WO2020189283A1 - 電荷輸送性化合物及びその製造方法、インク組成物、有機エレクトロルミネッセンス素子材料等 - Google Patents

電荷輸送性化合物及びその製造方法、インク組成物、有機エレクトロルミネッセンス素子材料等 Download PDF

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WO2020189283A1
WO2020189283A1 PCT/JP2020/009168 JP2020009168W WO2020189283A1 WO 2020189283 A1 WO2020189283 A1 WO 2020189283A1 JP 2020009168 W JP2020009168 W JP 2020009168W WO 2020189283 A1 WO2020189283 A1 WO 2020189283A1
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group
charge
ring
light emitting
layer
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French (fr)
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大樹 巽
隆太郎 菅原
一磨 小田
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Konica Minolta Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • 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

Definitions

  • the present invention relates to a charge transporting compound and a method for producing the same, an ink composition, an organic electroluminescence device material, a light emitting material, a luminescent thin film and an organic electroluminescent device, and particularly, the physical properties of the charge transfer / luminescent thin film over time of energization.
  • the present invention relates to a charge-transporting compound or the like that suppresses fluctuations and is excellent in light emission efficiency and light emitting device life.
  • an electric field is applied to an organic electronic device such as an organic electroluminescence element (hereinafter, also referred to as "organic EL element"), a solar cell, and an organic transistor to which an electric field is applied, and charge carriers (general term for electrons and holes).
  • organic EL element organic electroluminescence element
  • solar cell solar cell
  • organic transistor organic transistor to which an electric field is applied
  • charge carriers generally term for electrons and holes.
  • a charge transfer / light emitting thin film containing an organic material capable of transferring is used. Since the functional organic materials contained in the charge transfer / light emitting thin film are required to have various performances, their development has been active in recent years.
  • organic materials are basically isolated and rarely used as a single molecule, and in many cases, they always coexist with aggregates of the same molecules or with different molecules (including different materials such as metals and inorganic substances). Exists in form.
  • molecular design is basically performed for isolated and single molecules, and aggressively keeping in mind that multiple molecules coexist. In reality, such designs have rarely been performed, and a macro-stabilization technique focusing on the molecular aggregates formed has been desired.
  • the performance of the membrane or object should not change at all.
  • the required performance may be color, charge transfer, optical performance such as refractive index, etc., but in any case, the state of the film or object changes completely. Without it, performance would not change at all, meaning endurance would be infinite.
  • a charge transfer / light emitting thin film For example, as an example of a charge transfer / light emitting thin film, consider the life of a light emitting layer (light emitting thin film) constituting an organic EL element, particularly a light emitting layer that emits blue light.
  • the lowest excited single-term energy level (S 1 ) and the lowest excited triple-term energy level (T 1 ) of a blue light-emitting compound (lactone) may be higher than those of a green or red light-emitting compound. Since it is necessary in principle, the energy transfer from the excited state of the blue luminescent compound is the physical (spatial arrangement) state of the substance such as the luminescent compound existing in the light emitting layer, that is, the formation of the light emitting layer.
  • Concentration extinction that is easily affected by the shape state and is deactivated without radiation through the reverse energy transfer from the dopant to the host compound, etc., or the energy transfer between the same or different molecules due to the aggregation of a small amount of compound molecules. Etc. are likely to occur, the light emission efficiency is lowered over time of energization, and the life of the organic EL element is shortened.
  • Patent Document 1 increasing the number of isomers is effective in increasing entropy not only in the phosphorescent iridium complex but also in the heat-activated delayed fluorescent compound (“TADF compound”). It discloses that. However, all of the TADF compounds described in Patent Document 1 have emission colors from green to yellowish green, and specific examples of blue emission are not disclosed.
  • TADF compound heat-activated delayed fluorescent compound
  • Patent Document 2 discloses a technique for using 5CzBN as a host compound.
  • aromaticity of aromatic compounds having a carbazolyl group and aromatic compounds having a condensed nitrogen-containing aromatic ring group containing ⁇ electrons of 14 ⁇ electrons or more, such as 5CzBN was substituted by a hydrocarbon-based substituent. It is stronger than aromatic compounds, and the CH- ⁇ interaction works strongly. Therefore, the physical properties of the film fluctuate over time of energization or under high temperature storage, resulting in high density, aggregation, and crystallization. As a result, the luminous efficiency with time is lowered, and the life of the light emitting element is shortened.
  • the present invention has been made in view of the above problems and situations, and a solution to the problem is to suppress fluctuations in physical properties of a charge transfer / light emitting thin film over time of energization, and to carry charges excellent in luminous efficiency and light emitting device life.
  • the purpose is to provide a sex compound and a method for producing the same.
  • the present inventor has an atropy by having any one of the five substituents on the benzene ring of 5CzBN having an asymmetric chemical structure in the process of examining the cause of the above problems. It has been found that it becomes a mixture of isomers, and its entropy-increasing effect makes it possible to form a stable amorphous film even when energized and stored at a high temperature, and it is possible to improve the light emitting efficiency and the life of the light emitting element.
  • R 1 represents a group having an energy level of -2.19 eV or more in the lowest empty orbit of a compound having a structure represented by the following general formula (2).
  • D 1 to D 5 are each. Independently, it represents an electron-donating aromatic group, and at least one of D 1 to D 5 has a chirality generation site. Note that each of D 1 to D 5 independently has a substituent. May be.
  • a method for producing a charge-transporting compound which comprises introducing each of the above D 1 to D 5 by a nucleophilic substitution reaction.
  • An ink composition comprising the charge-transporting compound according to any one of items 1 to 5.
  • a charge transporting compound which suppresses changes in physical properties of the charge transfer / light emitting thin film over time of energization and has excellent luminous efficiency and light emitting device life, and a method for producing the same. Further, it is possible to provide an ink composition containing the charge transporting compound, an organic electroluminescence device material, a light emitting material, a light emitting thin film, and an organic electroluminescence device.
  • a condensed nitrogen-containing aromatic compound containing ⁇ electrons of 14 ⁇ electrons or more and an aromatic compound having an aromatic ring group derived from such a compound as a substituent are aromatics having an aromatic hydrocarbon-based substituent. Since it is stronger than the compound and the CH- ⁇ interaction works strongly, the film physical properties of the charge transfer / luminescent thin film fluctuate over time of energization or under high temperature storage, resulting in high density, aggregation, and crystallization.
  • the charge-transporting compound of the present invention Since the charge-transporting compound of the present invention has an asymmetric chemical structure at any one of the five substituents on the benzene ring, it becomes a mixture of atropic isomers. Therefore, due to its entropy-increasing effect, the molecules of each molecule The intermolecular interaction derived from the enthalpy of the above is suppressed, and it becomes possible to form a stable amorphous film even when energized and stored at a high temperature.
  • the lowest empty orbital (LUMO) energy level is changed by changing the electron-withdrawing group that replaces the benzene ring from a cyano group to a weak acceptor substituent.
  • the rank can be higher.
  • the light emitting center moves from the vicinity of the interface between the light emitting layer and the electron transporting layer to the hole transporting side in the light emitting layer, and the light emitting center emits light more uniformly without being concentrated, so that the device life can be extended and good. It is presumed that a high luminous efficiency can be achieved. Furthermore, it is presumed that the emission color can be shortened by changing to a substituent of a weak acceptor.
  • Schematic diagram showing an example of a method for manufacturing an organic EL element using an inkjet printing method Schematic external view showing an example of the structure of an inkjet head applicable to an inkjet printing method. Schematic external view showing an example of the structure of an inkjet head applicable to an inkjet printing method. Schematic diagram of the lighting device Schematic diagram of the lighting device
  • the charge transporting compound of the present invention has a structure represented by the general formula (1), and the absolute value ⁇ Est of the energy difference between the lowest excited singlet energy level and the lowest excited triplet energy level is 0. It is characterized by being .30 eV or less.
  • this feature is a technical feature common to or corresponding to each of the following embodiments.
  • in the general formula (1) at least two of D 1 to D 5 having a chirality generating site is charged as an effect of increasing entropy by increasing the number of isomers. It is preferable in that the stability of the transfer / light emitting thin film can be improved. Since the CH- ⁇ interaction is less likely to occur between molecules because it is sterically shielded by five consecutively substituted aromatic groups at adjacent positions, stacking of molecules is suppressed and changes in film physical properties are caused. It is also preferable in that it becomes low.
  • D 1 to D 5 represent a carbazolyl group or a carbolinyl group which may have a substituent from the viewpoint of improving charge transfer.
  • R 1 is an aromatic group which may have a substituent from the viewpoint of chemical stability.
  • R 1 has a chirality generating site because it can enhance the stability of the charge transfer / luminescent thin film as an entropy increasing effect by increasing the number of isomers. ..
  • the method for producing a charge-transporting compound of the present invention is characterized by introducing D 1 to D 5 by a nucleophilic substitution reaction, respectively. As a result, there are few by-products and the product can be produced in good yield.
  • the charge-transporting compound of the present invention is suitably used for ink compositions, organic electroluminescence device materials, and luminescent thin films.
