EP2207865A1 - Utilisation de composés tris(diphénylamino)-triazine substitués dans des oled - Google Patents

Utilisation de composés tris(diphénylamino)-triazine substitués dans des oled

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Publication number
EP2207865A1
EP2207865A1 EP08841764A EP08841764A EP2207865A1 EP 2207865 A1 EP2207865 A1 EP 2207865A1 EP 08841764 A EP08841764 A EP 08841764A EP 08841764 A EP08841764 A EP 08841764A EP 2207865 A1 EP2207865 A1 EP 2207865A1
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Prior art keywords
alkyl
layer
radicals
aryl
formula
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German (de)
English (en)
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Evelyn Fuchs
Nicolle Moonen
Christian Lennartz
Peter Strohriegl
Michael Rothmann
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BASF SE
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BASF SE
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/50—Three nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission

Definitions

  • the present invention relates to an organic light-emitting diode containing at least one tris (diphenylamino) triazine compound having at least one alkoxy or aryloxy radical, a light-emitting layer containing at least one tris (diphenylamino) - triazine compound having at least one alkoxy or aryloxy, the use the abovementioned compounds as matrix material, hole / exciton blocker material, electron / exciton blocker material, hole injection material, electron injection material, hole conductor material and / or electron conductor material and a device selected from the group consisting of stationary screens, mobile screens and lighting units containing at least an organic light emitting diode according to the invention.
  • OLEDs organic light emitting diodes
  • the property of materials is used to emit light when excited by electric current.
  • OLEDs are of particular interest as an alternative to cathode ray tubes and to liquid crystal displays for the manufacture of flat panel displays. Due to the very compact design and the intrinsically low power consumption, devices containing OLEDs are particularly suitable for mobile applications, for example for applications in mobile phones, laptops, etc. as well as for lighting.
  • phosphorescent materials can be used in addition to fluorescent materials (fluorescence emitters).
  • the phosphorescence emitters are usually organometallic complexes, which exhibit triplet emission (triplet emitter) in contrast to fluorescence emitters which exhibit singlet emission (MA Baldow et al., Appl. Phys. Lett. 1999, 75, 4 to 6).
  • triplet emitter phosphorescence emitter
  • fluorescence emitters which exhibit singlet emission
  • Such device compositions may contain, for example, special matrix materials in which the actual light emitter is present in distributed form. Furthermore, nen the compositions contain blocker materials, which hole, Excitionen- and / or electron blocker may be present in the device compositions. In addition or alternatively, the device compositions may further comprise hole injection materials and / or electron injection materials and / or hole conductor materials and / or electron conductor materials. The selection of the above-mentioned materials, which are used in combination with the actual light emitter, has a significant influence, inter alia, on the efficiency and the lifetime of the OLEDs.
  • EP 1 701 394 A1 discloses OLEDs which have a light-emitting layer which is composed of a matrix polymer and two or more phosphorescent host materials and at least one phosphorescent dopant material.
  • the phosphorescent host materials may be triazine compounds.
  • Suitable triazine compounds are 2,4,6-tris (diarylamino) -1, 3,5-triazine, 2,4,6-tris (diphenylamino) -1, 3,5-triazine, 2,4,6-tris tricarbazolo-1, 3,5-triazine, 2,4,6-tris (N-phenyl-2-naphthylamino) -1, 3,5-triazine, 2,4,6-tris (N-phenyl-1-naphthylamino ) -1, 3,5-triazine and 2,4,6-trisbiphenyl-1,3,5-triazine.
  • EP 1 610 398 A2 discloses OLEDs which have a light-emitting layer composed of a doping material and a host material.
  • the host material comprises at least one hole transport compound and at least one compound which may be a triazine compound.
  • Suitable triazine compounds are 2,4,6-tris (diarylamino) -1, 3,5-triazine, 2,4,6-tris (diphenylamino) -1, 3,5-triazine, 2,4,6-tris tricarbazolo-1, 3,5-triazine, 2,4,6-tris (N-phenyl-2-naphthylamino) -1, 3,5-triazine, 2,4,6-tris (N-phenyl-1-naphthylamino ) -1, 3,5-triazine and 2,4,6-trisbiphenyl-1,3,5-triazine.
  • JP 10-302960 A relates to luminescent materials for OLEDs, which may inter alia be triazines.
  • JC Li et al., Chem. Mater. 2004, 16, 471 1-4714 relates to a study of three different types of amines (phenylenediamines, benzidines and dendritic arylamines) for their suitability as hole transport materials in OLEDs.
  • One example relates to methoxy-substituted tris (diphenylamino) triazine compounds, where the methoxy groups are arranged in the para position.
  • the example mentioned is not shown to be advantageous over the other examples mentioned.
  • US Pat. No. 5,716,722 discloses OLEDs which, as hole transport material, have a compound with a triazine ring with at least one directly bound diphenylamino group. According to US 5,716,722 hole transport materials are to be provided, which are difficult to crystallize, since the crystallization in the hole transport layer can lead to short circuits, so that no light emission takes place in the crystallized areas.
  • V. Vaitkeviciene et al., Mol. Cryst. Liq. Cryst, Vol. 468, pp. 141 / [493] -150 / [502], 2007 relates to aromatic triazine-based amines which are suitable as charge transport materials.
  • a symmetrical tris (ditolylamino) -substituted triazine is compared to unsymmetrical 6-phenyl-1,3,5-triazine.
  • a high thermal stability is found for the unsymmetrical triazine.
  • the unsymmetrical triazine is an amorphous material in the temperature range from 0 to 300 ° C., while the symmetrical triazine crystallizes. According to V.
  • Vaitkeviciene et al. the unsymmetrical triazine is a potential charge transport material for electroluminescent elements.
  • V. Vaitkeviciene et al. does not, however, show any example of the suitability of unsymmetrical triazine as a charge transport material in electroluminescent elements.
  • V. Vaitkeviciene et al. No information regarding an extension of the lifetime of OLEDs when using the unsymmetrical triazine.
