Classifications

• • 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
  • H10K85/10—Organic polymers or oligomers
  • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
  • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
• • 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
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
• • 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
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight

Definitions

• Liquid crystal display elements have been around for some time
• Electroluminescent device with a radiation source described consisting of a layer of an amorphous or predominantly amorphous polymer material with noticeable electric charge mobility and low ionization potential, a strong electron donor, a strong electron acceptor and
• At least one luminescent additive there is preferably at least one luminescent additive, electrical connections being provided through which an electrical current can be passed therethrough through the thickness of the layer to excite radiation.
• Conjugated polymers such as poly (p-phenylene vinylene) (see, for example, WO-A 90/13148) and non-conjugated polymers have been used as polymer materials (see, for example, I. Sokolik et al., J. Appl. Phys. 1 993, 74, 3584), wherein conjugated materials generally have the advantage of a higher Carrier mobility and thus better efficiencies and lower threshold voltages.
• electroluminescent materials in particular based on polymers, can in no way be regarded as complete, the manufacturers of lighting and display devices are interested in a wide variety of electroluminescent materials for such devices.
• Electroluminescent materials with the other components of the devices allow conclusions on the quality of the electroluminescent material.
• the object of the present invention was therefore to create new ones
• Lighting or display devices are suitable to improve the property profile of these devices.
• Triarylamine units are particularly suitable as electroluminescent materials.
• Such compounds are sometimes used as photosensitive components for Electrophotographic processes and known as sensitizers for electrically photosensitive dyes (US Pat. No. 4,323,203), a suitability as
• electroluminescent material cannot be derived from this.
• the invention therefore relates to an electroluminescent material comprising one or more polymers which contain structural units of the formula (I)
• Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 are the same or different and / or
• polynuclear optionally linked via one or more, preferably a bridge, and / or condensed aryl and / or
• Heteroaryl groups preferably with 4 to 400, particularly preferably 4 to 100, very particularly preferably 4 to 20 carbon atoms, which can optionally be substituted, two of Ar 1 , Ar 3 , Ar 5 and Ar 6 and of Ar 2 and Ar 4 each run out of a bond;
• R 1 is H, a hydrocarbon radical with 1 to 22 carbon atoms which may be optionally substituted, preferably with F, and may also contain heteroatoms, preferably 0, or Ar 7 , where Ar 7 has the same meanings as Ar 1, independently of Ar 1 -6 -6 has;
• n 0, 1 or 2, preferably 0 or 1, particularly preferably 0.
• the electroluminescent material according to the invention is characterized, inter alia, by a low threshold voltage for electroluminescence and high efficiency, even though the polymers are not conjugated. It is also particularly one of the components of multi-layer structures Hole conductor layer suitable.
• electroluminescent materials are materials which can be used as an active layer in an electroluminescent device.
• Active layer means that the layer is capable of emitting light when an electric field is applied (light-emitting layer) and / or that it improves the injection and / or the transport of the positive and / or negative charges (charge injection or charge transport layer).
• the invention therefore also relates to the use of a polymer containing structural units of the formula (I) as an electroluminescent material, in particular as a hole conductor layer.
• the polymers according to the invention generally have 2 to 1000,
• Ar 1 , Ar 3 , Ar 5 , Ar 6 are the same or different, preferably the same
• n 1 to 20, preferably 1, 2 or 3, particularly preferably 1,
• Ar 2 , Ar 4 identical or different from Ar 1 , Ar 3 , Ar 5 and Ar 6 , have the same meanings as Ar 1 , Ar 3 , Ar 5 and Ar 6 , only one of the two possible binding sites to the polymer is realized;
• Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 can be substituted identically or differently with one or more radicals R 2 -R 7 ;
• R 1 is H, a hydrocarbon radical having 1 to 22 carbon atoms or Ar 7 , where Ar 7 can have the same meanings as Ar 1 to Ar 6 ;
• R 2 -R 7 are identical or different H, an alkyl group with 1 to 22,
• R 8 identical or different from R 1 , has the same meanings as R 1 ; n is 0, 1 or 2, preferably 0 or 1, particularly preferably 0.
