WO2015001726A1 - Organic electroluminescent element - Google Patents

Organic electroluminescent element Download PDF

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Publication number
WO2015001726A1
WO2015001726A1 PCT/JP2014/003169 JP2014003169W WO2015001726A1 WO 2015001726 A1 WO2015001726 A1 WO 2015001726A1 JP 2014003169 W JP2014003169 W JP 2014003169W WO 2015001726 A1 WO2015001726 A1 WO 2015001726A1
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group
substituted
unsubstituted
atom
substituent
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PCT/JP2014/003169
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French (fr)
Japanese (ja)
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紀昌 横山
秀一 林
直朗 樺澤
剛史 山本
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保土谷化学工業株式会社
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Priority to JP2014557916A priority Critical patent/JP5749870B1/en
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    • 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
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/302—Details of OLEDs of OLED structures
    • H10K2102/3023—Direction of light emission
    • H10K2102/3026—Top emission
    • 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
    • H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Definitions

  • the present invention relates to an organic electroluminescence element (hereinafter abbreviated as an organic EL element) which is a self-luminous element suitable for various display devices, and more particularly to an organic EL element using a specific arylamine compound.
  • the present invention relates to an organic EL element in which the light extraction efficiency is greatly improved.
  • the organic EL element is a self-luminous element, it has been actively researched because it is brighter and more visible than a liquid crystal element and can be clearly displayed.
  • a light emitting element having a top emission structure in which a metal having a high work function is used for an anode and light is emitted from the upper part has been used.
  • a light emitting element having a bottom emission structure in which the area of the light emitting part is limited by the pixel circuit, a light emitting element having a top emission structure has an advantage that a wide light emitting part can be obtained.
  • a semitransparent electrode such as LiF / Al / Ag (for example, see Non-Patent Document 2), Ca / Mg (for example, see Non-Patent Document 3), LiF / MgAg, or the like is used as a cathode.
  • the effect of the capping layer in the light emitting device having the top emission structure is that a light emitting device using Ir (ppy) 3 as a light emitting material has a current efficiency of 38 cd / A when there is no capping layer.
  • a light emitting device using Ir (ppy) 3 has a current efficiency of 38 cd / A when there is no capping layer.
  • an efficiency improvement of about 1.7 times as 64 cd / A was recognized.
  • the maximum point of transmittance and the maximum point of efficiency of the translucent electrode and the capping layer do not necessarily coincide with each other, and the maximum point of light extraction efficiency is determined by the interference effect. (For example, refer nonpatent literature 3).
  • a metal mask with high definition for the formation of the capping layer, but such a metal mask has a problem that the alignment accuracy is deteriorated due to thermal distortion. That is, ZnSe has a high melting point of 1100 ° C. or higher (see, for example, Non-Patent Document 3), and cannot be deposited at an accurate position with a high-definition mask. Many inorganic substances have high deposition temperatures and are not suitable for use with high-definition masks, and may damage the light-emitting elements themselves. Further, in the film formation by the sputtering method, the light emitting element is damaged, and therefore a capping layer containing an inorganic material cannot be used.
  • Alq 3 is a green light-emitting material or electron transport.
  • organic EL material generally used as a material, it has weak absorption in the vicinity of 450 nm used for a blue light emitting element. Therefore, in the case of a blue light emitting element, there is a problem that both the color purity is lowered and the light extraction efficiency is lowered.
  • JP-A-8-048656 Japanese Patent No. 3194657 WO2013-038627
  • the object of the present invention is to improve the device characteristics of the organic EL device, in particular, to greatly improve the light extraction efficiency, and has a high refractive index and excellent thin film stability and durability.
  • An object of the present invention is to provide an organic EL device having a capping layer made of a material that does not absorb in the wavelength regions of blue, green and red.
  • the physical properties of the capping layer material suitable for the present invention include (1) high refractive index, (2) vapor deposition and no thermal decomposition, (3) stable thin film state, 4) The glass transition temperature is high.