  • the object of the present invention is to provide materials which are suitable for use in OLEDs, in particular for use as matrix material, in particular as matrix material in the light-emitting layer, hole / exciton blocker material, electron / exciton blocker material, hole injection material, Electron injection material, hole conductor material and / or Elektronenleiterma- material, which have improved compared to the materials mentioned in the prior art amorphous properties, that is, have a reduced tendency to crystallize, as well as the provision of OLEDs with an improved property profile, which in a improved performance, eg a prolonged life, good luminance, high quantum yields, etc., shows.
  • radicals R 1 to R 30 independently of one another have the following meanings:
  • R 1 , R “, R d , R 4 , R ö , R b , R ', R ö , R a , R ⁇ u , R 11 , R ⁇ ", R ⁇ d , R 14 , R ⁇ ö , R ⁇ b, R 17 ', R 18', R 19 ', R 20', R 21 ', R 22', R 23 ', R 24' and R 25 'independently of one another with respect to the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 have mentioned meanings;
  • the compounds of the formula I thus have at least one alkyloxy or aryloxy radical, preferably at least one alkyloxy radical, in the m-position relative to the binding site of the phenyl groups linked to the nitrogen atom of the diphenylamino groups. It has been found that compounds of the formula I which have one or more substituents in the m position are distinguished by a particularly low tendency to crystallize.
  • the present invention thus relates specifically substituted tris (diphenylamino) - triazine compounds having at least one alkoxy or aryloxy. It has been found that these compounds are distinguished by a particularly low crystallization tendency and are particularly suitable for use in OLEDs.
  • the compounds of the formula (I) can be used either as a matrix, in particular as a matrix in the light-emitting layer, as a hole / exciton blocker, as electron / exciton blocker, as hole injection materials, as electron injection materials, as Hole conductor and / or used as an electron conductor.
  • a hole / exciton blocker as a matrix in the light-emitting layer
  • electron / exciton blocker as hole injection materials
  • electron injection materials as Hole conductor and / or used as an electron conductor.
  • Corresponding layers of OLEDs are known to the person skilled in the art and are mentioned, for example, in WO 2005/113704 or WO 2005/019373.
  • Alkyl is to be understood as meaning substituted or unsubstituted C 1 -C 20 -alkyl radicals. Preference is given to C 1 - to C 10 -alkyl radicals, particularly preferably C 1 to C 6 -alkyl radicals.
  • the alkyl radicals can be both straight-chain and branched.
  • the alkyl radicals may be substituted with one or more substituents selected from the group consisting of CrC 2 o-alkoxy, halogen, preferably F, and C 6 -C 3 o-aryl, which in turn may be substituted or unsubstituted substituted. Suitable aryl substituents as well as suitable alkoxy and halogen substituents are mentioned below.
  • alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl, as well as C 6 -C 3 o-aryl, Ci-C 2O -AIkOXy- and / or halogen, especially F, substitutable substituted derivatives of said alkyl groups, for example CF 3 .
  • n-isomers of the radicals mentioned and branched isomers such as isopropyl, isobutyl, isopentyl, sec-butyl, tert-butyl, neopentyl, 3,3-dimethylbutyl, 3-ethylhexyl, etc. are included.
  • Preferred alkyl groups are methyl, ethyl, tert-butyl and CF 3 .
  • cycloalkyl substituted or unsubstituted C 3 -C 2 O-AI ky I radicals. Preference is given to C 3 - to Cio-alkyl radicals, more preferably C 3 - to C 8 -alkyl radicals.
  • the cycloalkyl radicals may carry one or more of the substituents mentioned with respect to the alkyl radicals.
  • cyclic alkyl groups which may likewise be unsubstituted or substituted by the radicals mentioned above with respect to the alkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. If appropriate, these may also be polycyclic ring systems, such as decalinyl, norbornyl, bornanyl or adamantyl.
  • Suitable O-alkyl and S-alkyl groups are Ci-C 2 o-alkoxy and C 1 -C 20 - alkylthio, and derive respectively from the above-mentioned C 1 -C 20 - alkyl radicals from.
  • C 3 H 7 , C 4 H 9 and C 8 H 17 include both the n-isomers and branched isomers such as isopropyl, isobutyl, sec-butyl, tert-butyl and 2-ethylhexyl.
  • Particularly preferred alkoxy or alkylthio groups are methoxy, ethoxy, n-octyloxy, 2-ethylhexyloxy and SCH 3 .
  • Suitable halogen radicals or halogen substituents for the purposes of the present application are fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine, particularly preferably fluorine and chlorine, very particularly preferably fluorine.
  • Suitable pseudohalogen radicals in the context of the present application are CN, SCN, OCN, N 3 and SeCN, CN and SCN being preferred. Most preferred is CN.
  • the term aryl for the second ring also means the saturated form (perhydroform) or the partially unsaturated form (for example the dihydroform or tetrahyroform), provided the respective forms are known and stable. That is, in the present invention, the term aryl includes, for example, bicyclic or tricyclic radicals in which both both and all three radicals are aromatic, as well as bicyclic or tricyclic radicals in which only one ring is aromatic, and tricyclic radicals wherein two rings are aromatic.
  • aryl examples include: phenyl, naphthyl, indanyl, 1, 2 Dihydronaphthenyl, 1,4-dihydronaphthenyl, indenyl, anthracenyl, phenanthrenyl or 1,2,3,4-tetrahydronaphthyl.
  • Particular preference is given to C 6 -C 10 -aryl radicals, for example phenyl or naphthyl, very particularly preferably C 6 -aryl radicals, for example phenyl.
  • the aryl radicals may be unsubstituted or substituted by one or more further radicals.
  • Suitable other radicals are selected from the group consisting of -C 2 -alkyl, C 6 -C 30 aryl or substituents having donor or acceptor, suitable substituents are mentioned with donor or acceptor below.