  • the charge-transporting compound of the present invention is preferably used as a light-emitting material, emits fluorescence, and the fluorescence is preferably delayed fluorescence.
  • the organic electroluminescence device of the present invention includes an anode, a cathode, and a light emitting layer provided between the anode and the cathode, and at least one layer of the light emitting layer contains the charge transporting compound of the present invention. It is characterized by doing. This makes it possible to provide an organic EL element that can improve the luminous efficiency and the life of the light emitting element and emit deep blue light.
  • the charge transporting compound of the present invention has a structure represented by the following general formula (1), and the absolute value ⁇ Est of the energy difference between the lowest excited singlet energy level and the lowest excited triplet energy level is 0. It is characterized by being .30 eV or less.
  • R 1 represents a group having an energy level of -2.19 eV or more in the lowest empty orbit of a compound having a structure represented by the following general formula (2).
  • D 1 to D 5 are each. Independently, it represents an electron-donating aromatic group, and at least one of D 1 to D 5 has a chirality generation site. Note that each of D 1 to D 5 independently has a substituent. May be.
  • R 1 represents a group in which the energy level of the lowest empty orbit of the compound having the structure represented by the general formula (2) is -2.19 eV or more.
  • R 1 is not particularly limited as long as it is a group having an energy level of -2.19 eV or more in the lowest empty orbit in the above calculation, but it is preferably an aromatic group that may have a substituent.
  • the aromatic group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group, and a group having an energy level of -2.19 eV or more can be selected from these groups.
  • aromatic hydrocarbon ring group examples include benzene ring, biphenyl, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysen ring, naphthalene ring, triphenylene ring, o-terphenyl ring, and m-terphenyl.
  • Ring p-terphenyl ring, acenaphthene ring, coronene ring, inden ring, fluorene ring, fluorantrene ring, naphthalene ring, pentacene ring, perylene ring, pentaphene ring, picene ring, pyrene ring, pyranethrene ring, anthrananthrene ring , Groups derived from tetraline and the like.
  • Examples of the aromatic heterocyclic group include a furan ring, a dibenzofuran ring, a thiophene ring, a dibenzothiophene ring, an oxazole ring, a pyrol ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazole ring, a benzimidazole ring, and an oxadi ring.
  • Azol ring triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, indazole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxalin ring, quinazoline ring, synnoline ring, quinoline ring, isoquinoline ring, phthalazine ring , Naftyrimidine ring, carbazole ring, carboline ring, diazacarbazole ring (a group derived from a ring in which one of the carbon atoms of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom) and the like. Can be done.
  • R 1 has a chirality generation site.
  • the type having a chirality generation site is preferably a molecule having a bond axis (atorop isomer axis) that imparts rotational isomerism, such as a biaryl group having a bulky substituent at the ortho position, a so-called axial asymmetric compound. ..
  • TADF thermoactive delayed fluorescence
  • ⁇ EST is obtained by using software for calculating the molecular orbital.
  • the structural optimization and the calculation of the electron density distribution by the molecular orbital calculation of the compound can be calculated by using the molecular orbital calculation software using B3LYP as a functional and 6-31G (d) as a basis function as the calculation method. it can.
  • As software for calculating the molecular orbital Gaussian09 (Revision C.01, MJ Frisch, et al, Gaussian, Inc., 2010.) manufactured by Gaussian, USA is used.
  • ⁇ Est calculated by using the same calculation method as described above is 0.3 eV or less, preferably 0.2 eV or less.
  • the energy level of the lowest empty orbital of the compound having the structure represented by the general formula (2) is also a molecular orbital calculation using B3LYP as a functional and 6-31G (d) as a basis function, as in the calculation of ⁇ Est. It can be calculated using the software for Gaussian 09 manufactured by Gaussian Co., Ltd. in the United States.
  • D 1 to D 5 independently represent electron-donating aromatic groups. At least one of D 1 to D 5 has a chirality generation site. In addition, D 1 to D 5 may have a substituent further independently of each other. In the general formula (1), at least two of D 1 to D 5 represent a structure having a chirality generation site, which is a charge transfer / luminescent thin film as an entropy increasing effect due to an increase in the number of isomers. It is preferable in that the stability of the
  • a structure such as an aromatic hydrocarbon derivative or a complex aromatic derivative is preferable as a structure having an electron-donating property and a chirality generating site according to the present invention.
  • the aromatic hydrocarbon derivative include benzene, naphthalene, anthracene, tetracene, pentacene, chrysene, and helicene
  • the complex aromatic derivative include furan, thiophene, pyrrole, oxazole, thiazole, imidazole, benzofuran, and benzo. Examples thereof include thiophene, indol, dibenzofuran, dibenzothiophene, carbazole, pyridine, pyrazine, pyrimidine, carboline and the like.
  • At least one of the D 1 to D 5 having a substituent having a structure represented by the following general formula (3) improves the charge transfer property. preferable.
  • X 101 is NR 101 , oxygen atom, sulfur atom, sulfinyl group, sulfonyl group, CR 102 R 103 or Si R 104 R 105.
  • Y 1 to y 8 independently represent CR 106 or nitrogen atom.
  • R 101 to R 106 independently represent hydrogen atom or substituent. They may be bonded to each other to form a ring.
  • N represents an integer of 1 to 4.
  • R 2 represents a substituent.
  • R 101 to R 106 in the general formula (3) independently represent a hydrogen atom or a substituent, and the substituents referred to here refer to those which may have a substituent as long as the function used in the present invention is not impaired. For example, it stipulates that a compound exhibiting the effects of the present invention is included in the present invention when a substituent is introduced in the synthetic scheme.
  • Examples of the substituent represented by R 101 to R 106 include a linear or branched alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, etc.
  • a linear or branched alkyl group eg, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, etc.
  • a benzene ring for example, a biphenyl, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a chrysen ring, a naphthacene ring, a triphenylene ring, an o-terphenyl ring, m.
  • non-aromatic hydrocarbon ring group eg, cyclopentyl group, cyclohexyl group, etc.
  • non-aromatic heterocyclic group eg, pyrrolidyl group, imidazolidyl group, morpholic group, oxazolidyl group, etc.
  • alkoxy Group eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.
  • cycloalkoxy group eg, cyclopentyloxy group, cyclohexyloxy group, etc.
  • aryloxy Group eg, phenoxy group, naphthyloxy group, etc.
  • alkylthio group eg, methylthio group, ethylthio group, propylthio group, pe Ntilthio group, hexylthio group,
  • substituents may be further substituted by the above substituents. Further, a plurality of these substituents may be bonded to each other to form a ring.
  • a compound in which X 101 is NR 101 , an oxygen atom or a sulfur atom is preferable. More preferably, the group formed together with X 101 and y 1 to y 8 represents a carbazolyl group or a carbolinyl group from the viewpoint of improving charge transfer.
  • n represents an integer of 1 to 4, preferably 1 to 2.
  • R 2 in the general formula (3) represents a substituent in the same manner as in R 101 to R 106 , but a substituent that improves solubility is preferable.
  • substituents include a linear or branched alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group and tetradecyl group. Group, pentadecyl group, etc.), aromatic hydrocarbon ring group (also referred to as aromatic carbocyclic group, aryl group, etc.
  • benzene ring biphenyl, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring.
  • Naphthalcene ring Triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaften ring, coronen ring, inden ring, fluorene ring, fluorantene ring, naphthacene ring, pentacene ring, perylene ring , Pentafene ring, Picene ring, Pyrene ring, Pyranthrene ring, Anthrananthrene ring, Tetraline, etc.), Aromatic heterocyclic group (for example, furan ring, dibenzofuran ring, thiophene ring, dibenzothiophene ring,
  • Examples of the charge transporting compound having the structure represented by the general formula (1) are shown below, but the compound is not limited thereto.
  • the method for producing a charge-transporting compound of the present invention is characterized in that the substituents D 1 to D 5 are introduced by a nucleophilic substitution reaction, respectively.
  • 2,3,4,5,6-pentafluorobenzo form is dissolved in a solvent (tetrahydrofuran (THF), dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), etc.) to make it strong. It can be produced by reacting carbazole, carboline, etc., which may have a substituent, in the presence of a base (potassium carbonate, cesium carbonate, sodium hydride, potassium hydride, etc.).
  • a solvent tetrahydrofuran (THF), dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), etc.
  • THF tetrahydrofuran
  • DMF dimethylformamide
  • NMP N-methyl-2-pyrrolidone
  • the organic EL device of the present invention is an organic electroluminescence device having at least a pair of electrodes and one or a plurality of light emitting layers, and at least one layer of the light emitting layer contains the charge transporting compound of the present invention. It is characterized by that.
  • Typical element configurations in the organic EL device of the present invention include, but are not limited to, the following configurations.
  • Anode / light emitting layer / cathode ii) anode / light emitting layer / electron transport layer / cathode (iii) anode / hole transport layer / light emitting layer / cathode (iv) anode / hole transport layer / light emitting layer / electron Transport layer / cathode (v) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (vi) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode ( vii) Anophode / hole injection layer / hole transport layer / (electron blocking layer /) light emitting layer / (hole blocking layer /) electron transport layer / electron injection layer / cathode
  • the light emitting layer according to the present invention is composed of a single layer or a plurality of layers, and when there are a plurality of light emitting layers, a non-light emitting intermediate layer may be provided between the light emitting layers.
