.Sodium carbonate (Na is added thereto2CO3) 2M solution (130mL), four (triphenylphosphine) palladium (0) [Pd (PPh3)4] (1.4g, 3mol%), it flows back 4 hours.After reaction, it is cooled to room temperature, will generate Mixture water and toluene extract 3 times.After separation of methylbenzene layer, it is dried with magnesium sulfate (magnesium sulfate), it will The filtrate decompression of filtering is distilled, and obtained mixture is utilized chloroform, re-crystallizing in ethyl acetate, to obtain compound Q -5 (19.6g, yield 72%；MS:[M+H]+=666).
Production Example 6: the manufacture of midbody compound S-4
Compound P-4 is replaced using compound R -3, using 2- ([1,1 '-biphenyl] -3- base) -4- chloro-6-phenyl -1,3, 5- triazine (2- ([1,1 '-biphenyl] -3-yl) -4-chloro-6-phenyl-1,3,5-triazine) (55.8g, 162.3mmol) replace the chloro- 4,6- diphenyl -1,3,5- triazine (2-chloro-4,6-diphenyl-1,3,5- of 2- Triazine) (17.6g, 162.3mmol), in addition to this, by identical with the manufacturing method of compound P-5 of Production Example 1 Method has manufactured compound S-3 (71.0g, yield 89%；MS:[M+H]+=492).
Compound S-3 (71g, 144.6mmol) is dissolved in the DMF of 500ml.Thereto be added NBS (29.60g, 166.3mmol), it is stirred 3 hours at 65 DEG C.After reaction, it is cooled to room temperature, adds water.The solid of generation is filtered, water is used It after washing, is recrystallized with toluene and ethyl acetate, to obtain compound S-4 (66.1g, yield 80%；MS:[M+H]+= 570)。
Production Example 7: the manufacture of midbody compound S-6
Compound P-4 is replaced using compound R -3, uses chloro- 4,6- diphenylpyrimidin (2-chloro-4, the 6- of 2- Diphenylpyrimidine) (43.3g, 162.3mmol) replaces the chloro- 4,6- diphenyl -1,3,5- triazine (2-chloro- of 2- 4,6-diphenyl-1,3,5-triazine) (17.6g, 162.3mmol) passes through the compound with Production Example 1 in addition to this The identical method of the manufacturing method of P-5 has manufactured compound S-5 (57.9g, yield 86%；MS:[M+H]+=415).
Compound S-5 (57.9g, 161.9mmol) is dissolved in the DMF of 500ml.Thereto be added NBS (28.63g, 160.83mmol), it is stirred 3 hours at 65 DEG C.After reaction, it is cooled to room temperature, adds water.The solid of generation is filtered, is used It after water washing, is recrystallized with toluene and ethyl acetate, to obtain compound S-6 (57.4g, yield 83%；MS:[M+H]+ =493).
<embodiment>
Embodiment 1: the manufacture of compound 1
By compound P-6 (20.0g, 38.1mmol) and 2- bromine spiral shell [indoles simultaneously [3,2,1-de] acridine -8,9 ' xanthene] (2- Bromospiro [indolo [3,2,1-de] acridine-8,9 '-xanthene]) (17.32g, 34.64mmol) be scattered in four After hydrogen furans (280ml), 2M wet chemical (aq.K is added2CO3) (57.2ml, 114.3mmol), four (triphenyls are added Phosphine) palladium [Pd (PPh3)4] after (1.2g, 3mol%), be stirred at reflux 6 hours.Room temperature is cooled the temperature to, the solid of generation is filtered. It by the solid chloroform of filtering and the re-crystallizing in ethyl acetate of 300ml, after filtering, is dried, to manufacture compound 1 (21.6g, yield 76%；MS:[M+H]+=819).