  • the C 6 -C 3 are preferably unsubstituted o-aryl radicals or substituted with one or more Ci-C2 o alkoxy, CN, CF 3, F or amino groups. Further preferred substitutions of the C 6 -C 30 aryl radicals are dependent on the intended use of the compounds of the general formula (I) and are mentioned below.
  • Suitable O-aryl and S-aryl groups are C 6 -C 3 o-aryloxy, C 6 -C 30 -alkyl kylthioreste and managerial th correspondingly from the aforementioned C 6 -C 30 -aryl radicals from. Particularly preferred are phenoxy and phenylthio.
  • Heteroaryl is to be understood as meaning unsubstituted or substituted heteroaryl radicals having 5 to 30 ring atoms, which may be monocyclic, bicyclic or tricyclic, some of which can be derived from the abovementioned aryl, in which at least one carbon atom in the aryl skeleton is replaced by a heteroatom , Preferred heteroatoms are N, O and S. Particularly preferably, the heteroaryl radicals have 5 to 13 ring atoms. Especially preferred is the backbone of the heteroaryl radicals selected from systems such as pyridine and five-membered heteroaromatics such as thiophene, pyrrole, imidazole or furan.
  • backbones may optionally be fused with one or two six-membered aromatic radicals.
  • Suitable anellated heteroaromatics are carbazolyl, benzimidazolyl, benzofuryl, dibenzofuryl or dibenzothiophenyl.
  • the backbone may be substituted at one, several or all substitutable positions, suitable substituents being the same as those already mentioned under the definition of C 6 -C 30 -aryl.
  • the heteroaryl radicals are unsubstituted.
  • Suitable heteroaryl radicals are, for example, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thiophen-2-yl, thiophen-3-yl, pyrrol-2-yl, pyrrol-3-yl, furan-2 - yl, furan-3-yl and imidazol-2-yl and the corresponding benzanell faced radicals, in particular carbazolyl, benzimidazolyl, benzofuryl, dibenzofuryl or dibenzothiophenyl.
  • Amino groups are radicals of the general formula -NR 31 R 32 , suitable radicals R 31 and R 32 being mentioned below.
  • suitable amino groups are diarylamino groups such as diphenylamino and dialkylamino groups such as dimethylamino, diethylamino and arylalkylamino groups such as phenylmethylamino.
  • groups / substituents with donor or acceptor action are understood to mean the following groups:
  • Preferred substituents with donor or acceptor action are selected from the group consisting of:
  • C 1 to C 20 -alkoxy preferably C 1 -C 6 -alkoxy, particularly preferably ethoxy or methoxy
  • C6-C 30 -aryloxy preferably, C 6 -C 0 aryloxy, most preferably phenyloxy
  • SiR 31 R 32 R 33 wherein R 31 , R 32 and R 33 are preferably each independently substituted or unsubstituted alkyl or substituted or unsubstituted phenyl, suitable substituents being mentioned above, wherein SiR 31 R 32 R 33 eg SiMe 3 ;
  • Halogen radicals preferably F, Cl, Br, particularly preferably F or Cl, very particularly preferably F, halogenated C 1 -C 20 -alkyl radicals, preferably halogenated C 1 -C 6 -alkyl radicals, very particularly preferably fluorinated C 1 -C 6 -alkyl radicals, eg.
  • CF 3 CH 2 F, CHF 2 or C 2 F 5 ;
  • Amino preferably dimethylamino, diethylamino or diphenylamino;
  • OH pseudohalogen radicals, preferably CN, SCN or OCN, more preferably CN, -C (O) OC r C 4 alkyl, preferably -C (O) OMe, P (O) R 2 , preferably P (O) Ph 2 or SO 2 R 2 , preferably SO 2 Ph.
  • Very particularly preferred substituents having donor or acceptor selected from the group consisting of methoxy, phenyloxy, halogenated CrC 4 - alkyl, preferably CF 3, CH 2 F, CHF 2, C 2 F 5, halogen, preferably F, CN, SiR 14 R 15 R 16 , where suitable radicals R 31 , R 32 and R 33 are already mentioned, diphenylamino, -C (O) OCrC 4 -alkyl, preferably -C (O) OMe, P (O) Ph 2 , SO 2 Ph.
  • radicals R 31 , R 32 and R 33 mentioned in the abovementioned groups with donor or acceptor action have the meanings already mentioned above, ie R 31 , R 32 , R 33 independently of one another
  • O-alkyl radicals which are preferably suitable in the compounds of the formula I are C 2 - to C 8 -alkyl radicals, preferably methoxy, ethoxy, n-propyloxy, isopropoxy, n-butoxy, isobutoxy, sec-butyloxy -, tert-Butyloxyreste, more preferably methoxy or ethoxy radicals, most preferably methoxy radicals.
  • O-aryl radicals which are suitable in the compounds of the formula I are 0-C 6 - to C 20 -aryl radicals, preferably phenyloxy- and naphthyloxy radicals, more preferably phenoxy radicals, which may optionally be substituted by C 1 - to C 6 -alkyl radicals. Particularly preferred are unsubstituted phenyloxy, 4-alkylphenyloxy and 2,4,6-trialkylphenyloxy.
  • radicals R 1 ' R 2' R 3 ' R 4' R 5 ' R 6' R 7 ' R 8' R 9 ' R 10' R 11 ' R 12' R 13 ' R 14' R 15 ' R 16 ' R 17' , R 18 ' , R 19' , R 20 ' , R 21' , R 22 ' , R 23' , R 24 ' and R 25' independently of one another with respect to the radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 have meanings mentioned.
  • Suitable alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, OH, O-alkyl, O-aryl, O-Heterorayl, SH, S-alkyl, S-aryl, halogen, pseudohalogen - or amino radicals are mentioned above.
