WO2014073683A1 - Élément organique électroluminescent, et procédé pour sa fabrication - Google Patents

Élément organique électroluminescent, et procédé pour sa fabrication Download PDF

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WO2014073683A1
WO2014073683A1 PCT/JP2013/080443 JP2013080443W WO2014073683A1 WO 2014073683 A1 WO2014073683 A1 WO 2014073683A1 JP 2013080443 W JP2013080443 W JP 2013080443W WO 2014073683 A1 WO2014073683 A1 WO 2014073683A1
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group
ring
layer
hole injection
hole
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PCT/JP2013/080443
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English (en)
Japanese (ja)
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友和 梅基
淑 杉山
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三菱化学株式会社
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/854—Arrangements for extracting light from the devices comprising scattering means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom

Definitions

  • the present invention relates to an organic electroluminescent device and a method for producing the same.
  • organic electroluminescent element (hereinafter sometimes referred to as “organic EL (electroluminescence)”) includes an anode and a cathode on a glass substrate, and a light emitting layer formed between both electrodes.
  • the light generated in the light emitting layer by energizing both electrodes passes through the anode (for example, a transparent electrode such as ITO) and the glass substrate and is extracted outside.
  • the anode for example, a transparent electrode such as ITO
  • ITO transparent electrode
  • the reflection caused by the refractive index difference occurs at the interface between the light emitting layer and ITO, ITO and glass substrate, and the glass substrate and the atmosphere, most of the emitted light cannot be extracted outside, It is known that the light extracted outside is about 20% of the emitted light.
  • a method of introducing a light scattering layer is known.
  • the effect of the light scattering layer varies depending on the position where it is introduced, and the highest light extraction effect is obtained when it is provided between the light emitting layer and the anode (ITO or the like). This is because a scattering effect can be given to emitted light reflected at all interfaces of the light emitting layer and ITO, ITO and glass substrate, and the glass substrate and air.
  • a method of forming a light scattering layer between a light emitting layer and an anode (ITO or the like) by a coating method that is simple and has high productivity has been reported.
  • a light scattering layer is formed by applying a material in which inorganic conductive fine particles such as ITO are dispersed to a general-purpose organic resin polymer such as polymethyl methacrylate.
  • Patent Document 2 hole transport in which silicon oxide particles or silver nanoparticles are dispersed in poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (hereinafter, PEDOT / PSS), which is a hole injecting and transporting material.
  • PEDOT / PSS polystyrene sulfonic acid
  • Patent Document 3 the luminous efficiency of the organic electric field element is improved by using a PEDOT / PSS layer in which silicon oxide particles having a particle diameter of 1 to 100 nm and titanium oxide particles having a particle diameter of 100 to 1000 nm are co-dispersed. It has been reported.
  • the light scattering layer described in Patent Document 1 uses a general-purpose organic resin (generally having a refractive index of less than 1.5 to 1.6) as a binder component, the formed light scattering layer and light emitting layer (generally refracting) It is expected that the light extraction effect is low because total reflection occurs at the interface with the rate of 1.7 or more.
  • the publication describes that the film thickness is 4 ⁇ m or more.
  • general-purpose organic resin is inferior in solvent resistance and heat resistance, and has a large thermal expansion coefficient, restrictions occur when manufacturing an organic electroluminescent element. Further, it is additionally formed for the purpose of obtaining only the light scattering function, and there is a problem that an additional process is required in the production of the organic electroluminescent element.
  • Patent Document 2 a particle-containing hole injection layer is formed by spin-coating a dispersion obtained by mixing particles with PEDOT / PSS which is a hole transport material.
  • PEDOT / PSS which is a hole transport material.
  • the light extraction effect was not acquired as shown in the comparative examples 1 and 2 mentioned later. If the particle diameter is about 20 to 30 nm and the hole transport layer thickness is less than 100 nm, the light scattering property is weak and it is presumed that the light extraction effect was not exhibited.
  • Patent Document 3 discloses an organic electric field device using a PEDOT / PSS layer in which silicon oxide particles having a particle size of 20 to 30 nm and titanium oxide particles having a particle size of 20 to 130 nm are co-dispersed, thereby improving luminous efficiency.
  • PEDOT / PSS has DMSO, which is a high boiling point solvent, to improve conductivity, and the light emission efficiency may have been improved by adding DMSO and lowering the driving voltage. There is. Therefore, it is considered that Patent Document 3 does not clearly describe the improvement of the light extraction efficiency by the particles.
  • PEDOT / PSS is generally provided only in a dilute dispersion, it is practically difficult to obtain a sufficient film thickness.
  • the particles When a sufficient film thickness cannot be obtained with PEDOT / PSS as a binder, the particles may become protrusions on the surface of the coating film. This causes a short circuit and non-light emission of the organic electroluminescent element.
  • the film thickness of the hole transport layer is not described at all.
  • attempts to form a light scattering film by applying a hole transporting material containing particles have been reported so far, but have not yet reached a practical technique. This is because in order to obtain a hole injecting and transporting layer having an effective light scattering ability, many conditions such as the structure of the hole transporting material, the condition of the particles, the film thickness, and the surface shape are necessary.
  • An object of the present invention is to provide an organic electroluminescence device using a light-scattering hole injecting and transporting layer which can be easily formed by coating or the like and has excellent light extraction efficiency.
  • the present inventors have determined that the thickness of at least one layer selected from a hole injection layer and a hole transport layer is 100 nm or more and 1000 nm or less, and the hole injection layer And the present invention has been completed by finding that the above problems can be solved by dispersing particles in at least one layer selected from the hole transport layer. That is, the present invention is as follows.
  • An organic electroluminescent device comprising an anode and a cathode, and at least one layer selected from a hole injection layer and a hole transport layer formed between the anode and the cathode, Particles are dispersed in at least one layer selected from the hole injection layer and the hole transport layer, and the film thickness of at least one layer selected from the hole injection layer and the hole transport layer Is an organic electroluminescent element which is 100 nm or more and 1000 nm or less.
  • the organic electroluminescence of [1] wherein the hole injection / transport material contained in at least one layer selected from the hole injection layer and the hole transport layer is an aromatic tertiary amine polymer compound element.
  • the organic electroluminescence device according to [1] or [2], wherein the particles are at least one selected from metal oxides, composite oxides, and polymer materials.
  • the organic electroluminescent element according to any one of [1] to [3], wherein the average particle diameter of the particles is 10 nm or more and 300 nm or less.
  • An organic EL display device comprising the organic electroluminescent element according to any one of [1] to [6].
  • Organic EL illumination including the organic electroluminescent element according to any one of [1] to [6].
  • an organic electroluminescence device using at least one layer selected from a light-scattering hole injection layer and a hole transport layer, which can be easily formed by coating or the like and has excellent light extraction efficiency Can be provided.
  • FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of an organic electroluminescent element of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing another example of the embodiment of the organic electroluminescent element of the present invention.
  • An organic electroluminescent device comprising an anode and a cathode, and at least one layer selected from a hole injection layer and a hole transport layer formed between the anode and the cathode, the hole injection layer And particles are dispersed in at least one layer selected from the hole transport layer and the film thickness of at least one layer selected from the hole injection layer and the hole transport layer is 100 nm or more and 1000 nm.
  • the organic electroluminescent element of the present invention includes an anode and a cathode, and includes at least one layer selected from a hole injection layer and a hole transport layer formed between the anode and the cathode.
  • at least one layer selected from the hole injection layer and the hole transport layer an organic semiconductor layer that may be formed between the anode and the cathode will be described later.
  • the hole injection layer and the hole transport layer may be collectively referred to as a “hole injection / transport layer”.
  • the hole injection / transport layer (1, 2) of the present invention has a function of injecting and transporting holes from the anode 6 side to the light emitting layer 3 side. It is a layer that bears and is formed adjacent to the anode 6.
  • the hole injection / transport layers (1, 2) are preferably formed in that the function of injecting and transporting holes from the anode 6 to the light emitting layer 3 side is enhanced.
  • the film thickness of the hole injection / transport layer (1, 2) is usually 100 nm or more, preferably 120 nm or more, more preferably 150 nm or more.
  • both the hole injection layer 1 and the hole transport layer 2 may be formed with the film thickness, or one of them may be formed with the film thickness.
  • the layer in which particles described later are dispersed is preferably formed with the above film thickness.
  • the hole injection / transport layer (1, 2) preferably contains a hole injection / transport compound, and more preferably contains a hole injection / transport compound and an electron accepting compound. Further, the hole injection layer preferably contains a cation radical compound, and particularly preferably contains a cation radical compound and a hole injection / transport compound.
  • the hole injection layer of the present invention is formed by a wet film formation method. Below, the formation method of a positive hole injection layer is demonstrated.
  • the composition for forming a hole injection / transport layer prepared as a precursor of the hole injection / transport layer usually contains a hole injection / transport compound that becomes a hole injection / transport layer.
  • a solvent is usually further contained.
  • the composition for forming a hole injecting / transporting layer preferably has a high hole injecting / transporting property and can efficiently transport injected holes. For this reason, it is preferable that the hole mobility is large and impurities that become traps are less likely to be generated during production or use. Moreover, it is preferable that it is excellent in stability, has a small ionization potential, and has high transparency to visible light. In particular, when the hole injection layer is in contact with the light emitting layer, those that do not quench the light emitted from the light emitting layer or those that form an exciplex with the light emitting layer and do not decrease the light emission efficiency are preferable.
  • the hole injection / transport compound is preferably a compound having an ionization potential of 4.5 eV to 6.0 eV from the viewpoint of a charge injection barrier from the anode to the hole injection / transport layer.
  • hole injecting and transporting compounds include aromatic amine compounds, phthalocyanine compounds, porphyrin compounds, oligothiophene compounds, polythiophene compounds, benzylphenyl compounds, compounds in which tertiary amines are linked by a fluorene group, Examples include hydrazone compounds, silazane compounds, and quinacridone compounds.
  • aromatic amine compounds are preferable, and aromatic tertiary amine polymer compounds are particularly preferable from the viewpoints of amorphousness and visible light transmittance.
  • the aromatic tertiary amine polymer compound is a compound having an aromatic tertiary amine structure, and includes a compound having a group derived from an aromatic tertiary amine.
  • the type of the aromatic tertiary amine polymer compound is not particularly limited, but a polymer compound having a weight average molecular weight of 3000 or more and 1000000 or less (polymerization in which repeating units are linked) is easy to obtain uniform light emission due to the surface smoothing effect. Type compound) is preferably used.
  • the aromatic tertiary amine polymer compound solution can be regarded as a uniform dispersion medium. Therefore, it is possible to disperse the particles uniformly, and the film obtained by forming the film can obtain a film in which the particles are uniformly dispersed.
  • PEDOT / PSS solution described in Patent Documents 2 and 3 PEDOT and PSS are combined to form a cluster. That is, this is a dispersion in which the dispersoid clusters are dispersed in an aqueous solvent as a dispersion medium.
