Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
  • C08G73/026—Wholly aromatic polyamines
  • C08G73/0266—Polyanilines or derivatives thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
  • H01B1/124—Intrinsically conductive polymers
  • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
• • 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
  • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
• • 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
• • 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]
  • H10K50/17—Carrier injection 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
  • H10K85/10—Organic polymers or oligomers
  • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene

Definitions

• the present invention relates to a charge-transporting varnish, and more specifically, for example, a charge-transporting varnish capable of forming a charge-transporting thin film capable of preventing current and charge concentration phenomena and improving electrical characteristics and life characteristics. It is about.
• This charge-transporting varnish can be used for organic electorum luminescence (hereinafter abbreviated as EL) elements, capacitor elements, antistatic films, and the like.
• EL organic electorum luminescence
• Organic EL devices especially low-molecular organic EL (hereinafter abbreviated as OLED) devices, have their characteristics such as extremely thin organic layers and separation of functions by multi-layering by Eastman Kodak Co., Ltd. Greatly improved (Applied Physics Letters, USA, 1987, 51, p. 91 3-915).
• OLED organic EL
• PLED EL
• PLED polymeric light-emitting materials
• the oligoaniline compound when the oligoaniline compound is formed into a thin film having a charge transporting property, it is usually necessary to perform firing at a high temperature for a long time in the presence of oxygen. For this reason, when a low-molecular-weight oligoaniline-based material is used as a hole injection layer in an OLED element or a PLED element, the time required to manufacture the element increases, resulting in a decrease in productivity. Therefore, it has been required to reduce the baking time after film formation. Disclosure of the invention
• An object of the present invention is to provide a charge transporting varnish capable of exhibiting excellent conductive properties in a short time firing in a system using an oligoaniline compound and a charge-accepting dopant material.
• the present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that a charge transporting substance comprising an oligoaniline compound represented by the following formula (1) is dissolved or uniformly dispersed in a solvent.
• a conductive varnish it was found that a thin film having the same conductivity as the conventional one can be formed only by baking for a short time after film formation, and thus completed the present invention.
• the present invention provides the following inventions [1] to [8].
• a charge transport material comprising an oligoaniline compound represented by the formula (1) and at least one solvent, wherein the charge transport material is dissolved or uniformly dispersed in the solvent.
• a charge-transporting varnish characterized in that:
• R 1 represents a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group, an organooxy group or an acyl group
• R 2 and R 3 each independently represent a hydrogen atom
• R 4 to R 7 each independently represent a hydrogen atom, a hydroxyl group, an unsubstituted or substituted monovalent hydrocarbon group, an organooxy group, an acyl group or a sulfonic acid group
• n are each independently an integer of 1 or more, and satisfy m + 2n ⁇ 20, and the quinoid moiety is present at any position in the structural formula due to tautomerism.
• R 1 represents a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group, an organooxy group or an acyl group
• R 2 and R 3 each independently represent a hydrogen atom
• R 4 to R 7 each independently represent a hydrogen atom, a hydroxyl group, an unsubstituted or substituted monovalent hydrocarbon group, an organooxy group, an acyl group or a sulfonic acid group
• n are each independently an integer of 1 or more, and satisfy m + 2 n ⁇ 20.
• D represents a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring or a heterocyclic ring
• R 8 and R 9 each independently represent a carboxyl group or a hydroxy group.
• a positive electrode prepared using the charge-transporting varnish of any of [1] to [4].
• An organic electroluminescent device including an injection layer.
• An organic electroluminescent device including a hole transport layer produced using the charge-transporting varnish of any one of [1] to [4].
• the charge-transporting varnish of the present invention is a charge-transporting varnish of a conventionally used aqueous solution. Unlike varnish, it can be used only with organic solvents.
• the charge transporting thin film of the present invention on the electrode surface, an electric short circuit can be prevented.
• this charge transporting thin film as the charge injection layer of an organic EL device, it is possible to lower the injection barrier by relaxing the ionization potential between the electrode and the organic layer.
