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  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
  • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
  • G03G5/0601—Acyclic or carbocyclic compounds
  • G03G5/0605—Carbocyclic compounds
  • G03G5/0607—Carbocyclic compounds containing at least one non-six-membered ring
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
  • G03G5/0601—Acyclic or carbocyclic compounds
  • G03G5/0612—Acyclic or carbocyclic compounds containing nitrogen
  • G03G5/0614—Amines
  • G03G5/06142—Amines arylamine
  • G03G5/06147—Amines arylamine alkenylarylamine
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
  • G03G5/0664—Dyes
  • G03G5/0666—Dyes containing a methine or polymethine group
  • G03G5/0672—Dyes containing a methine or polymethine group containing two or more methine or polymethine groups
• • 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
• • 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
  • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/02—Ortho- or ortho- and peri-condensed systems
  • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
  • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
  • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
  • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
  • C07C2603/18—Fluorenes; Hydrogenated fluorenes
• • 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
  • C09K2211/1011—Condensed systems
• • 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]
  • H10K50/14—Carrier transporting layers

Definitions

• the invention relates to novel arylamine derivatives of divinylfluorine and their use for electrophotographic applications and for organic light-emitting diodes and for new materials and active ingredients.
• triarylamines in electrophotography are well known. Furthermore, it has been found that triarylamine-derivatized hole-extended hole-hole promoters (defect-electron conductors) obtained by the incorporation of vinyl, butadienyl and styryl groups often have a much higher hole mobility than those without extension (EP795791 to Mitsubishi Chemical). Increasing hole mobility in charge transport materials is fundamental to increasing the efficiency of electrophotography in laser printers and copiers as well as electroluminescence in OLEDs.
• hole conductor materials with a much higher hole mobility than the standard hole conductors such as TPD (N 1 N'-diphenyl-N, N'-di-m-to! Yl-benzidine) or N, N'-diphenyl-N, N'-di-naphth-1-yl-benzidine ( ⁇ -NPD).
• TPD N 1 N'-diphenyl-N, N'-di-m-to! Yl-benzidine
• ⁇ -NPD N, N'-diphenyl-N, N'-di-naphth-1-yl-benzidine
• the concentration of charge transport material can be reduced and thus the stability of the hole transport layer can be increased.
• the printing speed is increased by using hole guides with high mobility.
• the subject of this patent is also the synthesis of divinyl fluorene compounds.
• dialkylation of the C-9 atom is carried out by means of alkyl bromide and sodium hydride. This is followed by reaction with paraformaldehyde and hydrogen bromide in acetic acid to give the corresponding 2,7-bis (bromomethyl) -9,9-dialkylfluorene. This is reacted by means of triethyl phosphite to give 2,7-bis (diethylphosphonatomethyl) -9,9-dialkylfluorene.
• the aim of the invention is a wear-resistant photoconductor with excellent durability, high sensitivity and low residual potential
• the object of the invention is to produce compounds and to propose their use as a hole conductor with substantially improved hole conductor mobility. These compounds should be new as substances or, if known, have not previously been considered for the intended purpose.
• the invention is based on the scientific idea of creating new potential hole conductors by introducing groups with readily polarizable ⁇ -electrons - such as vinyl groups - into arylamino structures which are in direct conjugation with a fluorene molecule, with high hole conductor mobility and suitability for electrophotographic applications.
• the present invention claims as compounds compounds of formula 1 and their use in electrophotography, in OLEDs and for new drugs and materials.
• the group Ar in the general chemical formula 1 represents a homoaromatic or heteroaromatic group which may optionally be benzoannelated, for example phenylene, naphthylene, thienylene, furylene or anthracenylene units, if appropriate substituted by alkyl, aryl or arylalkyl groups, biphenylene units according to formula 6, fluorenylene, dibenzofuranylene, dibenzothiophenylene, carbazolylene or dibenzosilolylene units according to formula 7, wherein the unit A is selected from the following structures.