  • the solid content concentration of the PEDOT / PSS dispersion is usually several percent or less, when any particle is dispersed in the dispersion, it is usually dispersed in the dispersion and it is difficult to disperse the particles in the dispersoid. It is. As a result, when the film is formed, the particles are aggregated, and it is difficult to obtain a film in which the particles are uniformly dispersed. Further, since PSS contains a sulfonic acid group, the PEDOT / PSS dispersion is acidic. If further mixed with a particle dispersion, the dispersibility of the particles deteriorates due to the acidity, and aggregation and precipitation occur. It becomes easy. Therefore, it is difficult to obtain a thin film in which particles are uniformly dispersed in PEDOT / PSS using such a dispersion.
  • the aromatic tertiary amine polymer compound will be described in detail.
  • the weight average molecular weight (Mw) of the aromatic tertiary amine polymer compound in the present invention is 3000 or more and 1000000 or less, which is suitable for use in an organic electroluminescence device.
  • Mw weight average molecular weight of the aromatic tertiary amine polymer compound
  • the solubility of the aromatic tertiary amine polymer compound in the organic solvent is good and a uniform film is formed during wet film formation.
  • purification is easy and industrial disadvantages are less likely to occur.
  • the weight average molecular weight is less than the lower limit, the glass transition temperature, melting point and vaporization temperature are lowered, so that the heat resistance may be significantly impaired.
  • the weight average molecular weight is preferably 100,000 or less, and preferably 60000 or less from the viewpoint of solubility, film forming property, and heat resistance. Further preferred.
  • the lower limit is preferably 5000 or more, and more preferably 10,000 or more.
  • the number average molecular weight (Mn) of the aromatic tertiary amine polymer compound in the present invention is usually 2,500,000 or less, preferably 750,000 or less, more preferably 400,000 or less, and usually 500 Above, preferably 1,500 or more, more preferably 3,000 or more.
  • the degree of dispersion (Mw / Mn) of the aromatic tertiary amine polymer compound in the present invention is usually 10 or less, preferably 2.5 or less, more preferably 2.0 or less, preferably 1.0 or more. More preferably, it is 1.1 or more, and particularly preferably 1.2 or more.
  • the weight average molecular weight (and number average molecular weight) in the present invention is determined by SEC (size exclusion chromatography) measurement.
  • SEC size exclusion chromatography
  • the elution time is shorter for higher molecular weight components and the elution time is longer for lower molecular weight components, but using the calibration curve calculated from the elution time of polystyrene (standard sample) with a known molecular weight, the elution time of the sample is changed to the molecular weight. By converting, the weight average molecular weight (and number average molecular weight) is calculated.
  • the aromatic tertiary amine polymer compound contained in the composition for organic electroluminescent elements of the present invention is preferably a polymer containing a repeating unit represented by the following formula (2).
  • m represents an integer of 0 to 3
  • Ar 31 and Ar 32 are each independently a direct bond, a divalent aromatic hydrocarbon ring which may have a substituent.
  • Ar 33 to Ar 35 each independently have an aromatic hydrocarbon ring group or a substituent which may have a substituent.
  • Ar 33 and Ar 35 represent a monovalent group
  • Ar 34 represents a divalent group, provided that Ar 31 and Ar 32 are a direct bond at the same time. There is no.
  • Ar 34 and Ar 35 may be the same or different.
  • Ar 31 and Ar 32 may each independently have a direct bond, a divalent aromatic hydrocarbon ring group which may have a substituent, or a substituent.
  • Each of Ar 33 to Ar 35 independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Represents.
  • Examples of the aromatic hydrocarbon ring group which may have a substituent include, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring having one or two free valences, Examples include a 6-membered monocyclic ring or a 2-5 condensed ring having one or two free valences such as a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
  • free valence can form bonds with other free valences as described in Organic Chemistry / Biochemical Nomenclature (above) (Revised 2nd edition, Nankodo, 1992). Say things.
  • aromatic heterocyclic group which may have a substituent, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring having one or two free valences, Imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole Ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quino
  • Ar 31 to Ar 35 may each independently have a substituent, a benzene ring or a naphthalene ring having one or two free valences.
  • An anthracene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a thiophene ring, a pyridine ring, and a fluorene ring are preferable.
  • Ar 31 to Ar 35 a group in which one or two or more rings selected from the above group are directly bonded or connected by a —CH ⁇ CH— group is preferable, and a biphenyl group, a terphenyl group, and the like are further included. preferable.
  • the aromatic hydrocarbon ring group that may have a substituent and the aromatic heterocyclic group that may have a substituent may have the following ⁇ substituent group Z > Groups.
  • Each of the above substituents may further have a substituent, and examples thereof include the groups exemplified in the substituent group Z.
  • the molecular weight of the substituent that the aromatic hydrocarbon ring group and aromatic heterocyclic group in Ar 31 to Ar 35 may have is preferably 500 or less, more preferably 250 or less, including the substituted group.
  • the substituents that the aromatic hydrocarbon ring group and the aromatic heterocyclic group in Ar 31 to Ar 35 may have are each independently an alkyl group having 1 to 12 carbon atoms. And an alkoxy group having 1 to 12 carbon atoms is preferred.
  • the repeating unit represented by the formula (2) has two or more Ar 34 and Ar 35 .
  • Ar 34 and Ar 35 may be the same or different.
  • Ar 34 and Ar 35 may be bonded to each other directly or via a linking group to form a cyclic structure.
  • M in Formula (2) represents an integer of 0 or more and 3 or less.
  • m is preferably 0 in that the solubility of the aromatic tertiary amine polymer compound in an organic solvent and the film formability are improved. Further, m is preferably 1 or more and 3 or less from the viewpoint of improving the hole transport ability of the aromatic tertiary amine polymer compound.
  • the aromatic tertiary amine polymer compound in the present invention is a conjugated polymer because it consists of a repeating unit having a conjugated structure and therefore has sufficient charge transporting ability and sufficient solubility in a solvent. It is preferable. More specifically, it is preferably a polymer composed of a repeating unit represented by the formula (2).
  • the aromatic tertiary amine polymer compound in the present invention is a conjugated polymer
  • the aromatic tertiary amine polymer compound further has an insolubilizing group from the viewpoint of easy lamination and excellent surface flatness during film formation. That is, the aromatic tertiary amine polymer compound in the present invention is preferably a conjugated polymer having an insolubilizing group.
  • the insolubilizing group is a group that reacts by irradiation with active energy rays such as heat and / or light, and is a group having an effect of lowering solubility in an organic solvent or water after the reaction than before the reaction.
  • the insolubilizing group is preferably a dissociable group or a crosslinkable group.
  • the aromatic tertiary amine polymer compound has a group containing an insolubilizing group as a substituent, but the position having the insolubilizing group may be in the repeating unit represented by the formula (2). You may have in parts other than the repeating unit represented by 2), for example, a terminal group.
  • an aromatic tertiary amine polymer compound having a dissociable group may be referred to as a “dissociable polymer”, and an aromatic tertiary amine polymer compound having a crosslinkable group may be referred to as a “crosslinkable polymer”.
  • the dissociable group is a group that is soluble in a solvent, and represents a group that is thermally dissociated at 70 ° C. or higher from a bonded group (for example, a hydrocarbon ring).
  • the dissociation of the dissociable group reduces the solubility of the polymer in the solvent.
  • a reaction in which other atoms are bonded after dissociation, for example, a group dissociated by hydrolysis is excluded.
  • a group dissociating by hydrolysis has an active proton in the molecule after dissociation. If this active proton is present in the device, the device characteristics may be affected.
  • Such a dissociable group is preferably bonded to a hydrocarbon ring, and the hydrocarbon ring is preferably condensed to an aromatic hydrocarbon ring having no polar group.
  • the group is thermally dissociated by a reverse Diels-Alder reaction. More preferably.
  • the temperature at which heat dissociates is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, preferably 300 ° C. or lower, more preferably 240 ° C. or lower.
  • the synthesis of the polymer is easy, and the compound does not easily decompose during film formation.
  • a group having a three-dimensional structure that suppresses intermolecular stacking is preferable because it is excellent in solubility.
  • An example of a reaction in which a dissociable group dissociates from a compound is shown below.
  • the dissociable group is a portion surrounded by a round frame having the structure shown below.
  • dissociable group dissociation examples include, for example, desulfinylacetamide (see JACS, V124, No. 30, 2002, 8813), deolefination, dealcoholization, dealkylation (H. Kwart and K. King, Department). of Chemistry, University of Delaware, Newware, Delaware 19771, p415-447 (1967), O. Diels and K. Alder, Ber., 62, 554 (1929) and MC KlotzelAc. (See 1948)), de-1,3-dioxole (see ND Field, J. Am. Chem. Soc., 83, 3504 (1961)), dediene (R. Huis). en, M. Seidel, G. Wallbilrich, and H.
  • the hydrocarbon ring to which the dissociable group is bonded is preferably an etheno group or a ring containing an ethano group from the viewpoint that the dissociable group is more stable and easy to synthesize.
  • a dissociable group can prevent stacking between molecules due to its bulky molecular structure before heat treatment, or the polymer can have good solubility in an organic coating solvent. .
  • the solubility of the compound after heating in the solvent can be remarkably suppressed, and the organic layer containing the compound is imparted with an organic solvent coating resistance. I can do it. Therefore, it becomes easy to further form an organic thin film on the organic layer formed using the dissociable polymer in the present invention by a wet film forming method.
  • group containing a dissociable group examples are as follows, but the present invention is not limited thereto.
  • a specific example in the case where the group containing a dissociable group is a divalent group is as shown in ⁇ Group group A containing a divalent dissociable group> below. ⁇ Group A containing divalent dissociable group>
  • dissociable group is a monovalent group
  • dissociable group is a monovalent group
  • the structure of the repeating unit and the like is not particularly limited.
  • the dissociative group is preferably bonded to a hydrocarbon ring condensed with the ring.
  • a conjugated polymer having a dissociative group containing a repeating unit having a partial structure in which an etheno group or a dissociative group containing an ethano group is bonded is preferable from the viewpoint of excellent film formability.
  • the etheno group or ethano group is preferably contained in a hydrocarbon ring, and the hydrocarbon ring is preferably a 6-membered ring.
  • the conjugated polymer having a dissociable group in the present invention includes a repeating unit having a partial structure represented by the following chemical formula (U3) or (U4) as a repeating unit having a partial structure to which the dissociable group is bonded. Is preferred.
  • the content of the repeating unit (U3) or (U4) in the polymer chain is preferably 10 mol% or more, more preferably 30 mol% or more.
  • ring A 1 represents an aromatic ring.
  • the aromatic ring may have a substituent.
  • the substituents may be directly or via a divalent linking group.
  • S 21 , S 22 and R 21 to R 26 may each independently have a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, or a substituent.
  • a good aromatic hydrocarbon ring group an aromatic heterocyclic group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent;
  • An aryloxy group which may have a substituent, an acyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent.
  • acyloxy group which may be substituted an arylamino group which may have a substituent, and a substituent .