• the charge transporting varnish of the present invention has a good thin film formation process, it is also useful for application to a capacitor electrode protective film and application to an antistatic film.
• FIG. 1 is an infrared absorption spectrum diagram of phenylpentaaniline synthesized in Example 1.
• FIG. 2 is an infrared absorption spectrum diagram of the oxidized phenylene penaniline synthesized in Example 1.
• the charge-transporting varnish of the present invention contains a charge-transporting substance and a solvent that are the main components of the charge-transporting mechanism, or a charge-transporting substance, a charge-accepting dopant substance that improves the charge-transporting ability of the charge-transporting substance, And a solvent.
• the charge-transporting substance (and the charge-accepting dopant substance) is either completely dissolved or uniformly dispersed in the solvent.
• the charge transporting property is synonymous with the conductivity, and means any of a hole transporting property, an electron transporting property, and a charge transporting property of both holes and electrons.
• the charge transporting varnish of the present invention may have a charge transporting property itself, or may have a charge transporting property in a solid film obtained by using the varnish.
• the charge transporting substance used in the present invention is an oligoaniline compound represented by the formula (1).
• R 1 represents a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group, an organooxy group or an acyl group
• R 2 and R 3 each independently represent a hydrogen atom
• R 4 to R 7 each independently represent a hydrogen atom, a hydroxyl group, an unsubstituted or substituted monovalent hydrocarbon group, an organooxy group, an acyl group or a sulfonic acid group
• m and n are each independently an integer of 1 or more, and satisfy m + 2n ⁇ 20, and the quinoid moiety is present at any position in the structural formula due to tautomerism.
• the substituent R 1 of the oligoaniline compound used in the present invention is hydrogen, an unsubstituted or substituted monovalent hydrocarbon group, an organooxy group or an acyl group, and R 2 and R 3 are each independently a hydrogen atom, It is a substituted or substituted monovalent hydrocarbon group or acyl group.
• the monovalent hydrocarbon group and the organooxy group preferably have 1 to 20 carbon atoms.
• the benzyl group those having 2 to 20 carbon atoms are preferable.
• Specific examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, t-butyl group, hexyl group, octyl group, and decyl group, cyclopentyl group, and cyclohexyl group.
• Cycloalkyl group such as sil group, bicycloalkyl group such as bicyclohexyl group, vinyl group, 1-propenyl group, 2-propenyl group, isopropyl group, 1-methyl-2-propenyl group Alkenyl group such as 1-, 2- or 3-butenyl group, hexenyl group, phenyl group, xylyl group, aryl group such as tril group, biphenyl group, naphthyl group, benzyl group, phenylethyl group, Examples thereof include aralkyl groups such as a phenylcyclohexyl group, and those in which part or all of the hydrogen atoms of these monovalent hydrocarbon groups are substituted with a halogen atom, a hydroxyl group, an alkoxy group, or the like. be able to.
• the organooxy group includes an alkoxy group, an alkenyloxy group and an aryl group.
• alkyl group, the alkenyl group, and the aryl group include the same as those described above.
• Examples of the acryl group include those having 2 to 10 carbon atoms, for example, an acetyl group, a propionyl group, a butyryl group, an isoptyryl group, a paleryl group, an isopaparyl group, and a benzoyl group.
• R 1 and R 2 preferably, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, or a substituent of an alkyl group or an alkoxy group having 1 to 4 carbon atoms, respectively.
• R 3 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may have an alkoxy group as a substituent.
• R 1 is a hydrogen atom and R 3 is a phenyl group, that is, it is preferable that both ends of the oligoaniline compound of the formula (1) are blocked with a phenyl group.
• the substituents R 4 to R 7 are each independently a hydrogen atom, a hydroxyl group, an unsubstituted or substituted monovalent hydrocarbon group, an organooxy group, an acyl group or a sulfonic acid group, and As the hydrogen group and the organooxy group, those having 1 to 20 carbon atoms are preferable, and as the acyl group, those having 2 to 20 carbon atoms are preferable.
• the same groups as those described for R 1 can be mentioned.