  • the physical characteristics of the element suitable for the present invention include (1) high light extraction efficiency, (2) no decrease in color purity, and (3) light transmission without change over time. (4) Long life can be mentioned.
  • the present inventors selected a specific arylamine compound having a high refractive index and capped the arylamine material, focusing on the excellent stability and durability of the thin film.
  • the present invention was completed.
  • the following organic EL elements are provided.
  • the capping layer is an arylamine compound represented by the following general formula (1)
  • An organic EL element including
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 may be the same or different from each other, and are substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted aromatic heterocyclic groups, substituted or unsubstituted Represents a substituted fused polycyclic aromatic group, and n represents an integer of 0 to 4.
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 is represented by the following structural formula (B) It is a monovalent group or has the monovalent group as a substituent.
  • R 1 , R 2 , R 3 and R 4 may be the same or different from each other, and may be a linking group, or a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group, substituent.
  • R 1 , R 2 , R 3 and R 4 may be the same or different from each other and have a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group or substituent.
  • An optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, and an optionally substituted carbon A linear or branched alkenyl group having 2 to 6 atoms, an optionally substituted linear or branched alkyloxy group having 1 to 6 carbon atoms, or a substituent.
  • R 1 , R 3 and R 4 may be the same or different from each other, and may have a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group or substituent.
  • R 3 and R 4 is a single bond, a substituted or unsubstituted methylene group, an oxygen atom, through a sulfur atom or N-Ar 8 may be bonded to each other to form a ring .
  • Ar 6, Ar 8 May be the same or different from each other, and each represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.
  • R 1 , R 2 , R 3 and R 4 may be the same or different from each other and have a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group or substituent.
  • An optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, and an optionally substituted carbon A linear or branched alkenyl group having 2 to 6 atoms, an optionally substituted linear or branched alkyloxy group having 1 to 6 carbon atoms, or a substituent.
  • R 1 , R 2 , R 3 and R 4 may be the same or different from each other and have a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group or substituent.
  • An optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, and an optionally substituted carbon A linear or branched alkenyl group having 2 to 6 atoms, an optionally substituted linear or branched alkyloxy group having 1 to 6 carbon atoms, or a substituent.
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 may be the same or different from each other, and may be a linking group, or a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group.
  • Ar 8 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, provided that Only one of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , Ar 5 , Ar 6 , Ar 7 is a linking group, X is a nitrogen atom, and Y is an oxygen atom Or except for the case of sulfur atoms.
  • any two of Ar 1 , Ar 2 , Ar 3 , Ar 4 are a monovalent group represented by the structural formula (B), or substituted for the monovalent group
  • the organic EL device according to 1) which is a group.
  • Ar 1 and Ar 4 are the monovalent group represented by the structural formula (B), or have the monovalent group as a substituent.
  • the organic EL element of description is the monovalent group represented by the structural formula (B), or have the monovalent group as a substituent.
  • Substituted or unsubstituted aromatic hydrocarbon group “substituted or unsubstituted aromatic heterocyclic group” represented by Ar 1 to Ar 4 in formula (1), or “substituted or unsubstituted condensed hydrocarbon group”
  • phenanthryl group fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyridyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, Indolyl group, carbazolyl group, benzotriazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group Benzimidazolyl group, a pyrazolyl group, and a dibenzofuranyl group, dibenzothienyl group, and carbolinyl group and the like.
  • Ar 1 and Ar 2 , or Ar 3 and Ar 4 may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or N—Ar 8 to form a ring.
  • N in “N—Ar 8 ” represents a nitrogen atom
  • Ar 8 represents “substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” or Examples of the “substituted or unsubstituted condensed polycyclic aromatic group” include the same groups as those exemplified above, and the substituents that these groups may have are also exemplified below. Substituents can be mentioned.