• Ar 1 , Ar 3 , Ar 5 , Ar 6 are the same or different
• n 1 to 20, preferably 1, 2 or 3, particularly preferably 1,
• Ar 2 , Ar 4 have the same or different meanings as Ar 1 , Ar 3 ,
• Polymer is realized, or are
• R 9 -R 1 5 are the same or different F, Cl, a straight-chain or
• R 1 2-1 5 can also be H.
• the invention therefore also relates to polymers containing
• Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 are the same or different and / or
• polynuclear optionally linked via one or more, preferably a bridge, and / or condensed aryl and / or
• Heteroaryl groups preferably with 4 to 400, particularly preferably 4 to 100, very particularly preferably 4 to 20 carbon atoms, which can optionally be substituted, two of Ar 1 , Ar 3 , Ar 5 and Ar 6 and of Ar 2 and Ar 4 each run out of a bond;
• R 1 is a carbon hydrogen residue with 1 to 22 carbon atoms
• Ar 7 may optionally be substituted, preferably with F, and may also contain heteroatoms, preferably O, or Ar 7 , where Ar 7 has the same meanings as Ar 1 -6 independently of Ar 1 -6 ;
• n 0, 1 or 2, preferably 0 or 1, particularly preferably 0.
• Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 and R 1 are those given in formula (I)
• Ar 6 has the meanings given in the formula (I) and Z represents C 1 -C 22 alkoxy, preferably ethoxy, or aryl radicals, preferably phenyl.
• Condensing agent preferably of potassium tert-butoxide or sodium hydride.
• the polycondensation is advantageously carried out in such a way that the equimolar mixture of the starting components (II) and (III) in one
• Solvent is introduced and, under an inert gas atmosphere and stirring, preferably at least molar amounts of condensing agent are introduced in solution or suspension.
• the condensing agent can also be introduced alone or with the biscetone in a solvent and the
• Bisphosphorus component are added. Benzene, toluene, xylene or dimethylformamide are preferably used as solvents Reaction temperature is preferably 60 to 1 20 ° C and the reaction time 0.1 to 20, preferably 0.1 to 5, particularly preferably 0.1 to 1 hour. The implementations are almost quantitative.
• Working up can be carried out by adding water, if appropriate an acid, such as acetic acid, and removing the organic reaction phases.
• the condensation products obtained can be extracted for purification, e.g. with alcohols or acetic acid, or from solution in a solvent using a non-solvent.
• This manufacturing process is generally described, for example, in DD 84 272,
• the radicals R 1 in the formula (I) may also have different meanings. Furthermore, by delayed addition of given at least one of the comonomers the possibility of producing block copolymers.
• Such compounds are suitable, especially in a mixture with the
• Polymers according to the invention also as electroluminescent materials.
• Macrocyclic compounds can form in the polymerization of starting compounds with meta-substituted structural elements.
• the polymers according to the invention or used according to the invention can therefore also be present in a mixture with these macrocyclic compounds, which does not interfere with their use as electroluminescent material.
• the preparation takes place under reaction conditions which are known and suitable for the reactions mentioned. It can also by itself
• the bis (diphenylphosphine oxides) or bis (phosphonic acid esters) required as condensation components are easily accessible, for example, using the MichaelisArbusov reaction from the corresponding bis (halogenomethyl) compounds with ethyl diphenylphosphinate (C 6 H 5 ) 2 POC 2 H 5 or with triethyl phosphite.
• aldehydes can be derived from bis-carboxylic acid derivatives controlled reduction with reducing agents such as lithium tris-alkoxyalanates or H 2 / Pd ("Rosenmund reduction”) can be obtained:
• Bisaldehydes can be obtained from bischloromethyl precursors, for example, by the sommelet reaction
• R 1 in formula (I) is not hydrogen, bisketones are considered as Starting materials used.