  • a hole blocking layer also referred to as a hole barrier layer
  • an electron injection layer also referred to as a cathode buffer layer
  • An electron blocking layer also referred to as an electron barrier layer
  • a hole injection layer also referred to as an anode buffer layer
  • the electron transport layer according to the present invention is a layer having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. Further, it may be composed of a plurality of layers.
  • the hole transport layer according to the present invention is a layer having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. Further, it may be composed of a plurality of layers. In the above typical device configuration, the layer excluding the anode and the cathode is also referred to as an "organic layer".
  • the organic EL element of the present invention may be an element having a so-called tandem structure in which a plurality of light emitting units including at least one light emitting layer are laminated.
  • tandem structure As a typical element configuration of the tandem structure, for example, the following configuration can be mentioned.
  • the first light emitting unit, the second light emitting unit, and the third light emitting unit may all be the same or different. Further, the two light emitting units may be the same, and the remaining one may be different. Further, the third light emitting unit may not be provided, while a light emitting unit or an intermediate layer may be further provided between the third light emitting unit and the electrode.
  • the plurality of light emitting units may be directly laminated or may be laminated via an intermediate layer, and the intermediate layer is generally an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, or an intermediate layer.
  • a known material and structure can be used as long as it is also called an insulating layer and has a function of supplying electrons to the adjacent layer on the anode side and holes to the adjacent layer on the cathode side.
  • Examples of the material used for the intermediate layer include ITO (inorganic tin oxide), IZO (inorganic zinc oxide), ZnO 2 , TiN, ZrN, HfN, TiOx, VOx, CuI, InN, GaN, and CuAlO 2.
  • Preferred configurations in the light emitting unit include, for example, configurations in which the anode and the cathode are removed from the configurations (i) to (vii) mentioned in the above typical element configurations, but the present invention is limited thereto. Not done.
  • tandem organic EL element examples include, for example, US Pat. No. 6,337,492, US Pat. No. 7,420,203, US Pat. No. 7,473,923, US Pat. No. 6,872,472, US Pat. No. 6,107,734, US Pat. No. 6,337,492, International. Publication No. 2005/09087, Japanese Patent Application Laid-Open No. 2006-228712, Japanese Patent Application Laid-Open No. 2006-24791, Japanese Patent Application Laid-Open No. 2006-49393, Japanese Patent Application Laid-Open No. 2006-49394, Japanese Patent Application Laid-Open No. 2006-49396, Japanese Patent Application Laid-Open No. 2011 -96679, Japanese Patent Application Laid-Open No.
  • the light emitting layer according to the present invention is a layer that provides a place where electrons and holes injected from an electrode or an adjacent layer are recombined and emit light via excitons, and the light emitting portion is a layer of the light emitting layer. It may be inside or at the interface between the light emitting layer and the adjacent layer.
  • the total thickness of the light emitting layer is not particularly limited, but the homogeneity of the formed layer, prevention of applying an unnecessary high voltage at the time of light emission, and improvement of the stability of the light emitting color with respect to the driving current are improved. From the viewpoint, it is preferably adjusted within the range of 2 nm to 5 ⁇ m, more preferably adjusted within the range of 2 to 500 nm, and further preferably adjusted within the range of 5 to 200 nm.
  • each light emitting layer is preferably adjusted within the range of 2 nm to 1 ⁇ m, more preferably adjusted within the range of 2 to 200 nm, and further preferably adjusted within the range of 3 to 150 nm. ..
  • the light emitting layer preferably contains a light emitting dopant (a light emitting dopant compound, a dopant compound, also simply referred to as a dopant) and a host compound (a matrix material, a light emitting host compound, also simply referred to as a host).
  • a light emitting dopant a light emitting dopant compound, a dopant compound, also simply referred to as a dopant
  • a host compound a matrix material, a light emitting host compound, also simply referred to as a host.
  • the light-emitting dopant includes a fluorescent dopant (also referred to as a fluorescent dopant or a fluorescent compound), a delayed fluorescent dopant, or a phosphorescent dopant (also referred to as a phosphorescent dopant or a phosphorescent compound). Is preferably used. In the present invention, it is preferable that at least one light emitting layer contains the charge transporting compound of the present invention.
  • the light emitting layer preferably contains the light emitting dopant in the range of 5 to 40% by mass, and more preferably in the range of 10 to 30% by mass.
  • the concentration of the light emitting dopant in the light emitting layer can be arbitrarily determined based on the specific light emitting dopant used and the requirements of the device, and is contained at a uniform concentration with respect to the thickness direction of the light emitting layer. It may have an arbitrary concentration distribution.
  • a plurality of types of light emitting dopants may be used in combination, and a combination of light emitting dopants having different structures, a ⁇ -conjugated compound of the present invention, or a combination of a fluorescent light emitting compound and a phosphorescent light emitting compound may be used. You may use it. Thereby, an arbitrary emission color can be obtained.
  • the color emitted by the organic EL element according to the present invention is shown in FIG. 4.16 on page 108 of the "New Color Science Handbook” (edited by the Japan Color Society, edited by the University of Tokyo Press, 1985). It is determined by the color when the result measured by Konica Minolta Co., Ltd. is applied to the CIE chromaticity coordinates.
  • the light emitting layer of one layer or a plurality of layers contains a plurality of light emitting dopants having different light emitting colors and exhibits white light emission.
  • the combination of luminescent dopants showing white color is not particularly limited, and examples thereof include a combination of blue and orange, a combination of blue and green and red, and the like.
  • the white color in the organic EL element according to the present invention is not particularly limited and may be white color closer to orange or white color closer to blue, but when the 2 degree viewing angle front luminance is measured by the above method.
  • Phosphorescent dopant A phosphorescent dopant according to the present invention (hereinafter, also referred to as “phosphorescent dopant”) will be described.
  • the phosphorescent dopant according to the present invention is a compound in which light emission from an excited triplet is observed, specifically, a compound that emits phosphorescent light at room temperature (25 ° C.), and has a phosphorescent quantum yield of 25. It is defined as a compound of 0.01 or more at ° C, but the preferred phosphorescence quantum yield is 0.1 or more.
  • the phosphorus photon yield can be measured by the method described on page 398 (1992 edition, Maruzen) of Spectroscopy II of the 4th edition Experimental Chemistry Course 7.
  • the phosphorescence quantum yield in a solution can be measured using various solvents, but the phosphorescence dopant according to the present invention can achieve the above phosphorescence quantum yield (0.01 or more) in any of any solvents. Just do it.
  • the phosphorescent dopant There are two types of light emission of the phosphorescent dopant in principle. One is that carrier recombination occurs on the host compound to which the carrier is transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent dopant. It is an energy transfer type that obtains light emission from a phosphorescent dopant. The other is a carrier trap type in which the phosphorescent dopant serves as a carrier trap, and carriers are recombined on the phosphorescent dopant to obtain light emission from the phosphorescent dopant. In either case, the excited state energy of the phosphorescent dopant is required to be lower than the excited state energy of the host compound.
  • the phosphorescent dopant that can be used in the present invention can be appropriately selected from known ones used for the light emitting layer of the organic EL element.
  • Specific examples of known phosphorescent dopants that can be used in the present invention include compounds described in the following documents.
  • a preferable phosphorescent dopant is an organometallic complex having Ir as a central metal. More preferably, a complex containing at least one coordination mode of metal-carbon bond, metal-nitrogen bond, metal-oxygen bond, and metal-sulfur bond is preferable.
  • Fluorescent dopant A fluorescent dopant according to the present invention (hereinafter, also referred to as “fluorescent dopant”) will be described.
  • the fluorescent dopant according to the present invention is a compound capable of emitting light from the excited singlet, and is not particularly limited as long as the emission from the excited singlet is observed.
  • the charge transporting compound of the present invention may be used, or a known fluorescent dopant or other delayed fluorescent dopant used in the light emitting layer of the organic EL device may be appropriately selected. You may use it.
  • Examples of the fluorescent dopant according to the present invention include anthracene derivatives, pyrene derivatives, chrysene derivatives, fluorantene derivatives, perylene derivatives, fluorene derivatives, arylacetylene derivatives, styrylarylene derivatives, styrylamine derivatives, arylamine derivatives, boron complexes and coumarin derivatives. , Pyran derivatives, cyanine derivatives, croconium derivatives, squalium derivatives, oxobenzanthracene derivatives, fluorescein derivatives, rhodamine derivatives, pyrylium derivatives, perylene derivatives, polythiophene derivatives, rare earth complex compounds and the like.
  • delayed fluorescent dopant examples include the compounds described in International Publication No. 2011/156793, Japanese Patent Application Laid-Open No. 2011-213643, Japanese Patent Application Laid-Open No. 2010-93181, and the like. Not limited.
  • the host compound according to the present invention is a compound mainly responsible for injection and transport of electric charges in the light emitting layer, and its own light emission is not substantially observed in the organic EL device.
  • a compound having a phosphorescent quantum yield of less than 0.1 at room temperature (25 ° C.) is preferable, and a compound having a phosphorescent quantum yield of less than 0.01 is more preferable.