• the substituents R 4 to R 7 are preferably a hydrogen atom, an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkenyl group, an acyl group, a sulfonic acid group, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms.
• R 4 to R 7 are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms in the alkoxy group.
• a phenyl group, a cyclohexyl group, a cyclopentyl group, a biphenyl group, a bicyclohexyl group or a phenylcyclohexyl group which may have Particularly, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxyalkyl group having 1 to 4 carbon atoms of the alkoxy group and 1 to 4 carbon atoms of the alkyl group, and a pinyl group , A 2-propenyl group, an acetyl group, a benzoyl group, a sulfonate group, a hydroxyl group, and a substituent (the substituent is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms).
• Examples thereof include a phenyl group, a cyclohexyl group, a biphenyl group, a bicyclohexyl group and a phenylcyclohexyl group which may be possessed.
• the substituents with the same symbol may be the same or different.
• the numbers m and n in the oligoaniline moiety are each independently an integer of 1 or more.
• the ratio of m to n is preferably 2 or more.
• m + 2n is preferably 20 or less.
• the concentration is preferably 10 or less, particularly preferably 5 or less.
• the charge transporting substance of the formula (1) can be obtained by oxidizing the oligoaniline compound represented by the formula (2).
• the oligoaniline compound represented by the formula (2) has no molecular weight distribution, in other words, an oligoaniline compound having a dispersity of 1 in consideration of improving solubility and uniform charge transport. preferable.
• oligoaniline compound examples include an oligoaniline compound that is soluble in an organic solvent such as phenyltetraaniline and phenylpenaniline.
• organic solvent such as phenyltetraaniline and phenylpenaniline.
• the oxidation treatment performed on the oligoaniline compound of the formula (2) may be, for example, a method of dissolving the oligoaniline compound in an appropriate solvent and then chemically oxidizing with an appropriate oxidizing agent, or a method of powdering the oligoaniline compound or a powder thereof.
• a method of stirring and oxidizing the solution in the air or in the presence of oxygen while heating the solution may be mentioned, but the method is not limited thereto.
• solvent used for the oxidation treatment examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N'-dimethylimidazolidinone, dimethylsulfoxide, Solvents such as chloroform, tetrahydrofuran, 1,4-dioxane, toluene, and xylene are mentioned, but are not particularly limited as long as they can dissolve the oligoaniline compound. These may be used alone or as a mixture.
• oxidizing agent used in the oxidation treatment include halogens such as chlorine, bromine and iodine, inorganic acids such as nitric acid and sulfuric acid, ozone, hydrogen peroxide, potassium permanganate, and potassium dichromate.
• Organic oxidants such as 5,6-dicyano 1,4-benzoquinone (DDQ), chlorale, and bromanil can be mentioned, but are not limited thereto.
• an electron-accepting dopant substance is used for the hole-transporting substance
• a hole-accepting dopant substance is used for the electron-transporting substance. It is desirable to have receptivity.
• the solubility is not particularly limited as long as it is soluble in at least one kind of solvent.
• the electron-accepting dopant include inorganic strong acids such as hydrogen chloride, sulfuric acid, nitric acid, and phosphoric acid, aluminum chloride ( ⁇ ) (A 1 C 1, titanium tetrachloride 0V) (T i C l), boron tribromide (BBr 3), boron trifluoride ether complex (BF 3 - OE t 2) , iron chloride (IE) (FeC 1 3) , copper chloride ( ⁇ ) (CuC 1 2) pentachloride antimony (V) (SBC 1 5), arsenic pentafluoride (V) (As F 5), phosphorus pentafluoride (PF 5), tris (4-Buromofueniru) Aminiumu to Kisakuro port anti Mona Doo (T Lewis acids such as BPAH), strong organic acids such as benzenesulfonic acid, tosylic acid, camphorsulfonic acid, hydroxybenzenesulfonic
• hole-accepting dopants include alkali metals (L i, Na, K, C s), lithium quinolinolate (L i Q), and lithium acetyl acetonate (L i (acac)).