• Bisketones can also be produced by Friedel-Crafts acylation:
• the starting compounds for bisaldehydes and bisketones are the tertiary, aromatic amines (IV) and (V). They can be classified according to the known
• tertiary aromatic Amines for example, can also be prepared by the process given in Scheme 1.
• N- (alkylaryl) diarylamines can be obtained, for example:
• R alkyl, preferably C 1 -C 22 , particularly preferably t-butyl or neopentyl.
• the starting material for compounds in which Ar 3 is a biphenyl group can, for example, be the commercially available (from HW Sands, Jupiter, Fl., USA) N, N'-diphenyl-N, N'-di-m-tolylbenzidine.
• the invention therefore also relates to a process for producing an electroluminescent material, characterized in that a) an organophosphorus compound of the formula (III)
• Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 are the same or different and / or
• polynuclear optionally linked via one or more, preferably a bridge, and / or condensed aryl and / or
• Heteroaryl groups preferably with 4 to 400, particularly preferably 4 up to 100, very particularly preferably 4 to 20 carbon atoms, which can optionally be substituted, where Ar 1 , Ar 3 , Ar 5 and Ar 6 each have two bonds and Ar 2 and Ar 4 each have a bond;
• R 1 is a carbon hydrogen residue with 1 to 22 carbon atoms
• Ar 7 may optionally be substituted, preferably with F, and may also contain heteroatoms, preferably 0 or Ar 7 , where Ar 7 has the same meanings as Ar 1 -6 independently of Ar 1 -6 ;
• n 0, 1 or 2, preferably 0 or 1, particularly preferably 0. and b) the polymer thus obtained, containing structural units of the formula (I), is applied in the form of a film to a substrate which may also contain further layers.
• the invention further relates to an electroluminescent device with one or more active layers, at least one of these active layers containing one or more polymers according to the invention.
• the active layer can be, for example, a light-emitting layer and / or a
• Transport layer and / or a charge injection layer Transport layer and / or a charge injection layer.
• Electroluminescent devices containing polymers are described, for example, in
• Electrodes usually contain an electroluminescent layer between a cathode and an anode, at least one of the electrodes being transparent.
• electroluminescent layer between a cathode and an anode, at least one of the electrodes being transparent.
• Electron transport layers can be introduced and / or between the electroluminescent layer and the anode one or more
• Hole injection and / or hole transport layers can be introduced.
• Metals or metallic alloys e.g. Ca, Mg, Al, In, Mg / Ag serve.
• ITO indium oxide / tin oxide
• Substrate e.g. made of glass or a transparent polymer.
• the cathode is set to a negative potential with respect to the anode. Electrons are transferred from the cathode to the
• Electron injection layer Electron transport layer or injected directly into the light emitting layer. At the same time, holes are drilled from the anode into the hole injection layer / hole transport layer or directly into the
• the color of the emitted light can be varied by the materials used as the light-emitting layer.
• Electroluminescent devices are used e.g. as self-illuminating display elements, such as indicator lights, alphanumeric displays,
• Tg glass transition temperature
• VPO Vapor Pressure Osmometry (see e.g. Cherdron, Kern, Braun, Internship in Macromolecular Chemistry)
• UV / VIS UV / VIS spectroscopy
• Phosphoryl chloride and DMF are mixed with the exclusion of moisture and ice cooling, and the triphenylamine is added in portions after 20 minutes.
• the mixture is then stirred at 80 ° C. for eight hours, poured onto 300 g of crushed ice, allowed to come to room temperature and extracted with chloroform. After the solvent has been stripped off, the dark green oil is taken up in toluene and filtered through a glass filter frit charged with neutral aluminum oxide. The clear, yellow solution is evaporated to dryness and recrystallized from petroleum ether / toluene. Yellow crystals are obtained in 71% yield. Melting point 142 ° C.