  • X 1 and X 2 which represents an acylamino group which may have a hetero arylamino group or a substituent to the optionally be each independently a substituent having unprotected C6 more than 50
  • the following divalent aromatic hydrocarbon ring group or a divalent aromatic heterocyclic group having 5 to 50 carbon atoms which may have a substituent is represented.
  • ring B 1 represents an aromatic ring.
  • the aromatic ring may have a substituent.
  • the said substituents may form the ring directly or through the bivalent coupling group.
  • S 31 to S 34 , R 31 to R 36 , X 3 and X 4 are each independently the same as those shown as S 21 , S 22 , R 21 to R 26 , X 1 and X 2 .
  • n 1 to n 4 each independently represents an integer of 0 to 5.
  • ring A 1 and ring B 1 each represent an aromatic ring to which a dissociable group is bonded, and may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. However, since it is excellent in electrochemical stability and the charge is difficult to localize, an aromatic hydrocarbon ring is preferable.
  • the aromatic ring may have a substituent.
  • the substituents may form a ring directly or via a divalent linking group.
  • the number of nuclear carbons of the aromatic hydrocarbon ring is usually 6 or more. Moreover, it is 40 or less normally, Preferably it is 30 or less, More preferably, it is 20 or less.
  • the number of nuclear carbon atoms of the aromatic heterocycle is usually 3 or more, preferably 4 or more, more preferably 5 or more. Moreover, it is 50 or less normally, Preferably it is 30 or less, More preferably, it is 20 or less.
  • the aromatic hydrocarbon ring examples include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, chrysene ring, benzochrysene ring, triphenylene ring, fluoranthene ring, and fluorene ring.
  • the ring A 1 and the ring B 1 are independently selected from the group consisting of a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring.
  • aromatic heterocycle examples include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolo Pyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, quinoline ring, isoquinoline ring Quinoxaline ring, perimidine ring, quinazoline ring, quinazolinone
  • the ring A 1 and the ring B 1 have the same or different two or more kinds of ring structural units of 1 or more and 10 or less, directly, or an oxygen atom, a nitrogen atom, a sulfur atom, A structure in which a chain group which may contain a hetero atom having 1 to 20 nuclear carbon atoms and a divalent linking group having one or more divalent groups selected from aliphatic groups having 1 to 20 carbon atoms is used. It is also possible.
  • the ring structural unit to be connected may be the same or different aromatic hydrocarbon ring or aromatic heterocyclic ring as the above aromatic hydrocarbon ring or aromatic heterocyclic ring. Moreover, these aromatic hydrocarbon rings and aromatic heterocycles may have a substituent.
  • Examples of the substituent for ring A 1 or ring B 1 include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, an n-butyl group, an isobutyl group, and a tert-butyl group having 1 to 10 carbon atoms.
  • alkenyl group having 1 to 8 carbon atoms such as vinyl group, allyl group and 1-butenyl group; alkynyl group having 1 to 8 carbon atoms such as ethynyl group and propargyl group; benzyl group and the like
  • An acylamino group such as an amino group; an alkoxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, or a butoxy group; An acyloxyl group having 1 to
  • substituents may be directly with each other, or —O—, —S—,>CO,> SO 2 , — (C ⁇ H 2 ⁇ ) —, —O— (C ⁇ H 2 ⁇ ) —, substituted or unsubstituted. May be bonded via a divalent linking group such as an alkylidene group having 2 to 20 carbon atoms, an alkylene group having 2 to 20 carbon atoms which may have a substituent, and may form a cyclic structure. .
  • the above ⁇ and ⁇ each represent an integer of 1 or more and 20 or less. As for these substituents, only one type, or two or more types may be substituted in any combination, or two or more may be substituted with ring A 1 or ring B 1 .
  • S 21 , S 22 , R 21 to R 26 , S 31 to S 34 , and R 31 to R 36 are each independently a hydrogen atom; a hydroxyl group; a methyl group, an ethyl group , N-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group and the like, the carbon number which may have a substituent is usually 1 or more, usually 50 or less, preferably 10 or less.
  • aromatic heterocyclic groups Aralkyl groups having 6 or more, preferably 7 or more, and usually 50 or less, preferably 8 or less aralkyl groups which may have a substituent such as benzyl group; methoxy group, ethoxy Group, butoxy group, etc.
  • the dissociable group may be contained in a portion other than the repeating unit of the dissociative polymer.
  • the average number of dissociable groups contained in the dissociable polymer chain is preferably 5 or more, more preferably 10 or more, and more preferably 50 or more on average. Within the above range, it is preferable in that the solubility of the organic layer formed using the dissociative polymer in the organic solvent is sufficiently lowered.
  • n represents the number of repeating units.
  • the aromatic tertiary amine polymer compound in the present invention when it is a conjugated polymer, it has a crosslinkable group as an insolubilizing group, and a reaction (crosslinking) caused by heat and / or active energy ray irradiation. This is preferable in that a large difference in solubility in a solvent can be produced before and after the reaction.
  • the crosslinkable group refers to a group that reacts with the same or different groups of other molecules located nearby by irradiation with heat and / or active energy rays to form a new chemical bond.
  • Examples of the crosslinkable group include groups shown in the crosslinkable group group T in that crosslinking is easy. ⁇ Crosslinkable group T>
  • R 81 to R 85 each independently represent a hydrogen atom or an alkyl group.
  • Ar 41 may have an aromatic hydrocarbon ring group or a substituent which may have a substituent. Represents a good aromatic heterocyclic group, and the benzocyclobutene ring may have a substituent, and the substituents may be bonded to each other to form a ring.
  • Groups that are insolubilized by cationic polymerization, such as cyclic ether groups such as epoxy groups and oxetane groups, and vinyl ether groups are preferred because they are highly reactive and easily insolubilized.
  • an oxetane group is particularly preferable in terms of easy control of the rate of cationic polymerization, and a vinyl ether group is preferable in that a hydroxyl group that may cause deterioration of the device during cationic polymerization is difficult to generate.
  • An arylvinylcarbonyl group such as a cinnamoyl group and a group that undergoes a cycloaddition reaction such as a benzocyclobutene ring having one free valence are preferable in terms of further improving electrochemical stability.
  • a benzocyclobutene ring having one free valence is particularly preferable in that the structure after insolubilization is particularly stable.
  • the benzocyclobutene ring in formula (5) may have a substituent.
  • the substituents may be bonded to each other to form a ring.
  • the crosslinkable group may be directly bonded to an aromatic hydrocarbon ring group or an aromatic heterocyclic group in the molecule, or may be bonded via a divalent group.
  • a group selected from an —O— group, a —C ( ⁇ O) — group, or an (optionally substituted) —CH 2 — group may be selected from 1 to 30 in any order. It is preferable to bind to an aromatic hydrocarbon ring group or an aromatic heterocyclic group via a divalent group formed by individual linking.
  • crosslinkable group via these divalent groups that is, a group containing a crosslinkable group
  • a group containing a crosslinkable group are as shown in ⁇ Group group T ′ containing a crosslinkable group> below, but the present invention is not limited thereto. It is not something.
  • the number of crosslinkable groups possessed by the crosslinkable polymer in the present invention can be represented by the number per 1000 molecular weights.
  • the number of crosslinkable groups possessed by the crosslinkable polymer is usually 3.0 or less, preferably 2.0 or less, more preferably 1.0 or less per 1000 molecular weight. Moreover, it is usually 0.01 or more, preferably 0.05 or more.
  • the number of crosslinkable groups per 1000 molecular weight of the crosslinkable polymer is calculated from the molar ratio of the charged monomers at the time of synthesis and the structural formula, excluding the end groups from the crosslinkable polymer. For example, the case of the following compound will be described.
  • the average molecular weight of the repeating unit excluding the terminal group is 362.33, and the average number of crosslinkable groups is 0.05 per repeating unit.
  • the number of crosslinkable groups per 1000 molecular weight is calculated to be 0.138.
  • Specific preferred examples of the crosslinkable polymer in the present invention are shown below, but the present invention is not limited thereto.
  • the crosslinkable polymer in the present invention is a conjugated polymer having at least one repeating unit selected from the group consisting of the following repeating unit group A and at least one repeating unit selected from the group consisting of the following repeating unit group B. Is particularly preferable in terms of high charge transporting ability and excellent redox stability. ⁇ Repeating unit group A>
  • the glass transition temperature of the crosslinkable polymer in the present invention is usually 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and usually 300 ° C. from the viewpoint of driving stability including the heat resistance of the organic electroluminescent element. It is below °C.
  • the ionization potential of the conjugated polymer is usually 4.5 eV or more, preferably 4.8 eV or more, and usually 6.0 eV or less, preferably 5.7 eV or less, from the viewpoint of excellent charge transport ability.
  • crosslinkable groups do not always exist close to each other because the molecular motion of the crosslinkable polymer molecule itself is large, so the solution state below the heating temperature for insolubilization described later Then there is almost no possibility of crosslinking.
  • the aromatic tertiary amine polymer compound in the present invention is preferably a non-conjugated polymer.
  • the reason for this is that when the amine site becomes a cation radical due to the electron-accepting compound, the main chain is not conjugated, so that the cation radical is difficult to move in the absence of voltage application. That is, cation radicals are uniformly distributed in the polymer chain. For this reason, the cation radical propagates in the polymer chain, and the aggregation due to the localization of the polymer is difficult, which is preferable.
  • non-conjugated polymers it is preferable to include a repeating unit represented by the formula (2), and further includes a repeating unit represented by the following formula (1) because of high hole injection / transport properties.
  • a polymer is preferred.
  • Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon ring group which may have a substituent, or an aromatic heterocyclic group which may have a substituent.
  • Ar 3 to Ar 5 each independently represents a divalent aromatic hydrocarbon ring group which may have a substituent, or a divalent aromatic heterocyclic group which may have a substituent.
  • X represents a divalent linking group.
  • Ar 1 to Ar 5 each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent. In these, two groups bonded to the same N atom may be bonded to each other to form a ring.
  • Ar 1 and Ar 2 may each independently have a substituent from the viewpoint of solubility, heat resistance, hole injection / transport properties of the aromatic tertiary amine polymer compound, A benzene ring, naphthalene ring, phenanthrene ring, thiophene ring and pyridine ring having a free valence are preferred, and a phenyl group and a naphthyl group are preferred.
  • Ar 3 to Ar 5 are each independently a benzene ring, naphthalene ring, triphenylene ring having two free valences from the viewpoints of heat resistance and hole injection / transport properties including redox potential.
  • a phenanthrene ring is preferable, and a phenylene group, a biphenylene group, and a naphthylene group are preferable.
  • the substituent that the aromatic hydrocarbon ring group and aromatic heterocyclic group in Ar 1 to Ar 5 may have has the same meaning as in the above ⁇ Substituent group Z>. The same applies to preferred groups among these.
  • the molecular weight of the substituent is usually 400 or less, preferably about 250 or less.