• the present invention is not limited thereto. It is preferable that both the charge transporting substance and the charge accepting dopant substance are amorphous solids. If either one or both are not amorphous solids, both the charge transporting substance and the charge accepting dopant substance are used.
• a material system that exhibits amorphous solidity after film formation is preferable.
• At least one of the substances preferably has a random intermolecular interaction, and is a low-molecular compound.
• those having three or more different polar functional groups in the same molecule are preferable.
• Such a compound is not particularly limited, and examples thereof include tiron, dihydroxybenzenesulfonic acid, and a sulfonic acid derivative represented by the formula (3). Acid derivatives are preferred.
• Specific examples of the sulfonic acid derivative include a sulfosalicylic acid derivative, for example, 5-sulfosalicylic acid.
• R 8 and R 9 each independently represent a carbonyl group or a hydroxyl group.
• the solvent used for obtaining the charge-transporting varnish of the present invention is not particularly limited as long as it dissolves the oxidized charge-transporting substance, but the varnish may be completely dissolved or uniformly dispersed. It is preferable that it is in the state where it is.
• Specific examples of these solvents include water, methanol, N, N-dimethylformamide, N, N-dimethylacetoamide, N-methylpyrrolidone, N, N'-dimethylimidazolidinone, dimethylsulfoxide, chloroform-form, toluene and Examples of the solvent include methanol. These may be used alone or as a mixture.
• a high-viscosity solvent may be mixed for the purpose of obtaining the high-viscosity varnish as long as the solubility is not impaired.
• a solvent that imparts the flatness of the film during firing to the varnish for the purpose of improving the wettability to the substrate, adjusting the surface tension of the solvent, adjusting the polarity, adjusting the boiling point, etc. within a range that does not impair the solubility. May be used. Specific examples thereof include, but are not limited to, butyricol, butyl glycol monoethyl ether, dipropylene glycol monomethyl ether, ethyl carbitol, diacetone alcohol, acetylolactone, and ethyl lactate. .
• the concentration of the charge transporting substance in the solution can be controlled at 1 to 80% by mass, particularly 1 to 20% by mass.
• the charge transporting varnish is applied on a substrate, and the solvent is evaporated to form a charge transporting coating on the substrate.
• the coating method is not particularly limited, and examples thereof include a dip method, a spin coating method, a transfer printing method, a roll coating method, an ink jet method, a spray method, and brush coating.
• the method for evaporating the solvent is not particularly limited. It is possible to perform evaporation in a simple atmosphere, that is, in the atmosphere, an inert gas such as nitrogen, or in a vacuum.
• the firing temperature is not particularly limited as long as the solvent can be evaporated, but it is preferable to perform the firing at a temperature of 40 to 250 ° C. Two or more steps of temperature change may be applied in order to develop higher uniform film forming property and to make the reaction proceed on the substrate.
• the thickness of the charge transporting thin film obtained by the coating and evaporating operation is not particularly limited, but is preferably 5 to 200 nm when used as a charge injection layer in an organic EL device.
• a method of changing the film thickness there are a method of changing the solid content concentration in the varnish, and a method of changing the amount of the solution on the substrate at the time of coating.
• the method for producing an OLED device using the charge-transporting varnish of the present invention and the materials used can be listed as follows, but are not limited thereto.
• the electrode substrate to be used is preferably cleaned in advance by liquid washing with a detergent, alcohol, pure water, or the like, and the anode substrate is preferably subjected to a surface treatment such as an ozone treatment or an oxygen-plasma treatment immediately before use.
• a surface treatment such as an ozone treatment or an oxygen-plasma treatment immediately before use.
• the anode material is mainly composed of an organic substance, the surface treatment may not be performed.
• a hole transporting thin film is formed on the electrode by the above-mentioned method using the hole transporting varnish on the anode substrate. This is introduced into a vacuum deposition apparatus, and a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode metal are sequentially deposited to form an OLED element.
• a carrier block layer may be provided between any layers to control the light emitting region.
• the anode material include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZ ⁇ ), and those subjected to a flattening treatment are preferable. Polythiophene derivatives and polyanilines having high charge transport properties can also be used.