  • the further radicals R 1 to R 30 and R 1 to R 25 independently of one another preferably denote hydrogen, alkyl, cycloalkyl, O-alkyl, O-aryl, aryl, SH, S-alkyl, S-aryl, halogen, pseudohalogen or amino, particularly preferably hydrogen, C 1 - to C 6 -alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl or halogen-substituted d- to C 8 - Alkyl, for example CF 3 , aryl, especially phenyl, halogen, in particular F or Cl, pseudohalogen, in particular CN, O-alkyl, in particular OC r to C 8 alkyl, O-aryl, in particular OC 6 -aryl, or SiR 31 R 32 R 33 , wherein the radicals R 31 , R
  • the compounds of the formula I may have one or more O-alkyl or O-aryl radicals which may be present at any positions in the molecule, wherein at least one O-alkyl or O-aryl radical in the m position to the one with the Nitrogen atom of Diphenylamino phenomenon linked binding site of the phenyl groups is present.
  • the compounds of the formula I preferably have 1, 2, 3, 4, 5 or 6 O-alkyl and / or O-aryl radicals, more preferably 1, 2 or 3 O-alkyl and / or O-aryl radicals.
  • the present invention relates to compounds of the Formula I, wherein 1, 2, 3, 4, 5 or 6, preferably 1, 2 or 3 of the radicals R 2 , R 4 , R 7 , R 9 , R 12 , R 14 , R 17 , R 19 , R 22 , R 24 , R 27 or R 29 are O-alkyl and / or O-aryl.
  • Particularly suitable are, for example, compounds of the formula I in which R 2 , R 7 , R 12 , R 17 , R 22 and R 27 are O-alkyl- and / or O-aryl, and also compounds of the formula I in which R 2 , R 3 12 and R 22 is O-alkyl and / or O-aryl.
  • the radicals R 1 , R 5 , R 6 , R 10 , R 11 , R 15 , R 16 , R 20 , R 21 , R 25 , R 26 and R 30 are hydrogen. That is, in one embodiment of the present invention, the positions in the o-position to the bonding site of the phenyl groups linked to the nitrogen atom of the diphenylamino groups are substituted with hydrogen.
  • the positions in the p-position to the binding site of the phenyl groups, R 3 , R 8 , R 13 , R 18 , R 23 and R 28 linked to the nitrogen atom of the diphenylamino groups may each be independently substituted or unsubstituted (under "unsubstituted”). It is understood that the corresponding radicals are hydrogen). Suitable substituents are mentioned above.
  • the compounds of the formula I have the following formulas (Ia), (Ib), (Ic), (Id), (Ie) or (If):
  • R 3 , R 8 , R 13 , R 18 , R 23 and R 28 independently of one another preferably denote hydrogen, methyl, ethyl, F, CF 3 , SiMe 3 or CN.
  • R 3 , R 8 , R 13 , R 18 , R 23 and R 28 preferably independently of one another are methyl, ethyl, F, CF 3 , SiMe 3 or CN.
  • R 2 , R 4 , R 7 , R 9 , R 12 , R 14 , R 17 , R 22 , R 24 , R 27 and R 29 in the compounds of the formulas Ia, Ib, Ic, Id, Ie and If - unless they are OCH 3 - independently of one another have the meanings given above.
  • R 2, R 4, R 7, R 9, R 12, R 14, R 17, R 22, R 24, R 27 or R 29 represent - as far as they do not represent OCH 3 - hydrogen or d- to C 4 - alkyl.
  • the tris (diphenylamino) -triazine compounds of the general formula I used according to the invention are prepared by processes known to the person skilled in the art, for example by nucleophilic substitution of tris-1,3,5-trichloro-2,4,6-triazine with suitable Li-diarylamides, eg according to the method mentioned in H. Inomata et al., Chemistry of Materials 2004, 16, 1285.
  • the following scheme 1 shows by way of example a general reaction scheme for the preparation of the compounds of the formula I:
  • the compounds of the formula (I) are outstandingly suitable for use as matrix materials in organic light-emitting diodes.
  • they are as matrix materials in the light-emitting layer of the OLEDs, wherein the light-emitting layer preferably contains one or more triplet emitters as emitter compounds.
  • the compounds of the formula (I) are suitable as hole / exciton blocker material, electron / exciton blocker material, hole injection material, electron injection material, hole conductor material and / or electron conductor material, wherein they preferably together with at least one triplet emitter in the OLED invention are used.
  • the function of the compounds of formula (I) as a matrix material, preferably in the light-emitting layer, as a hole / Excitonenblockermaterial, as electron / Excitonenblockermaterial, as a hole-injection material, as an electron injection material, as a hole conductor material or as an electron conductor material is under - derem depending on the electronic properties of the compounds of formula (I), ie from the substitution pattern of the compounds of the formula (I), and furthermore from the electronic properties (relative positions of the HOMOs and LUMOs) of the respective layers used in the OLED according to the invention.
  • the LUMO of the block layer for electrons is higher in energy than the LUMO of the materials used in the light-emitting layer (both of the emitter material and optionally used matrix materials).
  • Suitable substitution patterns of the compounds of the formula (I) which are suitable as electron and / or exciton blocker materials are thus dependent inter alia on the electronic properties (in particular the position of the LUMO) of the materials used in the light-emitting layer.
  • the HOMO of the block layer for holes is lower in energy than the HOMOs of the materials present in the light-emitting layer (both of the emitter materials). and optionally present matrix materials).
  • Suitable substitution patterns of the compounds of the formula (I) which are suitable as hole and / or exciton blocker materials are thus dependent inter alia on the electronic properties (in particular the position of the HOMOs) of the materials present in the light-emitting layer.
  • the energies of the HOMOs and LUMOs of the materials used in the inventive OLED can be determined by different methods, e.g. by solution electrochemistry, e.g. Cyclic voltammetry.
  • the position of the LUMO of a given material can be calculated from the HOMO determined by ultraviolet photon electron spectroscopy (UPS) and the band gap determined optically by absorption spectroscopy.
  • UPS ultraviolet photon electron spectroscopy
  • Another object of the present invention is thus the use of tris (diphenylamino) -triazine compounds of the formula (I) as a matrix material, preferably as a matrix material in a light-emitting layer of the organic light emitting diode, and / or as a hole / Excitonenblockermaterial, electron / Excitonenblockermaterial, hole injection material, electron injection material, hole conductor material and / or E- lektronenleitermaterial, wherein the compounds of formula (I) are preferably used together with at least one triplet emitter in the organic light emitting diode.