• R 1 and R 2 are independently of one another a branched or linear alkyl group (C 1 to C 2 O alkyl group), a branched or linearly unsaturated hydrocarbon group, a cycloalkyl group (eg cyclohexyl group) or an aryl group (eg phenyl, alkylphenyi, naphthyl, alkylnaphthyl). Biphenylyl, alkylbiphenylyl, stilbenyl or tolanyl group), a branched or linear alkoxy group.
• a branched or linear alkyl group C 1 to C 2 O alkyl group
• a branched or linearly unsaturated hydrocarbon group eg cyclohexyl group
• aryl group eg phenyl, alkylphenyi, naphthyl, alkylnaphthyl.
• R 3 and R 4 are each independently phenyl, alkylphenyi, in particular methylphenyl, biphenylyl, alkylbiphenyl, naphthyl, alkylnaphthyl, phenanthrenyl, alkylphenanthrenyl, anthracenyl, alkylanthracenyl, fluorenyl, alkylfluorenyl, triarylmethyl-aryl or triarylsilyl-aryl.
• the compounds can be synthesized according to formula scheme 1.
• 9,9-Dialkylfluorene 2 is 2,7-bishalomethylated using paraformaldehyde and HBr.
• the intermediate 3 is reacted in the second step with triethyl phosphite to give the corresponding 2,7-bis (dialkylphosphonatomethyl) -9,9-dialkylfluorene 4, which provides the desired 2,7-divinylfluorene 1 in the third step by reaction with an aromatic aldehyde.
• These reactions are carried out analogously to the specification in US2006 / 0022193A1. Thus, no procedural protection for the synthesis be raised by divinylfluorenes.
• the group Ar in the general chemical formula 5 represents a homoaromatic or heteroaromatic group which may optionally be benzoannelated, for example phenylene, naphthylene, thienylene, furylene or anthracenylene units, optionally substituted by alkyl, aryl or arylalkyl groups, biphenylene units according to formula 6, fluorenylene, dibenzofuranylene, dibenzothiophenylene, carbazolylene or dibenzosilolylene units according to formula 7, wherein the unit A is selected from the following structures.
• R 3 and R 4 are each independently phenyl, alkylphenyl, in particular methylphenyl, biphenylyl, alkylbiphenyl, naphthyl, alkylnaphthyl, phenanthrenyl, alkylphenanthrenyl, anthracenyl, alkylanthracenyl, fluorenyl, alkylfluorenyl, triarylmethyl-aryl or triarylsilyl-aryl.
• R 1 and R 2 are each independently a branched or linear alkyl group (C 1 to C 2 O alkyl group), a branched or linear unsaturated hydrocarbon group, a cycloalkyl group (eg cyclohexyl group) or an aryl group (eg phenyl, alkylphenyl, naphthyl, alkylnaphthyl). Biphenylyl, alkylbiphenylyl, stilbenyl or tolanyl group), a branched or linear alkoxy group.
• a branched or linear alkyl group C 1 to C 2 O alkyl group
• a branched or linear unsaturated hydrocarbon group eg cyclohexyl group
• aryl group eg phenyl, alkylphenyl, naphthyl, alkylnaphthyl.
• R 3 and R 4 are each independently phenyl, alkylphenyl, in particular methylphenyl, biphenylyl, alkylbiphenyl, naphthyl, alkylnaphthyl, phenanthrenyl, alkylphenanthrenyl, anthracenyl, alkylanthracenyl, fluorenyl, alkylfluorenyl, triarylmethyl-aryl or triarylsilyl-aryl.
• R 3 and R 4 are each independently phenyl, alkylphenyl, in particular methylphenyl, biphenylyl, alkylbiphenyl, naphthyl, alkylnaphthyl, phenanthrenyl, alkylphenanthrenyl, anthracenyl, alkylanthracenyl, fluorenyl, alkylfluorenyl, triarylmethyl-aryl or triarylsilyl-aryl.