  • the mass ratio in the layer is preferably 20% or more.
  • the excited state energy of the host compound is higher than the excited state energy of the light emitting dopant contained in the same layer.
  • the host compound may be used alone or in combination of two or more. By using a plurality of types of host compounds, it is possible to adjust the charge transfer, and it is possible to improve the efficiency of the organic EL device.
  • the charge transporting compound of the present invention may be used, and there is no particular limitation, and a compound conventionally used in an organic EL device can be used. It may be a low molecular weight compound, a high molecular weight compound having a repeating unit, or a compound having a reactive group such as a vinyl group or an epoxy group.
  • those having an excitation energy higher than the excitation single-term energy level of the dopant are preferable, and those having an excitation triple-term energy higher than the excitation triple-term energy level of the dopant are more preferable.
  • the host compound is responsible for carrier transport and exciton generation in the light emitting layer. Therefore, it can exist stably in all active species in the cation radical state, the anion radical state, and the excited state, does not cause chemical changes such as decomposition and addition reaction, and further, the host molecule is present in the layer over time of energization. It is preferable not to move at the angstrom level.
  • the existence time of the excited triplet state of the TADF compound is long, so that the T 1 energy level of the host compound itself is high, and the host compounds are associated with each other.
  • the host compound itself has high electron hopping mobility, high hole hopping mobility, and a small structural change in the excited triplet state.
  • those having a high T 1 energy level such as a carbazole skeleton, an azacarbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton or an azadibenzofuran skeleton are preferably mentioned.
  • Tg glass transition temperature
  • the glass transition point (Tg) is a value obtained by a method based on JIS-K-7121 using DSC (Differential Scanning Calorimetry: differential scanning calorimetry).
  • the electron transport layer may be made of a material having a function of transporting electrons and may have a function of transmitting electrons injected from the cathode to the light emitting layer.
  • the total thickness of the electron transport layer in the present invention is not particularly limited, but is usually in the range of 2 nm to 5 ⁇ m, more preferably in the range of 2 to 500 nm, and further preferably in the range of 5 to 200 nm. is there.
  • the material used for the electron transport layer may have any of electron injection property, transport property, and hole barrier property, and the charge transport compound of the present invention. Or any of conventionally known compounds can be selected and used.
  • Conventionally known compounds include, for example, nitrogen-containing aromatic heterocyclic derivatives (carbazole derivatives, azacarbazole derivatives (one or more carbon atoms constituting the carbazole ring substituted with nitrogen atoms), pyridine derivatives, pyrimidine derivatives.
  • metal complexes having a quinolinol skeleton or a dibenzoquinolinol skeleton as ligands for example, tris (8-quinolinol) aluminum (Alq 3 ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7) -Dibromo-8-quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and metal complexes thereof.
  • a metal complex in which the central metal of the above is replaced with In, Mg, Cu, Ca, Sn, Ga or Pb can also be used as an electron transport material.
  • metal-free or metal phthalocyanines or those whose terminals are substituted with an alkyl group, a sulfonic acid group, or the like can also be preferably used as an electron transport material.
  • the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transporting material, and an inorganic semiconductor such as n-type-Si or n-type-SiC is used like the hole injection layer and the hole transporting layer. Can also be used as an electron transport material.
  • the electron transport layer may be doped with a doping material as a guest material to form a highly n-type (electron-rich) electron transport layer.
  • the doping material include n-type dopants such as metal compounds and metal compounds such as metal halides.
  • Specific examples of the electron transport layer having such a structure include, for example, JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, JP-A-2001-102175, J. Mol. Apple. Phys. , 95, 5773 (2004) and the like.
  • More preferable electron transporting materials in the present invention include pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, azacarbazole derivatives, and benzimidazole derivatives.
  • the electron transport material may be used alone or in combination of two or more.
  • the hole blocking layer is a layer having a function of an electron transporting layer in a broad sense, and is preferably made of a material having a function of transporting electrons and a small ability to transport holes, and a hole while transporting electrons. It is possible to improve the recombination probability of electrons and holes by blocking the above.
  • the hole blocking layer is preferably provided adjacent to the cathode side of the light emitting layer.
  • the thickness of the hole blocking layer is preferably in the range of 3 to 100 nm, and more preferably in the range of 5 to 30 nm.
  • the material used for the hole blocking layer As the material used for the hole blocking layer, the material used for the above-mentioned electron transporting layer containing the charge-transporting compound of the present invention is preferably used, and as the above-mentioned host compound containing the charge-transporting compound of the present invention. The material used is also preferably used for the hole blocking layer.
  • the electron injection layer (also referred to as “cathode buffer layer”) according to the present invention is a layer provided between the cathode and the light emitting layer in order to reduce the driving voltage and improve the emission brightness, and is “organic EL element and its addition”. It is described in detail in Volume 2, Chapter 2, "Electrode Materials” (pages 123-166) of "Forefront of Industrialization (published by NTS Co., Ltd. on November 30, 1998)”.
  • the electron injection layer may be provided as needed and may be present between the cathode and the light emitting layer or between the cathode and the electron transport layer as described above.
  • the electron injection layer is preferably a very thin film, and the thickness thereof is preferably in the range of 0.1 to 5 nm, although it depends on the material. Further, it may be a non-uniform film in which the constituent material is intermittently present.
  • the details of the electron-injected layer are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like, and specific examples of materials preferably used for the electron-injected layer include , Metals such as strontium and aluminum, alkali metal compounds such as lithium fluoride, sodium fluoride and potassium fluoride, alkaline earth metal compounds such as magnesium fluoride and calcium fluoride, oxidation Examples thereof include metal oxides typified by aluminum, metal complexes typified by lithium 8-hydroxyquinolate (Liq) and the like. It is also possible to use the above-mentioned electron transporting material containing the charge transporting compound of the present invention. Further, the material used for the above-mentioned electron injection layer may be used alone or in combination of two or more.
  • the hole transport layer may be made of a material having a function of transporting holes and may have a function of transmitting holes injected from the anode to the light emitting layer.
  • the total thickness of the hole transport layer is not particularly limited, but is usually in the range of 5 nm to 5 ⁇ m, more preferably in the range of 2 to 500 nm, and further preferably in the range of 5 to 200 nm. ..
  • the material used for the hole transport layer may have any of hole injection property, transport property, and electron barrier property, and has the charge transport property of the present invention.
  • a compound may be used, or any of conventionally known compounds can be selected and used.
  • porphyrin derivatives for example, porphyrin derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives, stillben derivatives, polyarylalkane derivatives, triarylamine derivatives, carbazole derivatives.
  • Indolocarbazole derivatives Indolocarbazole derivatives, isoindole derivatives, acene derivatives such as anthracene and naphthalene, fluorene derivatives, fluorenone derivatives, and polymer materials or oligomers in which polyvinylcarbazole and aromatic amines are introduced into the main chain or side chains, polysilane, conductivity.
  • examples thereof include sex polymers or oligomers (for example, PEDOT: PSS, aniline-based copolymers, polyaniline, polythiophene, etc.).
  • triarylamine derivative examples include a benzidine type represented by ⁇ -NPD, a starburst type represented by MTDATA, and a compound having fluorene or anthracene in the triarylamine connecting core portion.
  • Hexaazatriphenylene derivatives as described in JP-A-2003-591432 and JP-A-2006-135145 can also be used as the hole transport material in the same manner.
  • a hole transport layer having a high p property doped with impurities examples thereof include JP-A-4-297076, JP-A-2000-196140, and JP-A-2001-102175. Apple. Phys. , 95, 5773 (2004) and the like.
  • JP-A-11-251667 J. Am. Hung et. al. So-called p-type hole transporting materials and inorganic compounds such as p-type-Si and p-type-SiC, as described in the authored literature (Applied Physics Letters 80 (2002), p.139), can also be used.
  • an orthometalated organometallic complex having Ir or Pt in the central metal as represented by Ir (ppy) 3 is also preferably used.
  • the hole transporting material the above-mentioned materials can be used, but a triarylamine derivative, a carbazole derivative, an indolocarbazole derivative, an azatriphenylene derivative, an organic metal complex, and an aromatic amine are introduced into the main chain or side chain. High molecular weight materials or oligomers are preferably used.
  • Apple. Phys. Lett. 69,2160 (1996), J. Mol. Lumin. 72-74,985 (1997), Apple. Phys. Lett. 78,673 (2001), Apple. Phys. Lett. 90,183503 (2007), Apple. Phys. Lett. 90,183503 (2007), Apple. Phys. Lett. 51,913 (1987), Synth. Met. 87,171 (1997), Synth. Met. 91,209 (1997), Synth. Met. 111,421 (2000), SID Symposium Digist, 37,923 (2006), J. Mol. Mater. Chem. 3,319 (1993), Adv. Mater. 6,677 (1994), Chem. Mater.
  • the electron blocking layer is a layer having a function of a hole transporting layer in a broad sense, and is preferably made of a material having a function of transporting holes and a small ability to transport electrons, and is composed of a material having a small ability to transport electrons while transporting holes. It is possible to improve the recombination probability of electrons and holes by blocking the above.