• Magnetic stirrer and distillation bridge heated to 130 ° C, with ethyl bromide being distilled off.
• the mixture is heated to 1 90 ° C. within 1 hour and stirred at this temperature for a further 3 hours. Remaining for removal
• Triethyl phosphite is applied at this temperature for a further 30 minutes. After cooling, the residue solidifies to a waxy mass, which is recrystallized from petroleum ether. You get fine white crystals,
• a solution of the polymer from Example 4 in chlorobenzene (20 mg / ml) is applied under nitrogen by spin coating at 1000 rpm to a glass support (structured, structured, 2 mm wide) coated with ITO (indium tin oxide).
• the glass support is placed over a lock while maintaining the
• the diphenylaminobenzaldehyde and the bisphosphonate are placed under protective gas in 1,50 ml of toluene. While stirring, the potassium tert-butoxide is added in one portion at the boiling point, the mixture foaming strongly. The mixture is stirred for a further two hours at 80 ° C. and then hydrolyzed with 200 ml of a 10% acetic acid solution. The mixture is stirred vigorously and then transferred to a separatory funnel. The organic phase is shaken out several times with water and then dried over anhydrous sodium sulfate. It is strongly concentrated and the crude product is purified by column chromatography (neutral aluminum oxide, eluent toluene). After stripping off the solvent and drying, bright orange crystals are obtained in 82% yield.
• column chromatography neutral aluminum oxide, eluent toluene
• a solution of the polymer from Example 8 in chlorobenzene (20 mg / ml) is applied under nitrogen by spin coating at 1000 rpm to a glass support (structured, structured, strip 2 mm wide) coated with ITO (indium tin oxide).
• the glass support is placed over a lock while maintaining the
• Boiling heat then add another 200 ml of toluene and filter the hot solution from the slimy sediment. The filtrate is evaporated to dryness, in
• Example 11 An electroluminescent device with the polymer from Example 11 was produced analogously to Example 5. Threshold voltage: 2.8 V; Max. Efficient: 0.20% at 5.2 V and 7 mA, a light intensity of 100 Cd / m 2 was found.
• Phosphoryl chloride and DMF are mixed with the exclusion of moisture and ice cooling, and after 20 minutes the fluorotriphenylamine is added. The mixture is then stirred at 80 ° C. for eight hours, poured onto 300 g of crushed ice, allowed to come to room temperature and extracted with chloroform. After the solvent has been stripped off, the dirty brown solid is taken up in toluene and filtered through a glass filter frit charged with neutral aluminum oxide. The clear and yellow solution is evaporated to dryness and recrystallized from petroleum ether / toluene. Yellow crystals are obtained in 51% yield. Melting point: 204-205 ° C.
• the diphosphonate and the dialdehyde are dissolved under protective gas in 30 ml of toluene at the boiling point and mixed with the potassium tert-butoxide in solid form.
• the reaction mixture foams violently and suddenly becomes viscous.
• toluene is carefully metered in so that the mixture remains stirrable.
• the solvent is removed under reduced pressure, taken up in chloroform with heating and precipitated in isopropanol. After suction, the mixture is extracted with methanol for five hours. The polymer is obtained in yellow, stringy fibers in 78% yield.

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• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Electroluminescent Light Sources (AREA)
• Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
• Luminescent Compositions (AREA)

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• 1996
  • 1996-09-03 JP JP51085197A patent/JP2002515078A/ja not_active Ceased
  • 1996-09-03 EP EP96930152A patent/EP0848739A1/de not_active Withdrawn
  • 1996-09-03 KR KR10-1998-0701611A patent/KR100421569B1/ko not_active IP Right Cessation
  • 1996-09-03 WO PCT/EP1996/003852 patent/WO1997009394A1/de not_active Application Discontinuation
  • 1996-09-03 US US08/711,367 patent/US5814244A/en not_active Expired - Lifetime
  • 1996-09-03 CN CN96197502A patent/CN1125865C/zh not_active Expired - Fee Related

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