• Materials for forming the hole transport layer include (triphenylamine) dimer derivative (TPD), ( ⁇ -naphthyldiphenylamine) dimer (a-NPD), [(triphenylamine) dimer] and spiro dimer (Spiro).
• TPD triphenylamine dimer derivative
• a-NPD ⁇ -naphthyldiphenylamine dimer
• Spiro spiro dimer
• Materials for forming the light emitting layer include tris (8-quinolinolate) aluminum ( ⁇ ) (A 1 q 3 ), bis (8-quinolinolate), zinc (I) (Znq 2 ), and bis (2-methyl-18-quinolinolate) (P-phenylphenolate) aluminum ( ⁇ ) (BA 1 q) and 4,4, —bis (2,2-diphenylvinyl) biphenyl (DPVB i), etc.
• the light emitting layer may be formed by co-evaporating a hole transporting material and a light emitting dopant.
• Electron transport materials include A 1 Q 3 , BA 1 q, DPVB i, (2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole) (PBD), triazole Derivatives (TAZ), bathocuproin (BCP) and sialic derivatives.
• Materials forming the carrier block layer include PBD, TAZ, and BCP.
• lithium oxide Li i 2 0
• magnesium oxide Mg O
• alumina A 1 2 0 3
• lithium fluoride Li F
• magnesium fluoride magnesium fluoride
• the cathode material examples include aluminum, magnesium-silver alloy, aluminum-lithium alloy, lithium, sodium, potassium, and cesium.
• the charge-transporting varnish of the present invention is used for an OLED device, the following method can be used.
• An electron-transporting thin film is formed on the cathode substrate using the electron-transporting varnish, introduced into a vacuum evaporation apparatus, and formed using the same materials as described above for an electron-transporting layer, a light-emitting layer, a hole-transporting layer, After forming the hole injection layer, the anode material is formed into a film by a method such as sputtering to form an OLED element.
• the method for producing a PLED device using the charge-transporting varnish of the present invention is not particularly limited, and the following method is exemplified.
• the charge of the present invention is obtained by forming a luminescent charge transporting polymer layer instead of performing a vacuum deposition operation of the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer in the above-mentioned OLED device fabrication.
• a PLED device including a charge transporting thin film formed by a transporting varnish can be manufactured. Specifically, a hole-transporting thin film is formed on an electrode by using the hole-transporting varnish on the anode substrate by the above-described method, and a luminescent charge-transporting polymer layer is formed on the thin film. A cathode electrode is deposited to form a PLED element.
• an electron-transporting thin film is formed on an electrode using the electron-transporting varnish on the cathode substrate by the above-described method, a luminescent charge-transporting polymer layer is formed thereon, and the anode electrode is sputtered.
• PLED elements are manufactured by methods such as evaporation and spin coating.
• the same substances as those used in the production of the OLED element can be used, and the same cleaning treatment and surface treatment can be performed.
• a solvent is added to a luminescent charge transporting polymer material or a material to which a luminescent dopant is added, and the solution is dissolved or uniformly dispersed. After coating the electrode substrate on which the hole injection layer is formed, a method of forming a film by evaporating the solvent can be cited.
• Polyluminescent derivatives such as poly (9,9-dialkylfluorene) (PDAF), and poly (2-methoxy-5- (2'-ethylhexoxy) —1,4-phenyl)
• PDAF poly (9,9-dialkylfluorene
• PVCz polyvinyl carbazole
• Examples of the solvent include toluene, xylene and black form.
• Examples of the uniform dispersion method include a method of dissolving or uniformly dispersing by a method such as stirring, heating and stirring, and ultrasonic dispersion.
• the coating method is not particularly limited, and examples thereof include a dip method, a spin coating method, a transfer printing method, a roll coating method, an ink jet method, a spray method, and brush coating. It is desirable to apply these under an inert gas such as nitrogen or argon.
• Examples of the method of evaporating the solvent include a method of heating in an oven or a hot plate under an inert gas or in a vacuum.