• R 11 and R 12 are each independently H, a branched or linear alkyl group (C 1 to C 20 alkyl group), a branched or linear unsaturated hydrocarbon group, a cycloalkyl group (eg cyclohexyl group) or an aryl group (eg, phenyl, alkylphenyl, naphthyl, alkylnaphthyl, biphenylyl, alkylbiphenylyl, stilbenyl or tolanyl group), a branched or linear alkoxy group.
• a branched or linear alkyl group C 1 to C 20 alkyl group
• a branched or linear unsaturated hydrocarbon group eg. cycloalkyl group
• aryl group eg, phenyl, alkylphenyl, naphthyl, alkylnaphthyl, biphenylyl, alkylbiphenylyl, stilbenyl
• R 11 and R 12 are each, independently of one another, H or a methyl group which may be in the ortho-, metha- and para-position to the amino group.
• R 11 and R 12 each represents a methyl group in para position to the amino group.
• Finely powdered 9,9-dimethylfluorene (Sensient, 20.0 g, 102.9 mmol) and paraformaldehyde (15.0 g, 500 mmol) were placed in a 250 ml sulfonation flask with internal thermometer. Then, 100 ml of 33% HBr in glacial acetic acid and a magnetic stir bar were added. The flask was stoppered and stirred for 30 h at 45 0 C. The white solid that formed was filtered off with suction and washed with a little ice-cold water (2 ⁇ 25 ml) and ice-cold methanol (2 ⁇ 20 ml). Finally, it was recrystallized from glacial acetic acid.
• 2,7-Bis (bromomethyl) -9,9-dimethylfluorene (25.00 g, 66 mmol) and 25 ml of triethyl phosphite (150 mmol) are in a 100 ml three-necked flask with cross stirring, argon inlet, internal thermometer and distillation with Vigreux column under Argon purge entered. It is heated under standing oil bath carefully to 120-125 0 C. At 65-70 0 C began gas evolution and it formed a clear, stirrable mixture. The ethyl bromide was distilled off at 75-80 ° C. under a gentle stream of argon.
• a chromatography column 100 cm x 12 cm from Neubert and Kieselgel 60 (0.063-0.2 mm) Merck was used.
• the eluent was a mixture of cyclohexane and toluene (2: 1).
• To fill the column about 4 kg of silica gel with 9 liters of eluent mixture were mixed in several portions. Then a layer of sea sand (2 cm) was carefully applied.
• the crude product was dissolved in 1.5 liters of toluene and mixed with 300 g of silica gel. It was rotary evaporated to dryness on a rotary evaporator and the solid silica gel mixture was carefully positioned over the sand layer.
• Compound 12 meets the industry-specified solubility criterion of 1 g of substance / 6 ml of methylene chloride or THF. From this compound, scale up to 35 g was performed. The compound was replaced by conventional Ie cleaning method such. B. recrystallization or column chromatography to a HPLC purity of> 99.5%.
• the electrophotographic properties of the produced hole conductor were determined in a double layer system by the cooperation partner.
• an aluminized polyester substrate was coated with a dispersion of Y-titanyl phthalocyanine in polycarbonate / methylene chloride.
• the charge generation layer thus formed after drying was coated with a solution of the corresponding hole conductor in polycarbonate / methylene chloride and measured after drying.
• the layer sequence to be tested was negatively charged in the dark with a corotron wire (Uo). After a defined time, the device is exposed with a defined amount of light. The voltage drop until exposure is referred to as dark decay (U D ).
• U D dark decay
• the electrophotographic sensitivity results from the half-life of the discharge cycle multiplied by the irradiated light intensity. A typical discharge curve is shown in Figure 1. For commercial use, an electrophotographic sensitivity of at least 0.5 ⁇ J / cm 2 must be achieved with the layer sequence used.

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• 2006
  • 2006-12-13 DE DE102006059215A patent/DE102006059215A1/de not_active Withdrawn
• 2007
  • 2007-12-11 CN CN200780049771A patent/CN101641321A/zh active Pending
  • 2007-12-11 WO PCT/EP2007/010762 patent/WO2008071376A1/de active Application Filing
  • 2007-12-11 KR KR1020097014568A patent/KR20090107032A/ko not_active Ceased
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