  • linking group X is preferably a divalent linking group selected from the following ⁇ linking group group X ′>. ⁇ Linking group X '>
  • Ar 11 to Ar 28 each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
  • R 41 and R 42 each independently represents a hydrogen atom or an arbitrary substituent.
  • Ar 11 to Ar 28 include the same groups as Ar 1 to Ar 5 described above.
  • R 41 and R 42 are a hydrogen atom or a substituent.
  • the substituent include an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a silyl group, a siloxy group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, and the like and preferred examples thereof. Examples include those exemplified in the above ⁇ Substituent group Z>.
  • Examples of the substituent that the aromatic hydrocarbon ring group and aromatic heterocyclic group in Ar 11 to Ar 28 may have include those exemplified in the above-mentioned ⁇ Substituent group Z> section.
  • the aromatic tertiary amine polymer compound used in the present invention preferably has the following formula (1-1) because the hole injection / transport property is very high.
  • the formula (1-2) is more preferable.
  • R 1 to R 5 each independently represents a substituent.
  • P and q each independently represent an integer of 0 to 5.
  • r, s and t are each independently And represents an integer of 0 to 4.
  • X has the same meaning as in formula (1).
  • specific examples of R 1 to R 5 are examples of the substituents that Ar 1 to Ar 5 may have, that is, those exemplified in the substituent group Z. Applicable.
  • each R 1 to R 5 may be the same as or different from each other.
  • Ar 11 to Ar 17 each independently represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
  • Examples of Ar 11 to Ar 17 include the same groups as Ar 1 to Ar 5 described above, and preferred examples are also the same.
  • repeating unit of aromatic tertiary amine polymer compound (Specific example of repeating unit of aromatic tertiary amine polymer compound)
  • this invention is not limited to these.
  • P-1 to P-11, P-13 to P-18, P-20, P-21, P-23, P-25 are preferable in terms of heat resistance and charge transport ability.
  • P-26 repeating units more preferably P-1, P-3, P-4, P-6, P-9, P-10 repeating units, still more preferably P-1 to P -11, P-13 to P-18, P-20, P-21, P-23, P-25, P-26, and even more preferably P-1, P-3, P -4, P-6, P-9 and P-10, most preferably P-1 and P-4.
  • the aromatic tertiary amine polymer compound in the present invention may be a polymer containing two or more different repeating units.
  • Ar 1 to Ar 5 or the linking group X in the repeating unit represented by the formula (1) may be different to form different repeating units.
  • the content of the aromatic tertiary amine polymer compound in the organic electroluminescent element composition of the present invention is usually 1% by weight or more, preferably 2% by weight or more, and usually 6% by weight or less, preferably 5%. % By weight or less. If the content of the aromatic tertiary amine polymer compound is too small, the charge transport ability may be insufficient.
  • the electron accepting compound is preferably a compound having an oxidizing power and the ability to accept one electron from the above hole injecting and transporting compound. Specifically, a compound having an electron affinity of 4 eV or more is preferable, and 5 eV. The compound which is the above compound is further more preferable.
  • electron-accepting compounds include triarylboron compounds, metal halides, Lewis acids, organic acids, onium salts, salts of arylamines and metal halides, and salts of arylamines and Lewis acids. Examples thereof include one or more compounds selected from the group.
  • the electron-accepting compound contained in the composition for organic electroluminescent elements of the present invention is a long-period periodic table (hereinafter referred to as a “periodic table” unless otherwise specified).
  • an element belonging to Groups 15 to 17 is preferably an ionic compound having a structure in which at least one organic group is bonded with a carbon atom, and further includes the following formulas (I-1) to (I- It is preferable that it is a compound represented by either of 3).
  • R 51 , R 61 and R 71 each independently represents an organic group bonded to D 1 to D 3 via a carbon atom
  • R 52 , R 62 , R 63 and R 72 to R 74 each independently represent a substituent. Two or more adjacent groups of R 51 to R 74 may be bonded to each other to form a ring.
  • the type of R 51 , R 61 and R 71 is not particularly limited as long as it does not impair the effects of the present invention as long as it is an organic group having a carbon atom at the bonding portion with D 1 to D 3 .
  • the organic group in the present invention is a group containing at least one carbon atom.
  • the molecular weights of R 51 , R 61 and R 71 are each a value including the substituent, and are usually 1000 or less, preferably 500 or less.
  • Preferable examples of R 51 , R 61 and R 71 include an alkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group from the viewpoint of delocalizing the positive charge.
  • an aromatic hydrocarbon ring group or an aromatic heterocyclic group is preferable because it delocalizes positive charges and is thermally stable.
  • the aromatic hydrocarbon ring group is a 5- or 6-membered monocyclic ring or a 2-5 condensed ring having one free valence, and a group that can delocalize a positive charge on the group.
  • a group that can delocalize a positive charge on the group can be mentioned.
  • Specific examples thereof include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring and fluorene ring having one free valence.
  • Examples of the aromatic heterocyclic group include a group having a single free valence, which is a 5- or 6-membered monocyclic ring or a 2-4 condensed ring, and a positive charge can be delocalized on the group. It is done. Specific examples thereof include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, a triazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free valence.
  • alkyl group examples include linear, branched, or cyclic alkyl groups having a carbon number of usually 1 or more and usually 12 or less, preferably 6 or less. Specific examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group and the like.
  • alkenyl group include those having usually 2 or more, usually 12 or less, preferably 6 or less. Specific examples include vinyl group, allyl group, 1-butenyl group and the like.
  • alkynyl group examples include those having usually 2 or more, usually 12 or less, preferably 6 or less. Specific examples include ethynyl group and propargyl group.
  • the types of R 52 , R 62 , R 63 and R 72 to R 74 are not particularly limited as long as the effects of the present invention are not impaired.
  • the molecular weights of R 52 , R 62 , R 63 and R 72 to R 74 are each a value including the substituent, and are usually 1000 or less, preferably 500 or less.
  • R 52 , R 62 , R 63 and R 72 to R 74 include a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, an amino group, an alkoxy group, Aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, alkylthio group, arylthio group, sulfonyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, cyano group, hydroxyl group, thiol group, A silyl group etc. are mentioned.
  • an organic group having a carbon atom at the bond portion with D 1 to D 3 is preferable from the viewpoint of high electron acceptability.
  • examples thereof include an alkyl group, an alkenyl group, Alkynyl groups, aromatic hydrocarbon ring groups, and aromatic heterocyclic groups are preferred.
  • an aromatic hydrocarbon ring group or an aromatic heterocyclic group is preferable because it has a large electron accepting property and is thermally stable.
  • Examples of the alkyl group, alkenyl group, alkynyl group, aromatic hydrocarbon ring group and aromatic heterocyclic group are the same as those described above for R 51 , R 61 and R 31 .
  • Examples of the amino group include an alkylamino group, an arylamino group, and an acylamino group.
  • Examples of the alkylamino group include alkylamino groups having one or more alkyl groups usually having 1 or more carbon atoms and usually 12 or less, preferably 6 or less carbon atoms. Specific examples include methylamino group, dimethylamino group, diethylamino group, dibenzylamino group and the like.
  • arylamino group an arylamino group having at least one aromatic hydrocarbon ring group or aromatic heterocyclic group having usually 3 or more, preferably 4 or more, and usually 25 or less, preferably 15 or less is used.
  • arylamino group includes an acylamino group having one or more acyl groups having usually 2 or more carbon atoms and usually 25 or less, preferably 15 or less carbon atoms.
  • acetylamino group and a benzoylamino group include an acetylamino group and a benzoylamino group.
  • the alkoxy group includes an alkoxy group having usually 1 or more carbon atoms and usually 12 or less, preferably 6 or less. Specific examples include a methoxy group, an ethoxy group, and a butoxy group.
  • the aryloxy group include an aryloxy group having an aromatic hydrocarbon ring group or an aromatic heterocyclic group having usually 3 or more, preferably 4 or more, and usually 25 or less, preferably 15 or less. Specific examples include phenyloxy group, naphthyloxy group, pyridyloxy group, thienyloxy group and the like.
  • acyl group examples include acyl groups having usually 1 or more carbon atoms and usually 25 or less, preferably 15 or less. Specific examples include formyl group, acetyl group, benzoyl group and the like.
  • the alkoxycarbonyl group includes an alkoxycarbonyl group having usually 2 or more carbon atoms and usually 10 or less, preferably 7 or less. Specific examples include a methoxycarbonyl group and an ethoxycarbonyl group.
  • Examples of the aryloxycarbonyl group include those having an aromatic hydrocarbon ring group or aromatic heterocyclic group having usually 3 or more, preferably 4 or more, and usually 25 or less, preferably 15 or less. Specific examples include a phenoxycarbonyl group and a pyridyloxycarbonyl group.
  • Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having usually 2 or more carbon atoms and usually 10 or less, preferably 7 or less. Specific examples include an acetoxy group and a trifluoroacetoxy group.
  • the alkylthio group includes an alkylthio group having usually 1 or more carbon atoms and usually 12 or less, preferably 6 or less. Specific examples include a methylthio group and an ethylthio group.
  • the arylthio group includes an arylthio group having usually 3 or more, preferably 4 or more, and usually 25 or less, preferably 14 or less. Specific examples include a phenylthio group, a naphthylthio group, and a pyridylthio group.
  • alkylsulfonyl group and the arylsulfonyl group include a mesyl group and a tosyl group.
  • Specific examples of the sulfonyloxy group include a mesyloxy group and a tosyloxy group.
  • Specific examples of the silyl group include a trimethylsilyl group and a triphenylsilyl group.
  • R 51 , R 61 , R 71 and R 52 , R 62 , R 63 , R 72 to R 74 are further substituted with other substituents unless they are contrary to the spirit of the present invention. May be.
  • the type of the substituent is not particularly limited, and examples include R 51 , R 61 , R 71 and R 52 , R 62 , R 63 , R 72 to R 74, as well as halogen atoms, cyano Group, thiocyano group, nitro group and the like.
  • an alkyl group an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aromatic hydrocarbon ring group, an aromatic complex A cyclic group is preferred.
  • D 1 and D 2 are elements from the third period of the periodic table (specifically, the third to sixth periods), and D 3 is the second element in the periodic table. Elements after the period (specifically, the second to sixth periods), wherein D 1 represents an element belonging to Group 17 of the long-period periodic table, and D 2 represents an element belonging to Group 16 D 3 represents an element belonging to Group 15. Among these, from the viewpoint of electron acceptability and availability, elements before the fifth period of the periodic table are preferable.
  • D 1 is preferably any one of an iodine atom, a bromine atom, and a chlorine atom
  • D 2 is preferably any one of a tellurium atom, a selenium atom, and a sulfur atom
  • D 3 is preferably an antimony atom, an arsenic atom, Either a phosphorus atom or a nitrogen atom is preferable.
  • D 1 in the formula (I-1) is a bromine atom or iodine atom
  • D 2 in the formula (I-2) is a selenium atom or sulfur.
  • An electron-accepting compound that is an atom, and an electron-accepting compound in which D 3 in the formula (I-3) is a nitrogen atom are preferable.