  • the structure of the hole transport layer described above can be used as an electron blocking layer according to the present invention, if necessary.
  • the electron blocking layer is preferably provided adjacent to the anode side of the light emitting layer.
  • the thickness of the electron blocking layer is preferably in the range of 3 to 100 nm, and more preferably in the range of 5 to 30 nm.
  • the material used for the electron blocking layer As the material used for the electron blocking layer, the material used for the hole transporting layer described above containing the charge transporting compound of the present invention is preferably used, and the material used as the host compound described above is also preferably used for the electron blocking layer. Used.
  • the hole injection layer (also referred to as “anode buffer layer”) according to the present invention is a layer provided between the anode and the light emitting layer in order to reduce the driving voltage and improve the emission brightness, and is an “organic EL element”. It is described in detail in Volume 2, Chapter 2, "Electrode Materials” (pages 123-166) of "The Forefront of Industrialization (published by NTS Co., Ltd. on November 30, 1998)”.
  • the hole injection layer may be provided as needed and may be present between the anode and the light emitting layer or between the anode and the hole transport layer as described above.
  • the details of the hole injection layer are also described in JP-A-9-45479, 9-2660062, 8-288609, etc., and examples of the material used for the hole injection layer include , Materials used for the hole transport layer described above containing the charge transporting compound of the present invention and the like.
  • phthalocyanine derivatives typified by copper phthalocyanine, hexaazatriphenylene derivatives as described in JP-A-2003-591432 and JP-A-2006-135145, metal oxides typified by vanadium oxide, amorphous carbon.
  • Conductive polymers such as polyaniline (emeraldine) and polythiophene, orthometallated complexes typified by tris (2-phenylpyridine) iridium complexes, triarylamine derivatives and the like are preferable.
  • the material used for the hole injection layer described above may be used alone or in combination of two or more.
  • the organic layer in the present invention described above may further contain other additives.
  • the additive include halogen elements such as bromine, iodine and chlorine, halogenated compounds, alkali metals and alkaline earth metals such as Pd, Ca and Na, compounds and complexes of transition metals, salts and the like.
  • the content of the additive can be arbitrarily determined, but is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 50 ppm or less, based on the total mass% of the contained layer. .. However, it is not within this range depending on the purpose of improving the transportability of electrons and holes and the purpose of favoring the energy transfer of excitons.
  • anode in the organic EL element a metal, an alloy, an electrically conductive compound having a large work function (4 eV or more, preferably 4.5 V or more) and a mixture thereof as an electrode material are preferably used.
  • an electrode material include metals such as Au and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • a material such as IDIXO (In 2 O 3- ZnO) that is amorphous and can produce a transparent conductive film may be used.
  • a thin film may be formed by forming a thin film of these electrode materials by a method such as thin film deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not required so much (about 100 ⁇ m or more).
  • the pattern may be formed through a mask having a desired shape during vapor deposition or sputtering of the electrode material.
  • a coatable substance such as an organic conductive compound
  • a wet film forming method such as a printing method or a coating method can also be used.
  • the thickness of the anode depends on the material, but is usually selected in the range of 10 nm to 1 ⁇ m, preferably 10 to 200 nm.
  • a metal having a small work function (5 eV or less) (referred to as an electron-injectable metal), an alloy, an electrically conductive compound, or a mixture thereof as an electrode material is used.
  • electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, silver, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al). 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, aluminum, rare earth metals and the like.
  • a mixture of an electron injectable metal and a second metal which is a stable metal having a larger work function value than this for example, a magnesium / silver mixture.
  • a magnesium / silver mixture Magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) mixture, lithium / aluminum mixture, aluminum and the like are suitable.
  • the cathode can be produced by forming a thin film of these electrode substances by a method such as vapor deposition or sputtering. Alternatively, when a coatable substance such as metal nanoparticles is used, a wet film forming method such as a printing method or a coating method can also be used.
  • Sheet resistance as a cathode is several hundred ⁇ / sq. The following is preferable, and the thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the emission brightness is improved if either the anode or the cathode of the organic EL element is transparent or translucent.
  • a transparent or translucent cathode can be produced by producing the above metal on the cathode having a thickness of 1 to 20 nm and then producing the conductive transparent material mentioned in the description of the anode on the cathode. By applying the above, it is possible to manufacture an element in which both the anode and the cathode are transparent.
  • the type of support substrate (hereinafter, also referred to as a substrate, substrate, substrate, support, etc.) that can be used for the organic EL element in the present invention is not particularly limited in the types such as glass and plastic, and is transparent. It may be opaque. When light is taken out from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of imparting flexibility to the organic EL element.
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, and cellulose acetate propionate.
  • CAP cellulose acetate phthalate
  • cellulose esters such as cellulose nitrate or derivatives thereof
  • polyvinylidene chloride polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyether sulfone (PES), polyphenylene sulfide, polysulfones, polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylates, Arton (registered trademark) (manufactured by JSR) Alternatively, cycloolefin resins such as Apel (registered trademark) (manufactured by Mitsui Chemicals, Inc.) can be mentioned.
  • a film of an inorganic substance, an organic substance, or a hybrid film of both of them may be formed on the surface of the resin film, and the water vapor permeability (25 ⁇ 0.5 ° C.) measured by a method according to JIS K 7129-1992.
  • oxygen relative humidity (90 ⁇ 2)% RH) is preferably a barrier film of 0.01g / (m 2 ⁇ 24h) or less, still more, as measured by the method based on JIS K 7126-1987 the permeability, 10 -3 mL / (m 2 ⁇ 24h ⁇ atm) or less, the water vapor permeability is preferably 10 -5 g / (m 2 ⁇ 24h) or less of the high barrier film.
  • any material that causes deterioration of the element such as water and oxygen but has a function of suppressing infiltration can be used, and for example, silicon oxide, silicon dioxide, silicon nitride and the like can be used.
  • silicon oxide, silicon dioxide, silicon nitride and the like can be used.
  • the stacking order of the inorganic layer and the organic layer is not particularly limited, but it is preferable to stack the inorganic layer and the organic layer alternately a plurality of times.
  • the method for forming the gas barrier film is not particularly limited, and for example, vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma polymerization method.
  • Plasma CVD method, laser CVD method, thermal CVD method, coating method and the like can be used, but the atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.
  • the opaque support substrate examples include a metal plate such as aluminum and stainless steel, a film or opaque resin substrate, and a ceramic substrate.
  • the external extraction quantum efficiency of the light emission of the organic EL device according to the present invention at room temperature is preferably 1% or more, more preferably 5% or more.
  • the external extraction quantum efficiency (%) the number of photons emitted to the outside of the organic EL element / the number of electrons passed through the organic EL element ⁇ 100.
  • a hue improving filter such as a color filter may be used in combination, or a color conversion filter that converts the color emitted from the organic EL element into multiple colors using a phosphor may be used in combination.
  • the method for forming the organic layer is not particularly limited, and conventionally known methods such as a vacuum vapor deposition method and a wet method (also referred to as a wet process) can be used.
  • a wet method for example, in addition to printing methods such as gravure printing method, flexographic printing method, screen printing method, spin coating method, casting method, inkjet printing method, die coating method, blade coating method, bar coating method, roll coating method, etc.
  • a different film forming method may be applied to each layer.
  • the vapor deposition conditions vary depending on the type of compound used, but generally the boat heating temperature is 50 to 450 ° C, the degree of vacuum is 10-6 to 10-2 Pa, and the vapor deposition rate is 0.01 to. It is desirable to appropriately select in the range of 50 nm / sec, substrate temperature -50 to 300 ° C., thickness 0.1 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the formation of the organic layer in the present invention is preferably carried out consistently from the hole injection layer to the cathode by one vacuuming, but it may be taken out in the middle and a different film forming method may be applied. In that case, it is preferable to carry out the work in a dry inert gas atmosphere.
  • FIG. 1 is a schematic view showing an example of a method for manufacturing an organic EL element using an inkjet printing method.
  • FIG. 1 shows an ink composition (hereinafter, also referred to as a coating liquid) containing an organic functional material or the like that forms an organic layer of an organic EL element on a base material 2 using an inkjet printing apparatus provided with an inkjet head 30. An example of the method of discharging.) Is shown.
  • the ink composition of the present invention preferably contains the charge transporting compound of the present invention.
  • the organic functional material or the like is sequentially ejected as ink droplets onto the base material 2 by the inkjet head 30, and the organic EL is used.
  • the organic functional layer of the element 1 is formed.
  • the inkjet head 30 applicable to the method for manufacturing an organic EL element according to the present invention is not particularly limited.
  • the ink pressure chamber has a diaphragm provided with a piezoelectric element, and the ink pressure chamber using the diaphragm has a diaphragm.
  • It may be a shear mode type (piezo type) head that ejects the ink composition by a pressure change, or it has a heat generating element, and the heat energy from the heat generating element causes a sudden volume change due to the film boiling of the ink composition from the nozzle.
  • It may be a thermal type head that ejects the ink composition.
  • the inkjet head 30 is connected to a supply mechanism of an ink composition for injection.
  • the ink composition is supplied to the inkjet head 30 by the tank 38A.