  • the compound of the formula (I) is preferably used as the matrix material, with the matrix material particularly preferably being used together with a triplet emitter.
  • the compounds of the formula (I) can be used in OLEDs both as matrix material and as hole / exciton blocker material, electron / exciton blocker material, hole injection material, electron injection material, hole conductor material and / or electron conductor material. These may be the matrix material, the hole / exciton blocker material, the electron / exciton blocker material, the hole injection material, the electron injection material, the hole conductor material and / or the electron conductor material to the same or different compounds of formula (I).
  • Another object of the present invention is a light-emitting layer containing at least one compound of formula (I) and at least one emitter compound, wherein the emitter compound is preferably a triplet emitter.
  • the use of the compounds of the formula (I) as matrix materials and / or as hole / exciton blocker material, electron / exciton blocker material, hole injection material, electron injection material, hole conductor material and / or electron conductor material is not intended to preclude these compounds themselves also emitting light .
  • the matrix materials used according to the invention and / or hole / exciton blocker materials, electron / exciton blocker materials, hole injection materials, electron injection materials, hole conductor materials and / or electron conductor materials of the formula (I) have a tendency to crystallize which is lower than that of conventional materials.
  • OLEDs having an improved property profile resulting in improved performance e.g. extended lifetime, good luminance, high quantum efficiency, etc., shows
  • OLEDs organic light-emitting diodes
  • the OLED does not have all of the layers mentioned, for example, an OLED having the layers (1) (anode), (3) (light-emitting layer), and (6) (cathode) is also suitable the functions of the layers (2) (hole conductor layer) and (4) (hole / exciton block layer) and (5) (electron conductor layer) are taken over by the adjacent layers. OLEDs, the layers (1), (2), (3) and (6) or the Layers (1), (3), (4), (5) and (6) are also suitable. Furthermore, the OLEDs between the anode (1) and the hole conductor layer (2) may have a block layer for electrons / excitons.
  • the compounds of formula I can be used as charge-transporting or -blocking materials. However, they are preferably used as matrix materials in the light-emitting layer.
  • the compounds of the formula I can be present as the sole matrix material-without further additives-in the light-emitting layer. However, it is also possible that in addition to the compounds of the formula I used according to the invention further
  • a fluorescent dye may be present to match the emission color of the existing dye
  • a diluent material can be used.
  • This diluent material may be a polymer, for example, poly (N-vinylcarbazole) or polysilane.
  • the proportion of the at least one compound of the formula (I) in The light-emitting layer generally 10 to 99 wt .-%, preferably 50 to 99 wt .-%, particularly preferably 70 to 97 wt .-%.
  • the proportion of the emitter compound in the light-emitting layer is generally 1 to 90 wt .-%, preferablyl to 50 wt .-%, particularly preferably 3 to 30 wt .-%, wherein the proportions of the at least one compound of Formula (I) and the at least one emitter compound generally give 100 wt .-%.
  • the light-emitting layer may contain, in addition to the at least one compound of the formula (I) and the at least one emitter compound, further substances, for example further diluent material, suitable diluent material being mentioned above.
  • the individual of the abovementioned layers of the OLED can in turn be composed of 2 or more layers.
  • the hole-transporting layer can be made up of a layer into which holes from the electrode and a layer that transports the holes away from the hole-injecting layer into the light-emitting layer.
  • the electron-transporting layer may also consist of several layers, for example a layer in which electrons are injected through the electrode and a layer which receives electrons from the electron-injecting layer and transports them into the light-emitting layer.
  • These mentioned layers are each selected according to factors such as energy level, temperature resistance and charge carrier mobility, as well as the energy difference of said layers with the organic layers or the metal electrodes.
  • the person skilled in the art is able to choose the structure of the OLEDs in such a way that it is optimally adapted to the organic compounds used according to the invention as emitter substances.
  • the HOMO (highest occupied molecular orbital) of the hole-transporting layer should be aligned with the work function of the anode
  • the LUMO (lowest unoccupied molecular orbital) of the electron-transporting layer should be aligned with the work function of the cathode
  • the anode (1) is an electrode that provides positive charge carriers.
  • it may be constructed of materials including a metal, a mixture of various metals, a metal alloy, a metal oxide, or a mixture of various metal oxides.
  • the anode may be a conductive polymer.
  • Suitable metals include the metals of groups Ib, IVa, Va and VIa of the Periodic Table of the Elements and the transition metals of the group Villa.
  • mixed metal oxides of groups IIb, INb and IVb of the Periodic Table of the Elements for example indium tin oxide (ITO), are generally used.
  • the anode (1) contains an organic material, for example polyaniline, as described for example in Nature, Vol. 357, pages 477 to 479 (June 11, 1992). At least either the anode or the cathode should be at least partially transparent in order to be able to decouple the light formed.
  • the material used for the anode (1) is preferably ITO.
  • Suitable hole conductor materials for the layer (2) of the OLEDs according to the invention are disclosed, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 18, pages 837 to 860, 1996. Both hole transporting molecules and polymers can be used as hole transport material.
  • Commonly used hole transporting molecules are selected from the group consisting of tris- [N- (1-naphthyl) -N- (phenylamino)] triphenylamine (1-naphDATA), 4,4'-bis [N- (1-naphthyl) -N-phenyl-amino] biphenyl ( ⁇ -NPD), N, N'-diphenyl-N, N'-bis (3-methylphenyl) - [1, 1'-biphenyl] -4,4'-diamine (TPD ), 1, 1-bis [(di-4-tolylamino) phenyl] cyclohexane (TAPC), N, N'-bis (4-methylphenyl) -N, N'-bis (4-ethylphenyl) - [1, 1 '- (3,3'- dimethyl) biphenyl] -4,4'-diamine (ETPD), tetrakis (3-methylphenyl
  • Hole-transporting polymers commonly used are selected from the group consisting of polyvinylcarbazoles, (phenylmethyl) -polysilanes and polyanilines It is also possible to polymerize holes-transporting polymers by doping To obtain hole-transporting molecules in polymers such as polystyrene and polycarbonate The molecules mentioned above are the molecules already mentioned above.