  • an electron-accepting compound in which D 1 in the formula (I-1) is an iodine atom is an electron-accepting compound in which D 3 in formula (I-3) is a nitrogen atom.
  • Z 1 n1 to Z 3 n3 each independently represent a counter anion.
  • the type of the counter anion is not particularly limited, and may be a monoatomic ion or a complex ion. However, the larger the size of the counter anion, the more the negative charge is delocalized, and the positive charge is also delocalized thereby increasing the electron accepting ability. Therefore, the complex ion is preferable to the monoatomic ion.
  • n 1 to n 3 are each independently an arbitrary positive integer corresponding to the ionic value of the counter anion Z 1 n1 to Z 3 n3 .
  • the values of n 1 to n 3 are not particularly limited, but all are preferably 1 or 2, and most preferably 1.
  • Z 1 n1- to Z 3 n3- include hydroxide ions, fluoride ions, chloride ions, bromide ions, iodide ions, cyanide ions, nitrate ions, nitrite ions, sulfate ions, sulfite ions.
  • the counter anions Z 1 n1 to Z 3 n3 are represented by any one of the following formulas (I-4) to (I-6) from the viewpoint of the stability of the compound and the solubility in organic solvents.
  • the complex ions represented by formula (I-6) are preferable because the negative charges are delocalized and the positive charges are delocalized to increase the electron accepting ability. Ions are more preferred.
  • E 1 and E 3 each independently represent an element belonging to Group 13 of the long-period periodic table.
  • a boron atom, an aluminum atom, and a gallium atom are preferable, and a boron atom is preferable from the viewpoint of stability of the compound and ease of synthesis and purification.
  • E 2 represents an element belonging to Group 15 of the long-period periodic table.
  • a phosphorus atom, an arsenic atom, and an antimony atom are preferable, and a phosphorus atom is preferable from the viewpoint of stability of the compound, synthesis and purification, and toxicity.
  • Q 4 and Q 6 represent a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom, from the viewpoint that the stability, synthesis, and purification of the compound are easy. , A fluorine atom or a chlorine atom is preferable, and a fluorine atom is most preferable.
  • Ar 61 to Ar 64 each independently represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group. Examples of the aromatic hydrocarbon ring group and the aromatic heterocyclic group include a 5- or 6-membered ring having one free valence similar to those exemplified above for R 51 , R 61 and R 71 .
  • a single ring or a 2-4 condensed ring may be mentioned.
  • a benzene ring, naphthalene ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring and isoquinoline ring having one free valence are preferable from the viewpoint of stability and heat resistance of the compound. .
  • aromatic hydrocarbon ring group and aromatic heterocyclic group exemplified as Ar 61 to Ar 64 may be further substituted with another substituent, as long as not departing from the spirit of the present invention.
  • the type of the substituent is not particularly limited, and any substituent can be applied, but an electron-withdrawing group is preferable.
  • Examples of preferable electron-withdrawing groups as the substituent that Ar 61 to Ar 64 may have include halogen atoms such as fluorine atom, chlorine atom and bromine atom; cyano group; thiocyano group; nitro group; mesyl group Alkylsulfonyl groups such as tosyl group; arylsulfonyl groups such as tosyl group; acyl groups such as formyl group, acetyl group, benzoyl group and the like, usually having 1 or more, usually 12 or less, preferably 6 or less; methoxycarbonyl group, ethoxycarbonyl An alkoxycarbonyl group having 2 or more carbon atoms, usually 10 or less, preferably 7 or less; a phenoxycarbonyl group, a pyridyloxycarbonyl group or the like, and usually having 3 or more carbon atoms, preferably 4 or more and usually 25 or less.
  • halogen atoms such as fluorine
  • At least one group out of Ar 61 to Ar 64 has one or two or more fluorine atoms or chlorine atoms as substituents.
  • it is most preferably a perfluoroaryl group in which all of the hydrogen atoms of Ar 61 to Ar 64 are substituted with fluorine atoms from the viewpoint of efficiently delocalizing negative charges and having an appropriate sublimation property.
  • the perfluoroaryl group include a pentafluorophenyl group, a heptafluoro-2-naphthyl group, and a tetrafluoro-4-pyridyl group.
  • the molecular weight of the electron-accepting compound in the present invention is usually 100 or more, preferably 300 or more, more preferably 400 or more, and usually 5000 or less, preferably 3000 or less, more preferably 2000 or less. If the molecular weight of the electron-accepting compound is too small, delocalization of the positive charge and negative charge is insufficient, which may reduce the electron accepting ability. If the molecular weight of the electron-accepting compound is too large, the electron accepting compound The active compound itself may interfere with charge transport.
  • A-1 to 48, A-54, A-55, A-60 to 62, and A-64 to 75 are preferred in view of electron acceptability, heat resistance, and solubility in organic solvents.
  • the method for producing the electron-accepting compound described above is not particularly limited, and can be produced using various methods. As an example, Chem. Rev. 66, 243, 1966, and J. Am. Org. Chem. 53, page 5571, 1988, and the like.
  • the composition for organic electroluminescent elements of the present invention may contain any one of the above-described electron-accepting compounds alone, or may contain two or more kinds in any combination and ratio. Further, two or more electron-accepting compounds corresponding to any one of formulas (I-1) to (I-3) may be combined, and two or more electron-accepting compounds each corresponding to a different formula You may combine a compound.
  • a compound represented by the following formula (3) is particularly preferably used as the electron-accepting compound.
  • the content of the above-described electron-accepting compound in the composition for organic electroluminescent elements of the present invention is usually 0.1% by weight or more, preferably 1% by weight or more, based on the value of the above-described aromatic tertiary amine polymer compound. Moreover, it is 100 weight% or less normally, Preferably it is 40 weight% or less. If the content of the electron-accepting compound is too small, the driving voltage may increase. If the content of the electron-accepting compound is too large, the film forming property may be deteriorated. When two or more kinds of electron-accepting compounds are used in combination, the total content is included in the above range.
  • Particles Particles are dispersed in the hole injection / transport layer of the present invention. It is preferable that the particles have a small light absorption in the light emission wavelength region of the light emitting element, and more preferably have no light absorption.
  • the dispersed particles can be selected from metal oxides, composite oxides, and polymer materials.
  • Examples of the metal oxide include titanium oxide, zinc oxide, silicon oxide, aluminum oxide, zirconium oxide, cerium oxide, tin oxide, copper oxide, silver oxide, iron oxide, bismuth oxide, tungsten oxide, indium oxide, manganese oxide, Examples thereof include vanadium oxide, niobium oxide, strontium titanate, and barium titanate.
  • Examples of the composite oxide include indium-tin oxide (ITO), aluminum-zinc oxide (AZO), and gallium-zinc oxide (GZO).
  • the raw material, a manufacturing method, etc. are not specifically limited.
  • the metal oxide particles may be surface-treated.
  • a surface treatment agent is added to the metal oxide particle powder, and the mixture is uniformly mixed using a ball mill, a bead mill, a kneader or the like, or a heat treatment is used in combination.
  • Examples include a method of adsorbing a surface treatment agent on oxide particles or chemically bonding the surface treatment agent.
  • the chemical species introduced by the surface treatment include inorganic oxides such as aluminum hydroxide, silica and zirconium oxide, organic acids such as stearic acid, inorganic acids such as phosphoric acid, and silicone.
  • the polymer material examples include acrylic resin, polystyrene resin, polyurethane resin, and melamine resin.
  • the spherical particles of these polymer materials are commercially available and can be easily obtained.
  • the hole injecting / transporting layer is formed by a wet film forming method, it is more preferably a cross-linked polymer material having excellent resistance to dissolution in a dispersion medium.
  • polymer material particles for example, functional fine particles “trade name: Chemisnow” manufactured by Soken Chemical Co., Ltd., true spherical fine particle polymers “trade name: Techpolymer” manufactured by Sekisui Plastics Co., Ltd., Nissan Chemical Co., Ltd. Examples thereof include spherical resin fine particles “trade name: Opt Beads”, “trade name: Hypertec”, “trade name: Trepearl” manufactured by Toray Industries, Inc., and the like.
  • ⁇ Refractive index Although the scattering performance can be obtained even if the refractive index of the particles is higher or lower than the refractive index of the hole injection / transport compound (approximately 1.65 to 1.7), the hole injection has high scattering performance.
  • the refractive index of the particles has a difference of 0.05 or more, particularly 0.10 or more, and particularly 0.20 or more with respect to the refractive index of the hole injecting and transporting compound. Further, when the refractive index of the hole injection / transport layer is higher than the refractive index of the light emitting layer (approximately 1.7), loss due to total reflection at the interface does not occur. Higher is preferable.
  • the refractive index of the particles is preferably higher than the refractive index of the hole injecting and transporting compound itself, and the refractive index of the particles is 1.70 or more, more preferably 1.75 or more, still more preferably 1.85 or more, most Preferably it is 2.00 or more.
  • the particles are particularly preferably titanium oxide, barium titanate, zinc oxide, zirconium oxide, cerium oxide, tin oxide, and ITO.
  • the particles of the present invention may be either primary particles or secondary particles, and the average particle size of the particles is 10 nm to 300 nm, preferably 50 to 250 nm, more preferably 100 to 200 nm.
  • the average particle diameter in the present invention is a value measured by a dynamic light scattering method.
  • particles may be mixed singly with the hole injection / transport layer molding composition, or two or more kinds of particles may be mixed.
  • the mixing ratio of the hole injecting / transporting compound and the particles is not particularly limited and can be arbitrarily selected.
  • the solids weight ratio of the hole injecting and transporting compound to the particles is preferably 95: 5 to 20:80, more preferably 90:10 to 25:75, and still more preferably 80:20 to 30:70.
  • the solid content weight ratio of the particles is 5 or more, sufficient scattering performance can be obtained, and when it is 80 or less, the hole injection / transport layer can have sufficient conductivity.
  • the surface of the particle or the surface of the primary particle included in the secondary particle may be covered with a dispersant.
  • the weight of the particle may include the weight of the dispersant covering the particle. Good.
  • the particles may be mixed and dispersed with powder, or may be dispersed in a suitable solvent in advance and then mixed as a particle dispersion. Since it is easy to uniformly mix and disperse with the hole injection / transport layer forming composition, a method of mixing after preparing a particle dispersion in advance is more preferable.
  • a method for preparing the particle dispersion generally, a solvent and particles, and if necessary, a dispersant and beads for pulverization are mixed in advance so that the solid content concentration is 5 to 70% by weight, followed by dispersion treatment. A particle dispersion is prepared.
  • any dispersion method using an ultrasonic disperser, a sand mill, an attritor, a dyno mill, a bead mill, a ball mill, a fluidizer, a high speed mixer, a homogenizer, a dispersion method using a paint shaker, or the like can be used. Can do.
  • a low molecular dispersant or a high molecular dispersant that is usually marketed as a dispersant.
  • a polymer dispersant from the viewpoint of dispersion stability of particles in the hole injection / transport layer molding composition.