  • the liquid level in the tank is kept constant so that the pressure of the ink composition in the inkjet head 30 is always kept constant.
  • the ink composition is overflowed from the tank 38A and returned to the tank 38B by natural flow.
  • the ink composition is supplied from the tank 38B to the tank 38A by the pump 31, and the liquid level of the tank 38A is controlled to be stable and constant according to the injection conditions.
  • the ink composition When returning the ink composition to the tank 38A by the pump 31, it is performed after passing through the filter 32.
  • the ink composition is passed through a filter medium having an absolute filtration accuracy or a quasi-absolute filtration accuracy of 0.05 to 50 ⁇ m at least once before being supplied to the inkjet head 30.
  • the ink composition can be forcibly supplied from the tank 36 and the cleaning solvent can be forcibly supplied from the tank 37 to the inkjet head 30 by the pump 39 in order to perform the cleaning work and the liquid filling work of the inkjet head 30.
  • tank pumps may be divided into a plurality of parts with respect to the inkjet head 30, a branch of a pipe may be used, or a combination thereof may be used.
  • the pipe branch 33 is used. Further, in order to sufficiently remove the air in the inkjet head 30, the ink composition is forcibly sent from the tank 36 to the inkjet 30 by the pump 39, and the ink composition is extracted from the air bleeding pipe described below to be a waste liquid tank. It may be sent to 34.
  • FIG. 2A and 2B are schematic external views showing an example of a structure of an inkjet head applicable to an inkjet printing method.
  • FIG. 2A is a schematic perspective view showing an inkjet head 100 applicable to the present invention
  • FIG. 2B is a bottom view of the inkjet head 100.
  • the inkjet head 100 applicable to the present invention is mounted on an inkjet recording device (not shown), and includes a head chip that ejects ink from a nozzle, a wiring board on which the head chip is arranged, and this wiring.
  • a drive circuit board connected via a substrate and a flexible substrate, a manifold for introducing ink into a channel of a head chip via a filter, a housing 56 in which a manifold is housed inside, and a bottom opening of the housing 56.
  • the cap receiving plate 57 attached so as to close the above, the first and second joints 81a and 81b attached to the first ink port and the second ink port of the manifold, and the third ink port attached to the third ink port of the manifold.
  • It includes a 3-joint 82 and a cover member 59 attached to the housing 56. Further, mounting holes 68 for mounting the housing 56 on the printer main body side are formed.
  • the cap receiving plate 57 shown in FIG. B is formed as a substantially rectangular plate whose outer shape is long in the left-right direction corresponding to the shape of the cap receiving plate mounting portion 62, and a plurality of nozzles are formed in the substantially central portion thereof. In order to expose the arranged nozzle plate 61, a long nozzle opening 71 is provided in the left-right direction. Further, regarding the specific structure inside the inkjet head shown in FIG. 2A, for example, FIG. 2 and the like described in Japanese Patent Application Laid-Open No. 2012-140017 can be referred to.
  • FIGS. 2A and 2B A representative example of the inkjet head is shown in FIGS. 2A and 2B, but in addition to the above, for example, JP-A-2012-140017, JP-A-2013-010227, JP-A-2014-058171 and JP-A-2014. -097644, JP2015-142979, JP2015-142980, JP2016-002675, JP2016-002682, JP2016-107401, JP2017-109476
  • An inkjet head having the configuration described in Japanese Patent Application Laid-Open No. 2017-177626 and the like can be appropriately selected and applied.
  • the coating liquid used in the inkjet printing method may be a solution in which the material forming the organic layer is uniformly dissolved in the liquid medium, or a dispersion liquid in which the material is dispersed in the liquid medium as a solid content.
  • a dispersion method dispersion can be performed by a dispersion method such as ultrasonic waves, high shear force dispersion, or media dispersion.
  • the liquid medium is not particularly limited, and for example, halogen-based solvents such as chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, dichlorobenzene and dichlorohexanone, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone and n-propyl.
  • halogen-based solvents such as chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, dichlorobenzene and dichlorohexanone, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone and n-propyl.
  • Ketone solvents such as methyl ketone and cyclohexanone, aromatic solvents such as benzene, toluene, xylene, mesitylene and cyclohexylbenzene, aliphatic solvents such as cyclohexane, decalin and dodecane, ethyl acetate, n-propyl acetate, n-acetate Ester solvents such as butyl, methyl propionate, ethyl propionate, ⁇ -butyrolactone, diethyl carbonate, ether solvents such as tetrahydrofuran and dioxane, amide solvents such as dimethylformamide and dimethylacetamide, methanol, ethanol, 1-butanol, Examples thereof include alcohol solvents such as ethylene glycol, nitrile solvents such as acetonitrile and propionitrile, dimethyl sulfoxide, water, or a mixed solution medium thereof.
  • the boiling point of these liquid media is preferably a boiling point lower than the temperature of the drying treatment from the viewpoint of quickly drying the liquid medium, specifically in the range of 60 to 200 ° C, more preferably 80 to 180 ° C. Is within the range of.
  • the coating liquid contains a surfactant depending on the purpose of controlling the coating range and suppressing the liquid flow (for example, the liquid flow that causes a phenomenon called coffee ring) associated with the surface tension gradient after coating. Can be done.
  • surfactant examples include anionic or nonionic surfactants from the viewpoints of the influence of water contained in the solvent, leveling property, wettability to the substrate f1 and the like.
  • surfactants such as fluorine-containing activators and the like listed in International Publication No. 08/146681 and JP-A-2-41308 can be used.
  • the viscosity of the coating film can be appropriately selected depending on the function required as the organic layer and the solubility or dispersibility of the organic material. Specifically, for example, 0.3 to It can be selected within the range of 100 mPa ⁇ s.
  • the thickness of the coating film can be appropriately selected depending on the function required as the organic layer and the solubility or dispersibility of the organic material, and specifically, can be selected in the range of, for example, 1 to 90 ⁇ m.
  • the temperature of the drying step is not particularly limited, but it is preferable to perform the drying treatment at a temperature that does not damage the organic layer, the transparent electrode, or the base material. Specifically, it cannot be said unconditionally because it differs depending on the composition of the coating liquid and the like, but for example, the temperature can be set to 80 ° C. or higher, and the upper limit is considered to be a possible range up to about 300 ° C.
  • the time is preferably about 10 seconds or more and 10 minutes or less. Under such conditions, drying can be performed quickly.
  • sealing means used for sealing the organic EL element include a method of adhering the sealing member, the electrode, and the support substrate with an adhesive.
  • the sealing member may be arranged so as to cover the display area of the organic EL element, and may be intaglio-shaped or flat-plate-shaped. Further, transparency and electrical insulation are not particularly limited.
  • glass plates examples include glass plates, polymer plates / films, metal plates / films, and the like.
  • the glass plate include soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • the polymer plate examples include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • metal plate examples include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium and tantalum.
  • a polymer film or a metal film can be preferably used because the organic EL element can be thinned.
  • the polymer film is measured with an oxygen permeability measured by the method based on JIS K 7126-1987 is 1 ⁇ 10 -3 mL / m 2 ⁇ 24hr ⁇ atm or less, in conformity with JIS K 7129-1992 method and water vapor transmission rate (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)%) is preferably one of the following 1 ⁇ 10 -3 g / m 2 ⁇ 24hr. Sandblasting, chemical etching, etc. are used to process the sealing member into a concave shape.
  • the adhesive examples include a photocurable and thermosetting adhesive having a reactive vinyl group of an acrylic acid-based oligomer and a methacrylic acid-based oligomer, and a moisture-curable adhesive such as 2-cyanoacrylic acid ester. be able to.
  • heat and chemical curing type such as epoxy type can be mentioned.
  • hot melt type polyamide, polyester and polyolefin can be mentioned.
  • a cation-curable type ultraviolet-curable epoxy resin adhesive can be mentioned.
  • the organic EL element may be deteriorated by heat treatment, it is preferable that the organic EL element can be adhesively cured from room temperature to 80 ° C. Further, the desiccant may be dispersed in the adhesive. A commercially available dispenser may be used to apply the adhesive to the sealing portion, or printing may be performed as in screen printing.
  • the electrode and the organic layer on the outside of the electrode on the side facing the support substrate with the organic layer sandwiched therein, and form a layer of an inorganic substance or an organic substance in contact with the support substrate to form a sealing film.
  • the material for forming the sealing film may be any material having a function of suppressing infiltration of a material that causes deterioration of the element such as moisture and oxygen, and for example, silicon oxide, silicon dioxide, silicon nitride or the like is used. Can be done.
  • the sealing film In order to further improve the brittleness of the sealing film, it is preferable to have a laminated structure of these inorganic layers and layers made of an organic material.
  • the method for forming these films is not particularly limited, and for example, vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weight. Legal, plasma CVD method, laser CVD method, thermal CVD method, coating method and the like can be used.
  • an inert gas such as nitrogen or argon or an inert liquid such as fluorinated hydrocarbon or silicone oil may be injected into the gap between the sealing member and the display region of the organic EL element.
  • an inert gas such as nitrogen or argon or an inert liquid such as fluorinated hydrocarbon or silicone oil
  • hygroscopic compound examples include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide, etc.) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate, etc.).