Embodiment 2: the manufacture of compound 2
By compound P-6 (14.3g, 27.2mmol) and 10- bromine spiral shell [indoles simultaneously [3,2,1-de] acridine -8,9 ' xanthene] (10-bromospiro [indolo [3,2,1-de] acridine-8,9 '-xanthene]) (12.4g, 24.7mmol) is scattered in After tetrahydrofuran (250ml), 2M wet chemical (aq.K is added2CO3) (57.2ml, 114.3mmol), four (triphenyls are added Phosphine) palladium [Pd (PPh3)4] after (0.9g, 3mol%), be stirred at reflux 4 hours.Room temperature is cooled the temperature to, the solid of generation is filtered. It by the chloroform and re-crystallizing in ethyl acetate of the solid of filtering 260ml, after filtering, is dried, to manufacture compound 2 (16.2g, yield 80%；MS:[M+H]+=819).
Embodiment 3: the manufacture of compound 3
Compound P-6 is replaced using compound P-8 (14.1g, 23.5mmol), in addition to this, by same as Example 1 Method manufactured compound 3 (12.4g, yield 65%；MS:[M+H]+=894).
Embodiment 4: the manufacture of compound 4
Using compound P-10 (22.9g, 38.1mmol) replace compound P-6, in addition to this, by with 2 phase of embodiment Same method has manufactured compound 4 (20.3g, yield 7%；MS:[M+H]+=702).
Embodiment 5: the manufacture of compound 5
Use 2,4- diphenyl -6- (3- (4,4,5,5- tetramethyl -1,3,2- dioxaborolanes -2- base) phenyl) - 1,3,5- triazine (2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) Phenyl) -1,3,5-triazine) (14.1g, 32.4mmol) replace compound P-6, using compound Q -5 (19.6g, 29.5mmol) replace 2- bromine spiral shell [indoles simultaneously [3,2,1-de] acridine -8,9 '-xanthene] (2-bromospiro [indolo [3,2, 1-de] acridine-8,9 '-xanthene]), in addition to this, compound 5 is manufactured by method same as Example 1 (21.5g, yield 81%；MS:[M+H]+=895).
Embodiment 6: the manufacture of compound 6
Compound P-6 is replaced using compound S-4 (12.4g, 21.7mmol), uses spiral shell [indoles [3,2,1-de] acridine- 8,9 '-xanthenes] -2 '-ylboronic acids (spiro [indolo [3,2,1-de] acridine-8,9 '-xanthen] -2 ' - Ylboronic acid) (11.1g, 23.9mmol) replace 2- bromine spiral shell [indoles simultaneously [3,2,1-de] acridine -8,9 ' xanthene] (2- Bromospiro [indolo [3,2,1-de] acridine-8,9 '-xanthene]), in addition to this, by with 2 phase of embodiment Same method has manufactured compound 6 (13.3g, yield 67%；MS:[M+H]+=911).
Embodiment 7: the manufacture of compound 7
Compound P-6 is replaced using compound S-6 (15.3g, 31.1mmol), uses spiral shell [indoles [3,2,1-de] acridine- 8,9 '-xanthenes] -4 '-ylboronic acids (spiro [indolo [3,2,1-de] acridine-8,9 '-xanthen] -4 ' - Ylboronic acid) (15.9g, 34.2mmol) replace 2- bromine spiral shell [indoles simultaneously [3,2,1-de] acridine -8,9 ' xanthene] (2- Bromospiro [indolo [3,2,1-de] acridine-8,9 '-xanthene]), in addition to this, by with 2 phase of embodiment Same method has manufactured compound 7 (16.8g, yield 65%；MS:[M+H]+=834).
<experimental example 1>
Comparative experiments example 1-1
It will be withThickness thin film be coated with the glass substrate of ITO (tin indium oxide, indium tin oxide) and put Enter in the distilled water dissolved with detergent, is washed using ultrasonic wave.At this moment, detergent uses Fei Xier company (Fischer Co.) product, distilled water is used to be filtered twice by the filter (Filter) that Millipore Corp. (Millipore Co.) is manufactured Distilled water.It is repeated twice after ITO is washed 30 minutes with distilled water and carries out 10 minutes ultrasonic washings.In distillation water washing knot Shu Hou is delivered to plasma washing machine after being carried out ultrasonic washing with the solvent of isopropanol, acetone and methanol and dried. In addition, after five minutes by aforesaid substrate cleaning, delivering the substrate to vacuum evaporation plating machine using oxygen plasma.