  • carbene complexes can be used as hole conductor materials, wherein the band gap of the at least one hole conductor material is generally greater than the band gap of the emitter material used.
  • band gap is to be understood as the triplet energy.
  • Suitable carbene complexes are e.g. Carbene complexes, as described in WO 2005/019373 A2, WO 2006/056418 A2 and WO 2005/1 13704 and in the older, not previously published European Applications EP 06 1 12 228.9 and EP 06 1 12 198.4.
  • the light-emitting layer (3) contains at least one emitter material.
  • it may be a fluorescence or phosphorescence emitter, suitable emitter materials being known to the person skilled in the art.
  • the at least one emitter material is a phosphorescence emitter.
  • the preferably used Phosphoreszenzmitter compounds are based on metal complexes, in particular the complexes of the metals Ru, Rh, Ir, Os, Pd and Pt, especially the complexes of Ir have gained importance.
  • the compounds of the formula I used according to the invention are particularly suitable for use together with such metal complexes.
  • the compounds of the formula (I) are used as matrix materials and / or hole / exciton and / or electron / exciton blocker materials.
  • they are suitable for use as matrix materials and / or hole / exciton and / or electron / exciton blocker materials along with complexes of Ru, Rh, Ir, Os, Pd and Pt, particularly preferred for use with complexes of the invention Ir suitable.
  • Suitable metal complexes for use in the OLEDs according to the invention are described, for example, in the publications WO 02/60910 A1, US 2001/0015432 A1, US 2001/0019782 A1, US 2002/0055014 A1, US 2002/0024293 A1, US 2002/0048689 A1, EP 1 191 612 A2, EP 1 191 613 A2, EP 1 211 257 A2, US 2002/0094453 A1, WO 02/02714 A2, WO 00 / 70655 A2, WO 01/41512 A1, WO 02/15645 A1, WO 2005/019373 A2, WO 2005/1 13704 A2, WO 2006/1 15301 A1, WO 2006/067074 A1 and WO 2006/056418.
  • metal complexes are the commercially available metal complexes tris (2-phenylpyridine) iridium (III), iridium (III) tris (2- (4-tolyl) pyridinato-N, C 2 '), iridium (III) tris (1 -phenylisoquinoline), iridium (III) bis (2-2'-benzothienyl) pyridinato-N, C 3 ') (acetylacetonate), iridium (III) bis (2- (4,6-difluorophenyl) pyridinato-N, C 2 ) picolinate, iridium (III) bis (1-phenylisoquinoline) (acetylacetaonate), iridium (III) bis (di-benzo [f, h] quinoxaline) (acetylacetonate), iridium (III) bis (2-methyldi-benzo [f, h] quinoxaline) (ace
  • triplet emitters are carbene complexes.
  • the compounds of the formula (I) are used in the light-emitting layer as matrix material together with carbene complexes as triplet emitters. Suitable carbene complexes are known to the person skilled in the art and are mentioned in some of the aforementioned applications and below.
  • the compounds of the formula (I) are used as hole / exciton blocker material together with carbene complexes as triplet emitters.
  • the compounds of the formula (I) can furthermore be used both as matrix materials and as hole / exciton blocker materials together with carbene complexes as triplet emitters.
  • Formula I as matrix materials and / or hole / exciton and / or electron / exciton blocker materials in OLEDs are therefore also, for example, carbene complexes, as described in WO 2005/019373 A2, WO 2006/056418 A2 and WO 2005/1 13704 and in the older unpublished European applications EP 06 112 228.9 and EP 06 1 12 198.4 are described.
  • the disclosure of said WO and EP applications is hereby explicitly incorporated by reference and these disclosures are to be considered incorporated into the content of the present application.
  • the block layer for holes / excitons (4) can typically comprise hole blocker materials used in OLEDs, such as 2,9-dimethyl-4,7-diphenyl-1, 10-phenanthroline (bathocuproine, (BCP)), bis (2-methyl-8 -quinolinato) -4-phenyl-phenylato) -aluminium (III) (BAIq), phenothiazine-S, S-dioxide derivatives and 1,3,5-tris (N-phenyl-2-benzylimidazole) -benzene) (TPBI), wherein TPBI and BAIq are also suitable as electron-conducting materials.
  • hole blocker materials used in OLEDs such as 2,9-dimethyl-4,7-diphenyl-1, 10-phenanthroline (bathocuproine, (BCP)), bis (2-methyl-8 -quinolinato) -4-phenyl-phenylato) -aluminium (III) (BAIq), pheno
  • compounds containing aromatic or heteroaromatic groups containing carbonyl groups via groups as disclosed in WO2006 / 100298 can be used as a blocking layer for holes / excitons (4) or as matrix materials in the light-emitting layer (3 ) are used.
  • the present invention relates to an OLED according to the invention comprising the layers (1) anode, (2) hole conductor layer, (3) light-emitting layer, (4) block layer for holes / excitons, (5) electron conductor layer and (6 ) Cathode, and optionally further layers, wherein the block layer for holes / excitons contains at least one compound of formula (I).
  • the present invention relates to an OLED according to the invention comprising the layers (1) anode, (2) hole conductor layer, (3) light-emitting layer, (4) block layer for holes / excitons, (5) electron layer and 6) cathode, and optionally further layers, wherein the light-emitting layer (3) contains at least one compound of formula (I) and the block layer for holes / excitons at least one compound of formula (I).