  • the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester. And the like, and the like.
  • dispersants can be used alone or in admixture of two or more.
  • the content of the dispersant with respect to the particles is preferably 0.1 to 50% by weight, more preferably 0.5 to 35% by weight, still more preferably 1 to 30% by weight, Most preferred is 2 to 25% by weight. If the content ratio of the dispersant to the particles is less than 0.1% by weight, the dispersion stability of the particles in the dispersion may be deteriorated, and if it exceeds 50% by weight, the hole mobility of the hole injection / transport layer may be decreased. There is a risk of lowering.
  • a dispersant that destabilizes the above-mentioned cation radical compound should not be used.
  • a dispersant having an amino group or an ammonium cation group is used in combination with a system in which an aromatic tertiary amine polymer compound is cation radicalized with 4-isopropyl-4-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate
  • the cation radicals are gradually lost, the conductivity of the hole injection / transport layer is lowered, and as a result, the drive voltage of the organic electroluminescence device is increased.
  • a material that usually becomes a hole injection / transport layer that is, a material comprising a hole-injection / transport compound and particles in the present invention
  • a film-forming composition hole injection / transport layer forming composition
  • the layer forming composition is applied on a layer (usually an anode) corresponding to the lower layer of the hole injection layer, formed into a film, and then dried.
  • the layer can be appropriately formed by a known vapor deposition method.
  • the concentration of the hole injecting / transporting compound in the composition for forming a hole injecting / transporting layer and the concentration of the solids combined with the hole injecting / transporting compound and the particles are arbitrary as long as the effects of the present invention are not significantly impaired.
  • the lower one is preferable.
  • the higher one is preferable in that a defect is hardly generated in the hole injection / transport layer and a thick film is easily obtained.
  • it is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, particularly preferably 0.5% by weight or more, and on the other hand, 70% by weight. It is preferably not more than 60% by weight, more preferably not more than 60% by weight, particularly preferably not more than 50% by weight.
  • the film thickness of the hole injection / transport layer of the present invention is 100 nm or more and 1000 nm or less.
  • the hole injection / transport layer of a general organic electric field element is thicker than several tens of nanometers, in the present invention, in order to obtain the film thickness, it may be formed by one coating or repeated coating. It is a feature that it may be formed.
  • the hole injecting / transporting compound preferably has a crosslinkable group. In the case of having a crosslinkable group, the hole injecting / transporting compound is cross-linked by heating and drying after coating to improve the solvent resistance. The film can be efficiently increased without dissolving and decreasing. Moreover, since the particles are fixed in the coating film in a uniformly dispersed state by crosslinking, the problem that the particles aggregate and phase separate from the hole injecting and transporting compound can be avoided.
  • the hole injecting / transporting layer-containing composition containing no particles may be overcoated on the hole injecting / transporting layer containing particles.
  • the surface flatness of the hole injection / transport layer containing particles may be inferior, the surface flatness of the hole injection / transport layer can be improved by this method, and the hole injection / transport layer is in contact with the hole transport layer or the light emitting layer. The effect of improving the hole injection performance near the surface is expected.
  • the solvent for the hole injection / transport layer forming composition is selected from those that can dissolve the hole injection / transport compound and can stably disperse the particles.
  • the particle dispersion and the hole injection / transport compound solution are:
  • the use of the same solvent species is preferable in terms of storage stability of the composition for forming a hole injection / transport layer.
  • the solvent include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, and the like.
  • ether solvents include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA), 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, and anisole. , Aromatic ethers such as phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole and 2,4-dimethylanisole.
  • aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA), 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, and anisole.
  • Aromatic ethers such as phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-
  • ester solvent examples include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.
  • aromatic hydrocarbon solvent examples include toluene, xylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, cyclohexylbenzene, methylnaphthalene and the like. It is done.
  • amide solvent examples include N, N-dimethylformamide and N, N-dimethylacetamide.
  • the coating solution is used for coating after being filtered through a filter to remove fine dust and insoluble substances.
  • the composition for forming a hole injection / transport layer of the present invention is a coating liquid containing particles, the composition may not pass depending on the aperture size of the filter filter. In that case, a method of preparing a composition for forming a hole injection / transport layer by filtering the particle dispersion and the solution of the hole injection / transport compound with a filter having a suitable aperture size and then mixing them. It is good to take.
  • the viscosity of the composition for forming a hole injection / transport layer is about 0.5 mPa ⁇ s to 500 mPa ⁇ s from the viewpoint of coatability.
  • Formation of a hole injection / transport layer by a wet film formation method is usually performed after preparing a composition for forming a hole injection / transport layer, and this is a layer corresponding to a lower layer of a hole injection / transport layer (usually, The coating is performed on the anode) and dried.
  • the hole injection / transport layer is usually dried by heating, drying under reduced pressure, or the like after film formation.
  • the hole injection / transport layer may be cross-linked.
  • coating methods include spin coating, dip coating, die coating, bar coating, blade coating, roll coating, spray coating, capillary coating, nozzle coating, ink jet, screen printing, and gravure.
  • Known methods such as a printing method and a flexographic printing method can be used.
  • a spin coat method, a die coat method, and a dip coat method are preferred because surface flatness is easy to obtain and simple.
  • the film thickness generally does not exceed 100 nm.
  • the present inventor has unexpectedly found that when the particles are dispersed in the aromatic amine, the light extraction efficiency is improved by setting the film thickness to 100 nm or more.
  • the substrate serves as a support for the organic electroluminescent element, and usually a quartz or glass plate, a metal plate or a metal foil, a plastic film or a sheet is used. Of these, glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferable.
  • the substrate is preferably made of a material having a high gas barrier property since the organic electroluminescence device is hardly deteriorated by the outside air. For this reason, in particular, when a material having a low gas barrier property such as a synthetic resin substrate is used, it is preferable to provide a dense silicon oxide film or the like on at least one surface of the substrate to improve the gas barrier property.
  • the anode has a function of injecting holes into the layer on the light emitting layer side.
  • the anode is usually a metal such as aluminum, gold, silver, nickel, palladium, or platinum; a metal oxide such as an oxide of indium and / or tin; a metal halide such as copper iodide; a carbon black and a poly (3- Methylthiophene), polypyrrole, polyaniline and other conductive polymers.
  • the anode is usually formed by a dry method such as a sputtering method or a vacuum evaporation method.
  • an appropriate binder resin solution is used. It can also be formed by dispersing and coating on a substrate.
  • a conductive polymer a thin film can be directly formed on a substrate by electrolytic polymerization, or an anode can be formed by applying a conductive polymer on a substrate (Appl. Phys. Lett., 60). Volume, 2711, 1992).
  • the anode usually has a single layer structure, but may have a laminated structure as appropriate.
  • different conductive materials may be laminated on the first anode.
  • the thickness of the anode may be determined according to required transparency and material. In particular, when high transparency is required, a thickness at which visible light transmittance is 60% or more is preferable, and a thickness at which 80% or more is more preferable.
  • the thickness of the anode is usually 5 nm or more, preferably 10 nm or more, and is usually 1000 nm or less, preferably 500 nm or less.
  • the thickness of the anode may be arbitrarily set according to the required strength, and in this case, the anode may have the same thickness as the substrate.
  • the light-emitting layer is a layer that has a function of emitting light when excited by recombination of holes injected from the anode and electrons injected from the cathode when an electric field is applied between the pair of electrodes.
  • the light emitting layer is a layer formed between the anode and the cathode, and the light emitting layer is formed between the hole injection / transport layer and the cathode when there is a hole injection / transport layer on the anode, When there is a hole transport layer on the anode, it is formed between the hole transport layer and the cathode.
  • the thickness of the light emitting layer is arbitrary as long as the effects of the present invention are not significantly impaired. However, a thicker layer is preferable from the viewpoint that defects are unlikely to occur in the film, and a thinner layer is preferable from the viewpoint that a low driving voltage can be easily obtained. For this reason, it is preferably 3 nm or more, more preferably 5 nm or more, and on the other hand, it is usually preferably 200 nm or less, and more preferably 100 nm or less.
  • the light emitting layer contains at least a material having a light emitting property (light emitting material) and preferably contains a material having a charge transporting property (charge transporting material).
  • Luminescent material The light emitting material emits light at a desired light emission wavelength, and is not particularly limited as long as the effect of the present invention is not impaired, and a known light emitting material can be applied.
  • the light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, but a material having good light emission efficiency is preferable, and a phosphorescent light emitting material is preferable from the viewpoint of internal quantum efficiency.
  • Examples of the fluorescent light emitting material include the following materials.
  • Examples of the fluorescent light emitting material that gives blue light emission include naphthalene, perylene, pyrene, anthracene, coumarin, chrysene, p-bis (2-phenylethenyl) benzene, and derivatives thereof.
  • Examples of the fluorescent light emitting material that gives green light emission include quinacridone derivatives, coumarin derivatives, aluminum complexes such as Al (C 9 H 6 NO) 3, and the like.
  • fluorescent light-emitting material that gives yellow light
  • examples of fluorescent light-emitting materials include rubrene and perimidone derivatives.
  • fluorescent light-emitting materials red fluorescent light-emitting materials
  • DCM dimethyl-6- (p-dimethylaminostyryl) -4H-pyran
  • benzopyran derivatives rhodamine derivatives.
  • Benzothioxanthene derivatives azabenzothioxanthene and the like.
  • examples of the phosphorescent material include organometallic complexes containing a metal selected from Groups 7 to 11 of the long-period periodic table.
  • Preferred examples of the metal selected from Groups 7 to 11 of the periodic table include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold.
  • a ligand in which a (hetero) aryl group such as a (hetero) arylpyridine ligand or (hetero) arylpyrazole ligand and a pyridine, pyrazole, phenanthroline, or the like is connected is preferable.
  • a phenylpyridine ligand and a phenylpyrazole ligand are preferable.
  • (hetero) aryl represents an aryl group or a heteroaryl group.
  • Specific preferred phosphorescent materials include, for example, tris (2-phenylpyridine) iridium, tris (2-phenylpyridine) ruthenium, tris (2-phenylpyridine) palladium, bis (2-phenylpyridine) platinum, tris And phenylpyridine complexes such as (2-phenylpyridine) osmium and tris (2-phenylpyridine) rhenium, and porphyrin complexes such as octaethylplatinum porphyrin, octaphenylplatinum porphyrin, octaethylpalladium porphyrin, and octaphenylpalladium porphyrin.
  • Polymeric light-emitting materials include poly (9,9-dioctylfluorene-2,7-diyl), poly [(9,9-dioctylfluorene-2,7-diyl) -co- (4,4′- (N- (4-sec-butylphenyl)) diphenylamine)], poly [(9,9-dioctylfluorene-2,7-diyl) -co- (1,4-benzo-2 ⁇ 2,1'-3 ⁇ -Triazole)], and polyphenylene vinylene materials such as poly [2-methoxy-5- (2-hexylhexyloxy) -1,4-phenylene vinylene].