On the ito transparent electrode prepared in this way withThickness thermal vacuum vapor deposition following chemical formula six nitriles, six nitrogen Miscellaneous benzophenanthrene (hexaazatriphenylene；HAT) hole injection layer is formed.
[HAT]
On above-mentioned hole injection layer, following compounds 4,4 '-(9- benzene of the vacuum evaporation as the substance of transporting holes Base -9H- carbazole -3,6- diyl) bis- (N, N- diphenylaniline) (4,4 '-(9-phenyl-9H-carbazole-3,6-diyl) bis(N,N-diphenylaniline))[HT1]And form hole transmission layer.
[HT1]
Then, with film thickness on above-mentioned hole transmission layerThe following compounds of vacuum evaporation [EB1] and form Electronic barrier layer.
[EB1]
Then, with film thickness on above-mentioned electronic barrier layerFollowing BH and BD is carried out very with the weight ratio of 25:1 Sky is deposited and forms luminescent layer.
On above-mentioned luminescent layer on above-mentioned hole transmission layer, with film thicknessVacuum evaporation above compound [HB1] And form hole blocking layer.
Then, with weight ratio the vacuum evaporation compound ET1 and above compound LiQ of 1:1 on above-mentioned hole blocking layer (8-hydroxyquinoline lithium, Lithium Quinolate), thus withThickness form electron injection and transport layer.Upper State in electron injection and transport layer successively by lithium fluoride (LiF) withThickness, by aluminium withThickness is deposited, To form cathode.
In above process, the evaporation rate of organic matter maintainsThe lithium fluoride of cathode maintainsEvaporation rate, aluminium maintainEvaporation rate, vapor deposition when, vacuum degree maintain 2 × 10-7~5 × 10-6Support, to make organic illuminating element.
Experimental example 1-1 to 1-7
In above-mentioned comparative experiments example 1, ET1 is replaced using such as compound 1 recorded in table 1 to compound 7 respectively, removes this In addition, organic illuminating element has been made using method identical with comparative experiments example 1.
Comparative experiments example 1-2 and 1-3
In above-mentioned comparative experiments example 1, ET1 is replaced using the compound such as following ET2 and ET3 recorded in table 1 respectively, In addition to this, organic illuminating element has been made by method identical with above-mentioned comparative experiments example 1.
[ET 2]
[ET 3]
Electric current is applied to the organic illuminating element made by above-mentioned experimental example 1-1 to 1-7, comparative experiments example 1-1 to 1-3 When, measurement voltage, efficiency, chromaticity coordinates and service life, it the results are shown in following [tables 1].T95 indicates brightness from original intensity (1600nit) was reduced to the time needed for 95%.
[table 1]
As shown in Table 1 above, the organic illuminating element for the compound of the present application being used as electron transfer layer and being manufactured In the case where, excellent characteristic is shown in terms of the efficiency of organic illuminating element, driving voltage and/or stability.
The compound of the compound of the present application and comparative experiments example 1-2 and 1-3 that side is connected with to 2 substituent groups The organic illuminating element manufactured as electron transfer layer is compared, and shows low-voltage, high efficiency, the characteristic of long-life.
As shown in the result of above-mentioned table 1, it can be confirmed that the electron transport ability of compound according to the present invention is excellent, thus It is applicable to organic illuminating element.
<experimental example 2>
Comparative experiments example 2-1
In above-mentioned comparative experiments example 1-1, as luminescent layer, instead of BH and BD by following compound GH1 and GD with 20: 1 weight ratio and with film thicknessVacuum evaporation is carried out, to form luminescent layer.
Experimental example 2-1 to 2-7
In above-mentioned comparative experiments example 2-1, GH is replaced using the compound 1 to 7 recorded such as table 2 respectively, in addition to this, is led to It crosses method identical with comparative experiments example 2 and has made organic illuminating element.
Comparative experiments example 2-2 to 2-4
In above-mentioned comparative experiments example 2, GH1 is replaced using the compound of the following GH2 to GH4 recorded such as table 1 respectively, is removed Other than this, organic illuminating element has been made by method identical with above-mentioned comparative experiments example 2.