  • the present invention relates to an OLED according to the invention comprising the layers (1) anode, (2) hole conductor layer and / or (2 ') blocking layer for electrons / excitons (the OLED can comprise both the layers (2) and (2') and either the layer (2) or the layer (2 ')), (3) light-emitting layer, (4) block layer for holes / excitons, (5) electron conductor layer and (6) cathode, and optionally further layers, wherein the block layer for electrons / excitons and / or the hole conductor layer and optionally the light-emitting layer (3) contains at least one compound of the formula (I).
  • Suitable electron conductor materials for the layer (5) of the O-LEDs according to the invention comprise chelated metals such as tris (8-quinoline) with oxinoid compounds.
  • linolato) aluminum (Alq ⁇ ) bis (2-methyl-8-quinolinato) -4-phenyl-phenylato) aluminum (III) (BAIq)
  • hole conductor materials and electron conductor materials some may fulfill several functions.
  • some of the electron-conducting materials are simultaneously hole-blocking materials if they have a deep HOMO. These can be z.
  • the function as a hole / exciton blocker of the layer (5) is taken over, so that the layer (4) may be omitted.
  • the charge transport layers can also be electronically doped in order to improve the transport properties of the materials used, on the one hand to make the layer thicknesses more generous (avoidance of pinholes / short circuits) and on the other hand to minimize the operating voltage of the device.
  • the hole conductor materials can be doped with electron acceptors, for example phthalocyanines or arylamines such as TPD or TDTA can be doped with tetrafluorotetracyanchinodimethane (F4-TCNQ).
  • the electron conductor materials can be doped, for example, with alkali metals, for example Alq 3 with lithium.
  • the electronic doping is known to the person skilled in the art and described, for example, in W. Gao, A. Kahn, J.
  • the cathode (6) is an electrode which serves to introduce electrons or negative charge carriers.
  • Suitable materials for the cathode are selected from the group consisting of alkali metals of group Ia, for example Li, Cs, alkaline earth metals of group IIa, for example calcium, barium or magnesium, metals of group IIb of the Periodic Table of the Elements (old ILJPAC version) comprising the lanthanides and actinides, for example samarium.
  • metals such as aluminum or indium, as well as combinations of all mentioned metals can be used become.
  • lithium-containing organometallic compounds or LiF can be applied between the organic layer and the cathode to reduce the operating voltage.
  • the OLED according to the present invention may additionally contain further layers which are known to the person skilled in the art.
  • a layer can be applied between the layer (2) and the light-emitting layer (3), which facilitates the transport of the positive charge and / or adapts the band gap of the layers to one another.
  • this further layer can serve as a protective layer.
  • additional layers may be present between the light-emitting layer (3) and the layer (4) to facilitate the transport of the negative charge and / or to match the band gap between the layers.
  • this layer can serve as a protective layer.
  • the OLED according to the invention contains at least one of the further layers mentioned below:
  • Suitable materials for the individual layers are known to those skilled in the art and e.g. in WO 00/70655.
  • the layers used in the O-LED according to the invention are surface-treated in order to increase the efficiency of the charge carrier transport.
  • the selection of materials for each of said layers is preferably determined by obtaining an OLED having a high efficiency and lifetime.
  • the preparation of the OLEDs according to the invention can be carried out by methods known to the person skilled in the art.
  • the inventive OLED is produced by successive vapor deposition (vapor deposition) of the individual layers onto a suitable substrate.
  • Suitable substrates are, for example, glass, inorganic semiconductors or polymer films.
  • vapor deposition conventional techniques can be used such as thermal evaporation, chemical vapor deposition (CVD), Physical Vapor Deposition (PVD) and others.
  • the organic layers of the OLED can be applied from solutions or dispersions in suitable solvents, using coating techniques known to those skilled in the art.
  • the various layers have the following thicknesses: anode (1) 50 to 500 nm, preferably 100 to 200 nm; Hole-conductive layer (2) 5 to 100 nm, preferably 20 to 80 nm, light-emitting layer (3) 1 to 100 nm, preferably 10 to 80 nm, Block layer for holes / excitons (4) 2 to 100 nm, preferably 5 to 50 nm, electron-conducting layer (5) 5 to 100 nm, preferably 20 to 80 nm, cathode (6) 20 to 1000 nm, preferably 30 to 500 nm.
  • a. be influenced by the relative thickness of each layer.
  • the thickness of the electron transport layer should preferably be chosen such that the position of the recombination zone is tuned to the optical resonator property of the diode and thus to the emission wavelength of the emitter.
  • the ratio of the layer thicknesses of the individual layers in the OLED depends on the materials used.
  • the layer thicknesses of optionally used additional layers are known to the person skilled in the art. It is possible that the electron-conducting layer and / or the hole-conducting layer have larger thicknesses than the specified layer thicknesses when they are electrically doped.
  • the light-emitting layer and / or at least one of the further layers optionally present in the OLED according to the invention contains at least one compound of the general formula (I). While the at least one compound of the general formula (I) is present in the light-emitting layer as the matrix material, the at least one compound of the general formula (I) in the at least one further layer of the inventive OLED can each alone or together with at least one of the others for the corresponding layers suitable materials mentioned above are used. It is also possible for the light-emitting layer to contain, in addition to the compound of the formula (I), one or more further matrix materials.
  • the efficiency of the OLEDs according to the invention can be improved, for example, by optimizing the individual layers.
  • highly efficient cathodes such as Ca or Ba, optionally in combination with an intermediate layer of LiF, can be used.
  • Shaped substrates and new hole-transporting materials, which cause a reduction in the operating voltage or an increase in the quantum efficiency, can also be used in the inventive OLEDs.
  • Additional layers may be present in the OLEDs to adjust the energy levels of the various layers and to facilitate electroluminescence.
  • the OLEDs according to the invention can be used in all devices in which electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile screens and lighting units. Stationary screens are e.g. Screens of computers, televisions, screens in printers, kitchen appliances and billboards, lights and signboards. Mobile screens are e.g. Screens in cell phones, laptops, digital cameras, vehicles, and destination displays on buses and trains.
  • the compounds of formula I can be used in OLEDs with inverse structure.