  • the charge transport material is a material having a positive charge (hole) or negative charge (electron) transport property, and is not particularly limited as long as the effect of the present invention is not impaired, and a known light emitting material can be applied.
  • a compound or the like conventionally used in a light emitting layer of an organic electroluminescence device can be used, and a compound used as a host material of the light emitting layer is particularly preferable.
  • charge transporting materials include aromatic amine compounds, phthalocyanine compounds, porphyrin compounds, oligothiophene compounds, polythiophene compounds, benzylphenyl compounds, and compounds in which tertiary amines are linked by a fluorene group. , Hydrazone compounds, silazane compounds, silanamine compounds, phosphamine compounds, quinacridone compounds, and the like, examples of the hole injection / transport compound in the hole injection / transport layer include anthracene compounds, pyrene And electron transporting compounds such as benzene compounds, carbazole compounds, pyridine compounds, phenanthroline compounds, oxadiazole compounds, and silole compounds.
  • two or more condensed aromatic rings including two or more tertiary amines represented by 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl are substituted with nitrogen atoms.
  • Aromatic amine compounds having a starburst structure such as aromatic diamines (Japanese Patent Laid-Open No. 5-234681), 4,4 ′, 4 ′′ -tris (1-naphthylphenylamino) triphenylamine (J Lumin., 72-74, 985, 1997), an aromatic amine compound composed of a tetramer of triphenylamine (Chem.
  • 2- (4-biphenyl) -5- (p-tertiarybutylphenyl) -1,3,4-oxadiazole tBu-PBD
  • 2,5-bis (1-naphthyl)- Oxadiazole compounds such as 1,3,4-oxadiazole (BND)
  • Examples thereof include silole compounds such as diphenylsilole (PyPySPyPy) and phenanthroline compounds such as bathophenanthroline (BPhen) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP, bathocuproin).
  • the method for forming the light emitting layer may be a vacuum deposition method or a wet film formation method, but a wet film formation method is preferable and a spin coating method and an ink jet method are more preferable because of excellent film forming properties.
  • a wet film formation method it is usually the same as the case of forming the hole injection / transport layer described above by a wet film formation method, instead of the hole injection / transport layer forming composition.
  • the material for forming the light emitting layer is formed using a composition for forming a light emitting layer prepared by mixing a soluble solvent (solvent for the light emitting layer).
  • the solvent examples include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, alkane solvents, halogenated aromatic hydrocarbon solvents, and the like mentioned for the formation of the hole injection / transport layer, Examples thereof include aliphatic alcohol solvents, alicyclic alcohol solvents, aliphatic ketone solvents, and alicyclic ketone solvents. Although the specific example of a solvent is given to the following, as long as the effect of this invention is not impaired, it is not limited to these.
  • aliphatic ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2 -Aromatic ether solvents such as methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole, diphenyl ether; phenyl acetate, phenyl propionate, methyl benzoate, benzoic acid Aromatic ester solvents such as ethyl, ethyl benzoate, propyl benzoate, n-butyl benzoate; toluene, xylene, methicylene, cyclohexylbenzene, tetralin, 3-ilopropylb
  • a hole blocking layer may be provided between the light emitting layer and an electron injection layer described later.
  • the hole blocking layer is a layer stacked on the light emitting layer so as to be in contact with the cathode side interface of the light emitting layer.
  • the hole blocking layer has a role of blocking holes moving from the anode from reaching the cathode and a role of efficiently transporting electrons injected from the cathode toward the light emitting layer.
  • the physical properties required for the material constituting the hole blocking layer include high electron mobility, low hole mobility, large energy gap (difference between HOMO and LUMO), and excited triplet level (T1). It is expensive.
  • Examples of the hole blocking layer material satisfying such conditions include bis (2-methyl-8-quinolinolato) (phenolato) aluminum, bis (2-methyl-8-quinolinolato) (triphenylsilanolato) aluminum, and the like.
  • Mixed ligand complexes of, such as metal complexes such as bis (2-methyl-8-quinolato) aluminum- ⁇ -oxo-bis- (2-methyl-8-quinolinato) aluminum binuclear metal complexes, distyryl biphenyl derivatives, etc.
  • Triazole derivatives such as styryl compounds (Japanese Patent Laid-Open No.
  • a hole-blocking layer there is no restriction
  • the thickness of the hole blocking layer is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.3 nm or more, preferably 0.5 nm or more, and is usually 100 nm or less, preferably 50 nm or less. .
  • the electron transport layer is provided between the light emitting layer and the electron injection layer for the purpose of further improving the current efficiency of the device.
  • the electron transport layer is formed of a compound capable of efficiently transporting electrons injected from the cathode between the electrodes to which an electric field is applied in the direction of the light emitting layer.
  • the electron transporting compound used in the electron transporting layer is a compound that has high electron injection efficiency from the cathode or the electron injection layer and has high electron mobility and can efficiently transport injected electrons. It is necessary.
  • the electron transporting compound used for the electron transporting layer is usually preferably a compound that has high electron injection efficiency from the cathode or the electron injection layer and can efficiently transport the injected electrons.
  • the electron transporting compound include metal complexes such as an aluminum complex of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), a metal complex of 10-hydroxybenzo [h] quinoline, Oxadiazole derivatives, distyrylbiphenyl derivatives, silole derivatives, 3-hydroxyflavone metal complexes, 5-hydroxyflavone metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, trisbenzimidazolylbenzene (US Pat. No.
  • the film thickness of the electron transport layer is usually 1 nm or more, preferably 5 nm or more, and is usually 300 nm or less, preferably 100 nm or less.
  • the electron transport layer is formed by laminating on the hole blocking layer by a wet film formation method or a vacuum deposition method in the same manner as described above. Usually, a vacuum deposition method is used.
  • the electron injection layer plays a role of efficiently injecting electrons injected from the cathode into the electron transport layer or the light emitting layer.
  • the material for forming the electron injection layer is preferably a metal having a low work function. Examples include alkali metals such as sodium and cesium, and alkaline earth metals such as barium and calcium.
  • the film thickness is usually preferably from 0.1 nm to 5 nm.
  • an organic electron transport material represented by a metal complex such as a nitrogen-containing heterocyclic compound such as bathophenanthroline or an aluminum complex of 8-hydroxyquinoline is doped with an alkali metal such as sodium, potassium, cesium, lithium, rubidium ( (Described in Japanese Laid-Open Patent Publication No. 10-270171, Japanese Laid-Open Patent Publication No. 2002-1000047, Japanese Laid-Open Patent Publication No. 2002-1000048, etc.), which improves electron injection / transport properties and achieves excellent film quality. It is preferable because it becomes possible.
  • the film thickness is usually in the range of 5 nm or more, preferably 10 nm or more, and usually 200 nm or less, preferably 100 nm or less.
  • the electron injection layer is formed by laminating on the light emitting layer or the hole blocking layer thereon by a wet film formation method or a vacuum deposition method. The details in the case of the wet film forming method are the same as those in the case of the light emitting layer described above.
  • the cathode plays a role of injecting electrons into a layer on the light emitting layer side (such as an electron injection layer or a light emitting layer).
  • a metal having a low work function for efficient electron injection for example, tin, magnesium, indium
  • metals such as calcium, aluminum, and silver, or alloys thereof are used.
  • Specific examples include low work function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy.
  • a cathode made of a metal having a low work function by laminating a metal layer having a high work function and stable to the atmosphere on the cathode.
  • the metal to be laminated include metals such as aluminum, silver, copper, nickel, chromium, gold, and platinum.
  • the thickness of the cathode is usually the same as that of the anode. (Other layers)
  • the organic electroluminescent element of the present invention may further have other layers as long as the effects of the present invention are not significantly impaired. That is, any other layer described above may be provided between the anode and the cathode.
  • ⁇ Other element configuration> it is also possible to laminate
  • the organic electroluminescent element of the present invention When the organic electroluminescent element of the present invention is applied to an organic electroluminescent device, it may be used as a single organic electroluminescent element, or may be used in a configuration in which a plurality of organic electroluminescent elements are arranged in an array, The anode and the cathode may be used in a configuration in which they are arranged in an XY matrix.
  • Organic EL Display Device uses the above-described organic electroluminescent element of the present invention.
  • the organic EL display device of the present invention can be obtained by the method described in “Organic EL display” (Ohm, published on Aug. 20, 2004, Shizushi Tokito, Chiba Adachi, Hideyuki Murata). Can be formed.
  • Organic EL lighting uses the organic electroluminescent element of the present invention described above. There is no restriction
  • the present invention will be described more specifically with reference to production examples, examples and comparative examples.
  • the present invention is not limited to the following examples unless it exceeds the gist.
  • the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. It may be a range defined by a combination of values of the following examples or values of the examples.
  • the average particle size of the scattering particle dispersion was measured using a concentrated particle size analyzer (FPAR-1000 type, dynamic light scattering method) manufactured by Otsuka Electronics Co., Ltd. 2. Measurement of Film Thickness and Surface Roughness Ra The film thickness of the hole injection layer was measured using a step / surface roughness / fine shape measuring device (“P-15 type”) manufactured by KLA-Tencor Japan. As the surface roughness, an arithmetic average roughness Ra between 2000 ⁇ m was measured.
  • Example 1> Preparation of organic electroluminescent element 1) Preparation of organic electroluminescent element (A1) of the present invention ⁇ Preparation of particle dispersion 1> In a glass bottle with a lid of 30 ml, 1.20 g of titanium oxide powder “TTO-55 (C)” (average primary particle size 30 to 50 nm) manufactured by Ishihara Sangyo Co., Ltd.
  • ethyl benzoate ethyl benzoate, hereinafter “ 4.74 g, 0.12 g of “DISPERBYK-111” dispersant manufactured by BYK-Chemie, and 20 g of 0.5 mm ⁇ zirconia beads were taken, sealed, and shaken for 4 hours with a paint shaker (PC type) manufactured by Iwata Tekko. Finally, distributed processing was performed. This dispersion was filtered through a 200 mesh steel net to remove zirconia beads to obtain a particle dispersion 1. The average particle size of this dispersion was 166 nm.
  • HIL-1 hole injecting / transporting compound having a repeating unit shown below and 4-isopropyl-4-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate are mixed at a weight ratio of 100: 20. Ethyl benzoate was added so that it might become 5.0 weight%, and it heated and dissolved, and prepared the hole injection transportable composition 1.
  • An organic electroluminescent element was produced by the following method. 1. Preparation of substrate A 70-nm-thick ITO film is formed as an anode on an alkali-free glass substrate (Nippon Electric Glass Co., Ltd. glass substrate “OA-10G”, thickness 0.7 mm) so that the light emitting area is 2 mm square. In addition, an ITO patterned (hereinafter referred to as a 2 mm square element ITO substrate) was prepared.