[GH 2]
[GH 3]
[GH 4]
When applying electric current to the organic illuminating element made by experimental example 2-1 to 2-7, comparative experiments example 2-1 to 2-4, Voltage, efficiency, chromaticity coordinates and service life are measured, the results are shown in following [tables 2].T95 indicates brightness from original intensity (6000nit) was reduced to the time needed for 95%.
[table 2]
As shown in Table 2 above, the organic illuminating element for the compound of the present application being used as green light emitting layer and being manufactured In the case where, excellent characteristic is shown in terms of the efficiency of organic illuminating element, driving voltage and/or stability.
Be detached from the present application structure and use only comprising carbazyl, triazine radical compound in the case where, can be true Recognize life characteristic significant decrease.
The preferred embodiment of the present invention (electron transfer layer, green light emitting layer) is illustrated through the above, but The present invention is not limited to this, can be deformed into the range of the scope of protection of present invention and detailed description of the invention each It plants form and implements, this also belongs to the scope of invention.
Symbol description
1: substrate 2: anode
3: luminescent layer 4: cathode
5: hole injection layer 6: hole transmission layer
7: luminescent layer 8: electron transfer layer.

Claims (11)

1. a kind of compound indicated by following chemical formula 1:
Chemical formula 1
In institute's chemical formula 1,
X1It is O, S or NR1,
R1For substituted or unsubstituted unsubstituted C1-60Alkyl,
X2、X3And X4Be each independently N or CR ', wherein one of which the above are N,
R ' is hydrogen or substituted or unsubstituted C1-60Alkyl,
Ar1And Ar2It is each independently substituted or unsubstituted C6-60Aryl includes the more than one substitution in N, O and S Or unsubstituted C5-60Heteroaryl.
2. compound according to claim 1, wherein the compound indicated by the chemical formula 1 is selected from by followingization Any of the compound that formula 1-1 to 1-4 is indicated:
Chemical formula 1-1
Chemical formula 1-2
Chemical formula 1-3
Chemical formula 1-4
The chemical formula 1-1 into 1-4,
X1、X2、X3、X4、Ar1And Ar2It is identical as the definition in claim 1.
3. compound according to claim 2, wherein the chemical formula 1-1 is by following chemical formula 1-1a to 1-1c table Any of compound shown:
Chemical formula 1-1a
Chemical formula 1-1b
Chemical formula 1-1c
The chemical formula 1-1a into 1-1c,
X1、X2、X3、X4、Ar1And Ar2It is identical as the definition in claim 1.
4. compound according to claim 2, wherein the chemical formula 1-2 is by following chemical formula 1-2a or chemical formula The compound that 1-2b is indicated:
Chemical formula 1-2a
Chemical formula 1-2b
In the chemical formula 1-2a or 1-2b,
X1、X2、X3、X4、Ar1And Ar2It is identical as the definition in claim 1.
5. compound according to claim 2, wherein the chemical formula 1-3 is by following chemical formula 1-3a to 1-3c table Any of compound shown:
Chemical formula 1-3a
Chemical formula 1-3b
Chemical formula 1-3c
The chemical formula 1-3a into 1-3c,
X1、X2、X3、X4、Ar1And Ar2It is identical as the definition in claim 1.
6. compound according to claim 2, wherein the chemical formula 1-4 is by following chemical formula 1-4a or chemical formula The compound that 1-4b is indicated:
Chemical formula 1-4a
Chemical formula 1-4b
In the chemical formula 1-4a or 1-4b,
X1、X2、X3、X4、Ar1And Ar2It is identical as the definition in claim 1.
7. compound according to claim 1, wherein Ar1And Ar2It is each independently any in following radicals It is a:
8. compound according to claim 1, wherein Ar1And Ar2It is each independently
9. compound according to claim 1, wherein the compound indicated by the chemical formula 1 is selected from following chemical combination Any of object:
10. a kind of organic illuminating element comprising: first electrode, it is opposed with the first electrode and have second electricity Pole and has one layer or more of organic matter layer between the first electrode and the second electrode, the organic matter layer In one layer or more include compound described in claim 1 to any one of claim 9.
11. organic illuminating element according to claim 10, which is characterized in that the organic matter layer comprising the compound is Electron injecting layer, electron transfer layer or the layer for carrying out electron injection and electron-transport simultaneously.
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