• Formula (4) is shown with reference to the method described in Bulletin of Chemical Society of Japan, Vol. 67, p. 1749-1752, 1994.
• Phenylpenaniline (PPA) was obtained from the reaction of diaminodiphenylamine with monohydroxydiphenylamine.
• PP A The synthesis of PP A was performed according to the following procedure. That is, 1.00 g of p-diaminodiphenylamine is dissolved in 2 ml of toluene, and 10.21 g of tetra-n-butoxytitanium as a dehydrating condensing agent is added and dissolved. While maintaining the reaction solution in a nitrogen atmosphere at 110, 2.22 g of ⁇ -hydroxydiphenylamine dissolved in 42 ml of toluene was added, and the reaction was performed for 48 hours in a nitrogen atmosphere.
• the reaction solution cooled to room temperature was filtered, and the residue was washed with toluene and then with ethyl ether, and then dried to obtain a pale purple powder.
• the resulting powder is 4 0 parts of dioxane and 0.2 equivalents of hydrazine monohydrate were added, and the inside of the reaction system was replaced with nitrogen and dissolved by heating under reflux.
• 16 parts of toluene was added, the solution was suspended, and the mixture was heated under reflux, and the obtained solution was filtered while hot.
• the solid precipitated from the filtrate was recrystallized, washed successively with toluene-dioxane (1: 2.5) and ether in a nitrogen atmosphere, and then filtered.
• the synthesized PPA was oxidized by the following method. That is, 1.00 g of PPA was dissolved in a mixed solvent of 300 ml of toluene and 50 ml of dioxane, and the mixture was stirred at 110 ° C in the air for 48 hours to oxidize PPA. The obtained black liquid was filtered and the solvent was distilled off from the filtrate to obtain 0.93 g of a black powder (93% yield).
• FIG. 2 shows the infrared absorption spectrum of the obtained oxidized PPA.
• the intensity of the 3400 (; ! ⁇ ! ⁇ — ⁇ ! Stretching vibrations observed in Fig. 1 is reduced in Fig. 2.
• Example 2 After forming the hole transporting thin film on I TO glass substrate in the manner described in Example 1, was introduced into a vacuum deposition apparatus, shed one NPD, Al q 3, L i F, sequentially depositing A 1 did.
• Each film thickness 40 nm, 60 nm, 0.5 5 nm, and l O onm performs deposition operation after summer and a pressure of less than 8 X 10_ 4 P a, respectively, and the deposition rate 0.5 3 except L i F 0.4 nmZs, and 1 to 0.02 to 0.04 nmZs.
• the moving operation during the vapor deposition operation was performed in a vacuum. Table 2 shows the characteristics of the obtained OLE D element.
• Example 2 PPA obtained by synthesis and purification using the method described in Example 1 was subjected to 5-sulfosalicylic acid (5-SSA), N, N-dimethylacetamide (DMA c) and cyclohexanol. In addition, a varnish was prepared as described in Example 1.
• 5-SSA 5-sulfosalicylic acid
• DMA c N, N-dimethylacetamide
• cyclohexanol cyclohexanol
• Example 1 ITO glass substrate for 40 minutes immediately before spin coating with varnish Cleaning was performed.
• the obtained varnish was applied on an ITO glass substrate by the method described in Example 1, and baked at 160 ° C. and 180 ° C. in air to form a 30 nm thin film.
• Table 3 shows the firing temperature, firing time, and electrical conductivity at room temperature during film formation. It can be seen that Example 1 is different from Comparative Example 1 in that a short-time or low-temperature baking forms a thin film with high electrical conductivity.
• Example 2 After forming a hole transporting thin film on an ITO glass substrate by the method described in Comparative Example 1, it was introduced into a vacuum evaporation apparatus, and ⁇ -NPDA 1 q was used under the same conditions as in the method described in Example 1. 3 , LiFA1 was sequentially deposited. Table 4 shows the characteristics of the obtained OLED device.
• Example 2 an organic EL device having a low light-emission starting voltage and high efficiency can be produced by baking for a short time or at a low temperature as compared with Comparative Example 2.

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