  • the compounds of the formula I used according to the invention in these inverse OLEDs are preferably used in turn as matrix materials in the light-emitting layer.
  • the construction of inverse OLEDs and the materials usually used therein are known to the person skilled in the art.
  • the lithium-diphenylamine solution is added dropwise to the cyanuric chloride solution by means of a transfer cannula.
  • the reaction mixture is then refluxed for 6 hours. After cooling to room temperature, the solvent is evaporated and the residue is stirred for 10 minutes in 200 ml of water.
  • the white solid obtained by filtration is washed with diethyl ether, slurried in hot ethanol and filtered while hot. For further purification, the product is recrystallized in chlorobenzene and dried under high vacuum to obtain 3.55 g (61%) of 2,4,6-tris (diphenylamino) -1, 3,5-triazine (1) as a white solid.
  • Example d Triply substituted 2,4,6-trichloro-i, 3,5-triazine to give 2,4,6-tris (3-methoxydiphenylamino) -1,3,5-triazine (4) (according to the invention)
  • the unsubstituted 2, 4, 6-tris (diphenylamino) -1, 3,5-triazine (1) melts at 308 ° C. during the first heating. During the subsequent cooling, the compound crystallizes almost completely at a temperature of 264 0 C. when the compound heats up again, the amorphous part of the sample recrystallized at a temperature of 208 0 C.
  • Films deposited by vacuum evaporation or spin-coating crystallize immediately after or during production.
  • Example f (comparison)
  • the MEFA-methyl substituted (2) (comparison) showing the first heating has a melting point at 175 0 C.
  • the crystallization onspeak extends from 125 0 C to 90 0 C with multiple maxima. The most intense maximum is seen at a temperature of 102 0 C.
  • the crystallization enthalpy is 24 kJ / mol.
  • the next time it is heated the amorphous part of the sample recrystallizes at a temperature of 1 19 ° C.
  • Films produced by vacuum evaporation or spin-coating are amorphous for several hours to a day until a crystallization process begins.
  • 2,4-bis (3-methyldiphenylamino) -6- (3-methoxydiphenylamino) -1, 3,5-triazine (3) shows a melting point at 153 ° C. during the first heating. In the subsequent cooling, the compound solidifies glassy. The subsequent heating cycles show a glass transition at a temperature of 39 0 C. If heated further, this leads to a recrystallization at 100 0 C and a melting at 156 0 C. Upon cooling at 10K / min, no crystallization is observed.
  • Films made by vacuum evaporation or spin-coating are amorphous for two weeks until a crystallization process begins.
  • mete-methoxy-substituted 2,4,6-tris (3-methoxydiphenylamino) -1, 3,5-triazine (4) shows a melting point at 167 ° C. during the first heating. In all other heating and cooling cycles, none To observe crystallization or recrystallization. Upon heating, a glass transition at 37 0 C is measured.
  • Films made by vacuum evaporation or spin-coating are amorphous over the entire measurement period (more than 60 days).
  • the ITO substrate used as anode is first cleaned in an acetone / isopropanol mixture in an ultrasonic bath. To remove any organic residues, the substrate is cleaned for a further 10 minutes in (VPIasma.
  • the below-mentioned organic materials at a rate of about 0.5-5 nm / min at 10 "6 mbar are vapor-deposited on the cleaned substrate.
  • the hole conductor and exciton is N, N'-di (naphth-1-yl) -N , N'-diphenyl-benzidine ( ⁇ -NPD) (V1) is applied to the substrate at a thickness of 30 nm.
  • V1 The compounds ⁇ -NPD (V1), Flrpic (V2) and BAIq (V3) are commercially available.
  • electroluminescence spectra are recorded at different currents or voltages. Furthermore, the current-voltage characteristic in combination with the emitted light quantity is measured with a luminance meter.
  • the OLED was stored for one day under a nitrogen atmosphere at room temperature and measured again.
  • the ITO substrate used as anode is first cleaned in an acetone / isopropanol mixture in an ultrasonic bath. To remove any organic residues, the substrate is cleaned for a further 10 minutes in the O 2 plasma.
  • electroluminescence spectra are recorded at different currents or voltages. Furthermore, the current-voltage characteristic in combination with the emitted light quantity is measured with a luminance meter.
  • the OLED was stored for one day under a nitrogen atmosphere at room temperature and measured again.
  • Example I Production of an OLED containing 2 ! 4 ! 6-tris (3-methoxydiphenylamino) -1 ! 3,5-triazine (4) (according to the invention) as matrix material
  • the ITO substrate used as the anode is first cleaned in an acetone / isopropanol mixture in an ultrasonic bath. To remove any organic residues, the substrate is cleaned for a further 10 minutes in the O 2 plasma.
  • electroluminescence spectra are recorded at different currents or voltages. Furthermore, the current-voltage characteristic in combination with the emitted light quantity is measured with a luminance meter.
  • the OLED was stored for one day under a nitrogen atmosphere at room temperature and measured again.

Abstract

L'invention concerne une diode luminescente organique contenant au moins un composé tris(diphénylamino)-triazine comportant au moins un radical alkoxy ou aryloxy; une couche luminescente contenant au moins un composé tris(diphénylamino)-triazine comportant au moins un radical alkoxy ou aryloxy; l'utilisation desdits composés en tant que matériau matriciel, matériau bloqueur à trous/excitons, matériau bloqueur à électrons/excitons, matériau d'injection à trous, matériau d'injection à électrons, matériau conducteur à trous et/ou matériau conducteur à électrons; et un dispositif choisi dans le groupe des écrans stationnaires, écrans mobiles et unités d'éclairage contenant au moins une diode luminescente organique selon l'invention.
EP08841764A 2007-10-24 2008-10-15 Utilisation de composés tris(diphénylamino)-triazine substitués dans des oled Withdrawn EP2207865A1 (fr)

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US20100308308A1 (en) 2010-12-09
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WO2009053278A1 (fr) 2009-04-30
CN101910359A (zh) 2010-12-08

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