  • metal oxides for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide, etc.
  • sulfates for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate, etc.
  • Metal halides eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide, etc.
  • perchlorates eg barium perchlorate, etc. Magnesium perchlorate, etc.
  • anhydrous salts are preferably used for sulfates, metal halides and perchlorates.
  • a protective film or protective plate may be provided on the outside of the sealing film or the sealing film on the side facing the support substrate with the organic layer sandwiched in order to increase the mechanical strength of the element.
  • its mechanical strength is not necessarily high, so it is preferable to provide such a protective film and a protective plate.
  • a glass plate, a polymer plate / film, a metal plate / film, etc. similar to those used for the sealing can be used, but the polymer film is lightweight and thin. It is preferable to use.
  • the organic EL element in the present invention emits light inside a layer having a refractive index higher than that of air (within a refractive index of about 1.6 to 2.1), and 15% to 20% of the light generated in the light emitting layer. It is generally said that only a degree of light can be taken out. This is because light incident on the interface (intersection between the transparent substrate and air) at an angle ⁇ equal to or greater than the critical angle causes total internal reflection and cannot be taken out of the element, and the transparent electrode or light emitting layer and the transparent substrate This is because the light is totally reflected between them, the light is waveguideed through the transparent electrode or the light emitting layer, and as a result, the light escapes toward the side surface of the element.
  • a method for improving the efficiency of light extraction for example, a method of forming irregularities on the surface of a transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (for example, US Pat. No. 4,774,435), the substrate A method of improving efficiency by providing light-collecting property (for example, Japanese Patent Application Laid-Open No. 63-314795), a method of forming a reflective surface on a side surface of an element (for example, Japanese Patent Application Laid-Open No. 1-220394), a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the light emitting body and the light emitting body (for example, Japanese Patent Application Laid-Open No.
  • these methods can be used in combination with the organic EL element, but a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate and a transparent electrode layer.
  • a method of forming a diffraction grating between any layer (including between the substrate and the outside world) of the light emitting layer can be preferably used.
  • the low refractive index layer examples include airgel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally in the range of about 1.5 to 1.7, it is preferable that the low refractive index layer has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.
  • the thickness of the low refractive index medium is at least twice the wavelength in the medium. This is because the effect of the low refractive index layer diminishes when the thickness of the low refractive index medium becomes about the wavelength of light and the electromagnetic wave exuded by evanescent enters the substrate.
  • the method of introducing a diffraction grating into an interface that causes total reflection or in any of the media is characterized by a high effect of improving light extraction efficiency.
  • This method is generated from the light emitting layer by utilizing the property that the diffraction lattice can change the direction of light to a specific direction different from the refraction by so-called Bragg diffraction such as first-order diffraction or second-order diffraction.
  • Bragg diffraction such as first-order diffraction or second-order diffraction.
  • the light that cannot go out due to total reflection between the layers is diffracted by introducing a diffraction lattice into one of the layers or in the medium (inside the transparent substrate or in the transparent electrode). , Trying to get the light out.
  • the diffraction grating to be introduced has a two-dimensional periodic refractive index. This is because the light emitted by the light emitting layer is randomly generated in all directions, so a general one-dimensional diffraction grating that has a periodic refractive index distribution only in one direction diffracts only the light that travels in a specific direction. The light extraction efficiency does not increase so much. However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and the light extraction efficiency is improved.
  • the position where the diffraction grating is introduced may be in any of the layers or in the medium (inside the transparent substrate or in the transparent electrode), but it is desirable that the position is near the organic light emitting layer where light is generated.
  • the period of the diffraction grating is preferably in the range of about 1/2 to 3 times the wavelength of the light in the medium. It is preferable that the arrangement of the diffraction grating is two-dimensionally repeated, such as a square lattice shape, a triangular lattice shape, and a honeycomb lattice shape.
  • the organic EL element in the present invention is processed so as to provide a structure on a microlens array, for example, on the light extraction side of a support substrate (substrate), or by combining with a so-called condensing sheet, for example, an element By condensing light in the front direction with respect to the light emitting surface, it is possible to increase the brightness in a specific direction.
  • a quadrangular pyramid having a side of 30 ⁇ m and an apex angle of 90 degrees is arranged two-dimensionally on the light extraction side of the substrate.
  • One side is preferably in the range of 10 to 100 ⁇ m. If it is smaller than this, the effect of diffraction occurs and it is colored, and if it is too large, the thickness becomes thick, which is not preferable.
  • the condensing sheet for example, a sheet that has been put into practical use as an LED backlight of a liquid crystal display device can be used.
  • a sheet for example, a brightness increasing film (BEF) manufactured by Sumitomo 3M Ltd. can be used.
  • BEF brightness increasing film
  • the shape of the prism sheet may be, for example, a base material having a ⁇ -shaped stripe having an apex angle of 90 degrees and a pitch of 50 ⁇ m, or a shape having a rounded apex angle and a random pitch change. It may have a right angle or other shape.
  • a light diffusing plate / film may be used in combination with a condensing sheet in order to control the light emission angle from the organic EL element.
  • a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.
  • the organic EL element in the present invention can be used as a display device, a display, and various light emitting light sources.
  • Light sources include, for example, lighting devices (household lighting, interior lighting), clock and liquid crystal backlights, signage advertisements, traffic lights, optical storage medium light sources, electrophotographic copying machine light sources, optical communication processing machine light sources, and light Examples thereof include, but are not limited to, a light source for a sensor, but the light source can be effectively used as a backlight for a liquid crystal display device and a light source for lighting.
  • patterning may be performed by a metal mask, an inkjet printing method, or the like at the time of film formation.
  • patterning only the electrodes may be patterned, the electrodes and the light emitting layer may be patterned, or all the layers of the device may be patterned.
  • a conventionally known method is used. Can be done.
  • the non-light emitting surface of the organic EL element is covered with a glass case, a glass substrate having a thickness of 300 ⁇ m is used as a sealing substrate, and an epoxy-based photocurable adhesive (Luxtrac LC0629B manufactured by Toa Synthetic Co., Ltd.) is used as a sealing material around it. ) Is applied, and this is overlaid on the cathode and brought into close contact with the transparent support substrate, irradiated with UV light from the glass substrate side, cured, sealed, and an illuminating device as shown in FIGS. Can be formed.
  • an epoxy-based photocurable adhesive (Luxtrac LC0629B manufactured by Toa Synthetic Co., Ltd.)
  • FIG. 3 shows a schematic view of the lighting device, and the organic EL element 101 according to the present invention is covered with a glass cover 102 (note that the sealing operation with the glass cover brings the organic EL element 101 into contact with the atmosphere.
  • the glove box was carried out in a nitrogen atmosphere (in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more).
  • FIG. 4 shows a cross-sectional view of the lighting device.
  • 105 shows a cathode
  • 106 shows an organic EL layer
  • 107 shows a glass substrate with a transparent electrode.
  • the glass cover 102 is filled with nitrogen gas 108, and a water catching agent 109 is provided.
  • the luminescent thin film of the present invention is characterized by containing the charge transporting compound of the present invention.
  • the luminescent thin film of the present invention can be produced in the same manner as in the method for forming the organic layer (light emitting layer).
  • the method for forming the luminescent thin film of the present invention is not particularly limited, and conventionally known methods such as a vacuum vapor deposition method and a wet method (also referred to as a wet process) can be used.
  • Examples of the wet method include a spin coating method, a casting method, an inkjet method, a printing method, a die coating method, a blade coating method, a roll coating method, a spray coating method, a curtain coating method, and an LB method (Langmuir-Brojet method).
  • a method having high suitability for the roll-to-roll method such as a die coating method, a roll coating method, an inkjet method, and a spray coating method is preferable.
  • liquid medium used for forming the luminescent thin film of the present invention examples include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene and mesitylene.
  • Aromatic hydrocarbons such as cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin and dodecane, and organic solvents such as DMF and DMSO can be used.
  • dispersion can be performed by a dispersion method such as ultrasonic waves, high shear force dispersion, or media dispersion.
  • the vapor deposition conditions vary depending on the type of compound used, but generally the boat heating temperature is in the range of 50 to 450 ° C and the degree of vacuum is in the range of 10 -6 to 10-2 Pa.
  • the vapor deposition rate should be appropriately selected within the range of 0.01 to 50 nm / sec, the substrate temperature within the range of -50 to 300 ° C., the thickness within the range of 0.1 nm to 5 ⁇ m, and preferably within the range of 5 to 200 nm. desirable.
  • the spin coating method it is preferable to carry out the spin coater within the range of 100 to 1000 rpm and within the range of 10 to 120 seconds in a dry inert gas atmosphere.
  • the ink composition of the present invention is characterized by containing the charge transporting compound of the present invention.
  • the charge transporting compound By containing the charge transporting compound, it is possible to suppress fluctuations in physical properties of the charge transfer / light emitting thin film using the ink composition over time of energization, improve luminous efficiency and improve the life of the light emitting element, and deeply.
  • a composition capable of emitting blue light can be prepared.