  • the hole injection layer coating solution 1 is spin-coated at 2000 rpm for 30 seconds on the ITO substrate, and is temporarily cured by heating in a clean oven at 230 ° C. for 10 minutes. It was. The film thickness at this time was 99 nm. Further, the hole injection layer coating solution 1 was spin-coated at 2500 rpm for 30 seconds on the temporarily cured coating film, and again heated at 230 ° C. for 10 minutes to be temporarily cured. After confirming that the film thickness reached the target value (about 150 nm), the film was heated at 230 ° C. for 1 hour to be fully cured. As a result, a hole injection layer having a thickness of 149 nm was formed.
  • Lithium fluoride Lithium fluoride (LiF) was deposited on the electron transport layer by a vacuum vapor deposition method so as to have a film thickness of 0.5 nm.
  • a cathode was formed by vapor deposition by vacuum vapor deposition. 6).
  • This counterbore glass is bonded to a glass substrate so as to cover the laminated body from the light extraction film to the cathode, and only the region where the photocurable resin is applied is irradiated with ultraviolet light to cure the resin. Then, an organic electroluminescent element was obtained.
  • a schematic diagram of an organic electroluminescent device prepared by the above method is shown in FIG.
  • a value obtained by dividing the total luminous flux of the organic electroluminescent device (A1) of the present invention by the total luminous flux of the comparative organic electroluminescent device (B1) using the hole injection layer not containing particles is “light extraction magnification”. Calculated as When the light extraction magnification exceeds 1.00, the light extraction effect is recognized.
  • the organic electroluminescence device of the present invention had a light extraction magnification of 1.36, and a light extraction effect was recognized.
  • Examples 2 to 3 The organic electroluminescent elements (A2) and (A3) of the present invention and the comparative elements (B2) and (B3) according to the method described in Example 1, with the target thicknesses of the hole injection layer being about 480 nm and about 600 nm, respectively.
  • the target thicknesses of the hole injection layer being about 480 nm and about 600 nm, respectively.
  • Table 14 even when the hole injection layer had the thickness, the organic electroluminescence devices (A2) and (A3) of the present invention were found to have a light extraction effect.
  • Example 4> ⁇ Preparation of hole injection layer coating solutions 2 to 8>
  • the particle dispersions shown in Table 15 below and the hole injection / transport composition 1 were mixed to prepare hole injection layer coating solutions 2 to 8.
  • the hole injection layer coating solution 2 to the hole injection layer coating solution 6 are a hole injection layer coating solution 7 and a hole injection layer coating solution in which the solid weight ratio of the hole injection transporting compound and the particles is 53:47.
  • 8 is a composition in which the hole injection / transport composition 1 and the particle dispersion are mixed so that the solid weight ratio of the hole injection / transport compound to the particles is 50:50, and the hole injection layer coating liquid 2 to 8 was prepared.
  • organic electroluminescent elements (A4-1 to A4-7) shown in Table 16 and a comparative element (B4) were prepared in the same procedure as in Example 1. did.
  • the organic electroluminescent elements (A4-1 to A4-7) of the present invention were found to have a light extraction effect in any case.
  • Example 5 ⁇ Preparation of the organic electroluminescent element (A5) of the present invention> An organic electroluminescent element was produced by the following method. 1. Production of Substrate with Opening Bank An ITO film having a thickness of 70 nm was formed as an anode on an alkali-free glass substrate (Nippon Electric Glass Co., Ltd. glass substrate “OA-10G”, thickness 0.7 mm).
  • a negative photosensitive resin solution was prepared, spin-coated with a negative photosensitive resin solution on the anode, and exposed to ultraviolet light through a light-shielding mask having an opening area of 6 mm ⁇ 6 mm.
  • the bank was baked in a 260 ° C. hot air oven for 1 hour to form an opening bank having a bank wall height of 1.4 ⁇ m and an opening area of 6 mm ⁇ 6 mm.
  • HIL-2 hole injecting / transporting compound having a repeating unit shown below and 4-isopropyl-4-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate are mixed at a weight ratio of 100 to 2, and the concentration of the mixture is Ethyl benzoate was added to 6.0 wt%, and the mixture was heated and dissolved to prepare a hole injection / transport composition 2.
  • ⁇ Preparation of hole injection layer coating solution 9> The particle dispersion 1 and the hole injecting / transporting composition 2 were mixed at a ratio in which the weight ratio of the solid content of the hole injecting / transporting compound and the particles was 50:50 to prepare a hole injecting layer coating solution 9.
  • a hole injection layer was formed by spin coating the hole injection layer coating solution 9 on the anode surrounded by the opening bank.
  • a 6 mm square organic electroluminescent element (A5) was produced according to the procedure of Example 1.
  • a schematic view of the organic electroluminescent device prepared by the above method is shown in FIG.
  • An organic electroluminescent element (A6) was produced in the same procedure as the production of the organic electroluminescent element (A5) except that the hole injection layer coating solution 1 shown in Table 15 was used in the hole injection layer forming step. Further, (B5) and (B6) are the same as in the production of the organic electroluminescent element (A5) except that the hole injection / transport compositions 2 and 1 are used in the step of forming the hole injection layer. Was made.
  • the light extraction effect was recognized in the element of the present invention. Further, it was confirmed from the comparison between Example 1 and Example 6 that the light extraction effect of the present invention is increased (size-dependent effect) when the light emission area is large.
  • Hole injection layer coating liquids 12 and 13 were prepared (both were mixed at a ratio in which the weight ratio of solid content of PEDOT / PSS and particles was 50:50).
  • the hole injection layer coating solutions 10 to 13, and “Clevios P VP AL4083” and “Clevios P VP CH8000” are each spin-coated on a 2 mm square ITO substrate and dried on a hot plate at 135 ° C. for 10 minutes. Thus, a hole injection layer was formed. Thereafter, organic electroluminescent elements (C1-1 to C2-2) outside the invention and comparative elements (D1, D2) were produced according to the procedure described in Example 1. Table 20 shows.
  • the light extraction magnification was 1.00 or less, and the light extraction effect was not recognized.
  • a particle dispersion 1-2 was prepared.
  • the average particle size of the dispersion at this time was 118 nm.
  • 25 parts by weight of this particle dispersion 1-2 and 100 parts by weight of the hole injection / transport composition 1 prepared in the same manner as in Example 1 were mixed to prepare a hole injection layer coating liquid 14.
  • the solids weight ratio of the hole injecting and transporting compound to the particles in this composition is 54:46.
  • the hole injection layer coating solution 14 was spin-coated at 1000 rpm for 30 seconds on the same substrate as used in Example 1, and immediately put in a vacuum dryer and dried under reduced pressure for 1 minute.
  • the hole injection layer coating solution 14 is spin-coated at 1500 rpm for 30 seconds, immediately put into a vacuum dryer and dried under reduced pressure for 1 minute, and then on a 230 ° C. hot plate for 10 minutes.
  • a cured coating film was formed by heating.
  • a hole injection layer having a thickness of 1570 nm was formed on the substrate.
  • a hole transport layer, a light emitting layer, an electron injection layer, and a cathode were formed and sealed to obtain an organic electroluminescent device (E1).
  • Example 6> 1 Preparation of organic electroluminescent element (G1) of the present invention ⁇ Preparation of hole injection / transport composition 3> A hole injecting and transporting compound (HIL-3) having a repeating unit shown below and 4-isopropyl-4-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate are mixed at a weight ratio of 100 to 2, and the concentration of the mixture is Ethyl benzoate was added so that it might become 5.0 weight%, and it heated and dissolved and prepared the hole injection transportable composition 3.
  • HIL-3 hole injecting and transporting compound having a repeating unit shown below and 4-isopropyl-4-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate
  • ⁇ Preparation of hole injection layer coating solution 15> The particle dispersion 1-2 and the hole injecting / transporting composition 3 are mixed at a ratio in which the weight ratio of the solid content of the hole injecting / transporting compound and the particles is 54 to 46 to obtain the hole injecting layer coating liquid 15 Prepared.
  • the hole injection layer coating solution 15 was spin-coated at 1000 rpm for 30 seconds on the same substrate as used in Example 1, and immediately put into a vacuum dryer and dried under reduced pressure for 1 minute. Subsequently, it heated for 10 minutes with a 230 degreeC hotplate, and the cured coating film was formed. The film thickness at this time was 330 nm.
  • the hole injection layer coating solution 15 is spin-coated at 1500 rpm for 30 seconds on this cured coating film, immediately put into a vacuum dryer and dried under reduced pressure for 1 minute, and then on a 230 ° C. hot plate for 10 minutes. A cured coating film was formed by heating. As described above, a hole injection layer having a thickness of 530 nm was formed on the substrate. On the hole injection layer, as in Example 1, a hole transport layer, a light emitting layer, an electron injection layer, and a cathode were formed and sealed to obtain an organic electroluminescent device (G1).
  • G1 organic electroluminescent device

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention a pour objectif de proposer un élément organique électroluminescent qui utilise une couche de transport/d'injection de trous de diffusion de lumière qui puisse être formée facilement par enduction ou similaire et qui soit dotée d'une excellente efficacité d'extraction de lumière. Un élément organique électroluminescent selon la présente invention comprend : une électrode positive ; une électrode négative ; et au moins une couche qui est formée entre l'électrode positive et l'électrode négative, et qui est sélectionnée entre une couche d'injection de trous et une couche de transport de trous. Des particules sont dispersées dans la ou les couches qui ont été sélectionnées entre une couche d'injection de trous et une couche de transport de trous ; et la ou les couches qui ont été sélectionnées entre une couche d'injection de trous et une couche de transport de trous ont une épaisseur comprise entre 100 nm et 1000 nm (inclus).
PCT/JP2013/080443 2012-11-12 2013-11-11 Élément organique électroluminescent, et procédé pour sa fabrication WO2014073683A1 (fr)

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JP2018081824A (ja) * 2016-11-16 2018-05-24 株式会社Ｊｏｌｅｄ 有機電界発光パネルの製造方法および有機電界発光パネル
JP2018528285A (ja) * 2015-07-17 2018-09-27 日産化学株式会社 有機エレクトロニクスにおける使用に適した半金属ナノ粒子を含有する非水系インク組成物
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JP2007042875A (ja) * 2005-08-03 2007-02-15 Fujifilm Holdings Corp 有機電界発光素子
WO2009141903A1 (fr) * 2008-05-21 2009-11-26 パイオニア株式会社 Elément électroluminescent organique
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JP2018528285A (ja) * 2015-07-17 2018-09-27 日産化学株式会社 有機エレクトロニクスにおける使用に適した半金属ナノ粒子を含有する非水系インク組成物
WO2017164158A1 (fr) * 2016-03-24 2017-09-28 日産化学工業株式会社 Dérivé d'arylamine et utilisation correspondante
JPWO2017164158A1 (ja) * 2016-03-24 2019-02-14 日産化学株式会社 アリールアミン誘導体とその利用
JP2018081824A (ja) * 2016-11-16 2018-05-24 株式会社Ｊｏｌｅｄ 有機電界発光パネルの製造方法および有機電界発光パネル
WO2019124415A1 (fr) 2017-12-20 2019-06-27 日産化学株式会社 Vernis de transport de charge

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