  • the ink composition of the present invention includes, for example, a printing method such as a gravure printing method, a flexo printing method, a screen printing method, a spin coating method, a casting method, an inkjet printing method, a die coating method, a blade coating method, and a bar coating method. It is applied as a coating liquid for roll coating method, dip coating method, spray coating method, curtain coating method, doctor coating method, LB method (Langmuir-Bloget method), etc., but the ink composition should be applied easily and accurately. From the viewpoint of high productivity and high productivity, it is more preferable to apply by the above-mentioned inkjet printing method using an inkjet head.
  • a printing method such as a gravure printing method, a flexo printing method, a screen printing method, a spin coating method, a casting method, an inkjet printing method, a die coating method, a blade coating method, and a bar coating method. It is applied as a coating liquid for roll coating method,
  • the ink composition of the present invention is used as an organic EL element material.
  • the organic EL device material of the present invention is characterized by containing the charge transporting compound of the present invention.
  • the charge transporting compound By containing the charge transporting compound, it is possible to suppress fluctuations in physical properties of a charge transfer / light emitting thin film using the organic EL device material over time of energization, improve luminous efficiency and improve the life of the light emitting device, and also. It is possible to manufacture an organic EL element capable of emitting a deep blue light.
  • the organic EL device material of the present invention can be used as a material for the organic layer of the organic EL device described above, and includes a light emitting layer, an electron transport layer, a hole blocking layer, an electron injection layer, a hole transport layer, an electron blocking layer and the like. It can be used as a material such as a hole injection layer.
  • the light emitting material of the present invention contains the charge transporting compound of the present invention, and the charge transporting compound radiates fluorescence. That is, the charge transporting compound is contained as a light emitting material used for the light emitting layer. Further, in the light emitting material of the present invention, it is preferable that the charge transporting compound emits delayed fluorescence.
  • (0) (Pd 2 (dba) 3 ) (0.2 g, 0.2 mmol), K 2 CO 3 (1.7 g, 12.2 mmol), 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl ( S-Phos (0.3 g, 0.8 mmol) was added and the mixture was stirred at 110 ° C. for 6 hours. Water was added to the reaction solution, and the precipitate was collected by filtration. This was recrystallized to obtain 1.07 g of an intermediate.
  • Example 2 ⁇ Manufacturing of organic EL element 1-1> (Manufacturing of organic EL element 1-1) Patterning was performed on a substrate (NA45 manufactured by NH Techno Glass Co., Ltd.) in which ITO (indium tin oxide) was deposited at 100 nm on a glass substrate having a size of 100 mm ⁇ 100 mm ⁇ 1.1 mm as an anode. Then, the transparent support substrate provided with the ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone washed for 5 minutes.
  • a substrate NA45 manufactured by NH Techno Glass Co., Ltd.
  • ITO indium tin oxide
  • polystyrene sulfonate PEDOT / PSS, Bayer, Bayer P Al 4083
  • PEDOT / PSS polystyrene sulfonate
  • a thin film was formed by a spin coating method at 2000 rpm for 30 seconds using a solution of polyvinylcarbazole (weight average molecular weight Mw: 1100000) in 1,2dichlorobenzene, and then dried at 120 ° C. for 10 minutes.
  • a hole transport layer having a thickness of 15 nm was provided.
  • a thin film was prepared by a spin coating method under the conditions of 2000 rpm and 30 seconds using a solution prepared by dissolving comparative compound 1 as a luminescent compound and mCBP as a host compound in toluene so as to be 10% and 90% by weight, respectively. After forming, it was dried at 100 ° C. for 10 minutes to provide a light emitting layer having a thickness of 35 nm. Next, this substrate was fixed to a substrate holder of a commercially available vacuum vapor deposition apparatus.
  • Each of the vapor deposition crucibles in the vacuum vapor deposition apparatus was filled with the constituent materials of each layer in the optimum amount for manufacturing the device.
  • a crucible for vapor deposition a crucible made of molybdenum or tungsten made of a resistance heating material was used.
  • SF3-TRZ was vapor-deposited at a vapor deposition rate of 1.0 nm / sec to form a hole blocking layer having a thickness of 5 nm. Then, SF3-TRZ and LiQ (8-hydroxyquinolinolato-lithium) are co-deposited at a vapor deposition rate of 1.0 nm / sec so as to be 50% and 50% mol%, respectively, and electron transport with a layer thickness of 30 nm. A layer was formed.
  • an organic EL element 1-1 After forming lithium fluoride with a thickness of 0.5 nm, 100 nm of aluminum was vapor-deposited to form a cathode. The non-light emitting surface side of the element was covered with a can-shaped glass case in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more, and an electrode take-out wiring was installed to prepare an organic EL element 1-1.
  • Organic EL devices 1-2 to 1-6 were produced in the same manner as the organic EL device 1-1 except that the luminescent compounds were changed as shown in Table II.
  • Each of the above-produced organic EL elements is made to emit light at room temperature (about 25 ° C.) under a constant current condition of 2.5 mA / cm 2 , and the emission brightness immediately after the start of emission is measured by the spectral radiance meter CS-2000 (Konica Minolta). It was measured using (manufactured by the company). The obtained emission luminance was calculated as a relative value with respect to the emission luminance of the organic EL element 1-1, and this is shown in Table II as the luminous efficiency.
  • the charge-transporting compound of the present invention showed higher luminous efficiency than the comparative compound 1. Further, in each case, the charge-transporting compound of the present invention showed a higher emission luminance half-time than the comparative compound 1.
  • Example 3 ⁇ Manufacturing of organic EL element 2-1> Patterning was performed on a substrate (NA45 manufactured by AvanStrate Inc.) in which ITO was deposited at 100 nm on a glass substrate having a size of 100 mm ⁇ 100 mm ⁇ 1.1 mm as an anode. Then, the transparent support substrate provided with the ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone washed for 5 minutes.
  • polystyrene sulfonate PEDOT / PSS, Bayer, Bayer P Al 4083
  • PEDOT / PSS polystyrene sulfonate
  • a thin film was formed by a spin coating method using a solution of polyvinylcarbazole (weight average molecular weight Mw: 1100000) in 1,2dichlorobenzene under the conditions of 2000 rpm for 30 seconds, and then dried at 120 ° C. for 10 minutes. Then, a hole transport layer having a layer thickness of 15 nm was provided. Next, using an ink composition in which comparative compound 1 as a luminescent compound and mCBP as a host compound were dissolved in propylene glycol monomethyl ether acetate so as to be 10% and 90% by mass, respectively, the structure shown in FIG. 1 described above. After drying at 40 ° C.
  • the piezo type inkjet printer head "KM1024i” manufactured by Konica Minolta which is a piezo type inkjet printer head composed of After injection onto the hole transport layer under the condition that the layer thickness was 35 nm, it was dried at 120 ° C. for 30 minutes to form a light emitting layer.
  • this substrate was fixed to a substrate holder of a commercially available vacuum vapor deposition apparatus.
  • Each of the vapor deposition crucibles in the vacuum vapor deposition apparatus was filled with the constituent materials of each layer in the optimum amount for manufacturing the device.
  • a crucible for vapor deposition a crucible made of molybdenum or tungsten made of a resistance heating material was used.
  • SF3-TRZ was vapor-deposited at a vapor deposition rate of 1.0 nm / sec to form a hole blocking layer having a layer thickness of 5 nm.
  • SF3-TRZ and LiQ (8-hydroxyquinolinolato-lithium) are co-deposited at a vapor deposition rate of 1.0 nm / sec so as to be 50% and 50% mol%, respectively, and electron transport with a layer thickness of 30 nm. A layer was formed. Further, after forming lithium fluoride with a thickness of 0.5 nm, aluminum 100 nm was vapor-deposited to form a cathode. The non-light emitting surface side of the element was covered with a can-shaped glass case in an atmosphere of high-purity nitrogen gas having a purity of 99.999% or more, and an electrode take-out wiring was installed to prepare an organic EL element 2-1.
  • Organic EL devices 2-2 to 2-6 were produced in the same manner as the organic EL device 2-1 except that the luminescent compounds were changed as shown in Table III below.
  • Luminous efficiency and emission luminance half time were calculated by the same method as in Example 2, and shown as relative values with the values of the organic EL elements 2-1 as 100, respectively. The above results are shown in Table III.
  • the charge-transporting compound of the present invention showed higher luminous efficiency than the comparative compound 1. Moreover, in each case, the charge transporting compound of the present invention showed a higher luminance half-time than the comparative compound 1.
  • the charge transporting compound of the present invention suppresses fluctuations in physical properties of the charge transfer / light emitting thin film over time of energization, is excellent in light emission efficiency and light emitting device life, and is excellent in ink composition, organic electroluminescence device material, light emitting material, and the like. It can be preferably applied to a luminescent thin film and an organic electroluminescence device.

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JPWO2020189236A1 (https=) * 2019-03-18 2020-09-24
US20220190257A1 (en) * 2019-03-19 2022-06-16 Konica Minolta, Inc. Functional film, method for forming same, and organic electroluminescent element
WO2023140374A1 (ja) * 2022-01-24 2023-07-27 株式会社Kyulux 化合物、発光材料および発光素子

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