  • substituted aromatic hydrocarbon group “substituted aromatic heterocyclic group” or “substituted condensed polycyclic aromatic group” represented by Ar 1 to Ar 4 in the general formula (1), Specifically, deuterium atom, trifluoromethyl group, cyano group, nitro group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, a linear or branched alkyl group having 1 to 6 carbon atoms such as n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group; methyloxy group A linear or branched alkyloxy group having 1 to 6 carbon atoms such as ethyloxy group
  • N—Ar 8 means “substituted or unsubstituted aromatic hydrocarbon group” represented by Ar 1 to Ar 4 in the above general formula (1), “substituted or unsubstituted aromatic complex”. It means the same as “N—Ar 8 ” defined for “ring group” or “substituted or unsubstituted condensed polycyclic aromatic group”.
  • R 1 to R 8 A linear or branched alkyl group having 1 to 6 carbon atoms which may have ", a" cycloalkyl group having 5 to 10 carbon atoms which may have a substituent "or" a substituent.
  • “Straight or branched alkenyl group having 2 to 6 carbon atoms” which may have “straight or branched alkyl group having 1 to 6 carbon atoms”, “5 to 10 carbon atoms”
  • Specific examples of the cycloalkyl group or the linear or branched alkenyl group having 2 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Isobutyl group, tert-butyl group, n-pentyl group, isopentyl group , Neopentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-adamantyl group, vinyl group, allyl group, isopropenyl group and 2-butenyl group.
  • N—Ar 8 means “substituted or unsubstituted aromatic hydrocarbon group” represented by Ar 1 to Ar 4 in the above general formula (1), “substituted or unsubstituted aromatic complex”. It means the same as “N—Ar 8 ” defined for “ring group” or “substituted or unsubstituted condensed polycyclic aromatic group”.
  • “substituents” are represented by R 1 to R 8. Having a straight or branched alkyl group having 1 to 6 carbon atoms "," a cycloalkyl group having 5 to 10 carbon atoms having a substituent "or” straight chain having 2 to 6 carbon atoms having a substituent "
  • the “substituent” in the “like or branched alkenyl group” is the “substituted aromatic hydrocarbon group” or “substituted aromatic heterocyclic group” represented by Ar 1 to Ar 4 in the general formula (1).
  • lifted, and the aspect which can be taken can also mention the same thing.
  • “substituents” are represented by R 1 to R 8.
  • Specific examples of the “linear or branched alkyloxy group having 1 to 6 atoms” or “cycloalkyloxy group having 5 to 10 carbon atoms” specifically include a methyloxy group, an ethyloxy group, and an n-propyloxy group.
  • N—Ar 8 means “substituted or unsubstituted aromatic hydrocarbon group” represented by Ar 1 to Ar 4 in the above general formula (1), “substituted or unsubstituted aromatic complex”. It means the same as “N—Ar 8 ” defined for “ring group” or “substituted or unsubstituted condensed polycyclic aromatic group”.
  • “substituents” are represented by R 1 to R 8.
  • the “substituent” in the “straight-chain or branched alkyloxy group having 1 to 6 carbon atoms” or “cycloalkyloxy group having 5 to 10 carbon atoms having a substituent” includes the above general formula (1
  • R 1 to R 8 Represented by R 1 to R 8 in the structural formulas (B), (B-1), (B-2), (B-3), (B-4), (B ′), "Aromatic hydrocarbon group”, “Aromatic heterocyclic group” in “Substituted aromatic hydrocarbon group”, “Substituted or unsubstituted aromatic heterocyclic group” or “Substituted or unsubstituted condensed polycyclic aromatic group”
  • a “condensed polycyclic aromatic group” is a “substituted or unsubstituted aromatic hydrocarbon group” represented by Ar 1 to Ar 4 in the general formula (1), “substituted or unsubstituted aromatic group”
  • Ar 1 to Ar 4 in the general formula (1)
  • the “substituent” in the “hydrocarbon group”, “substituted aromatic heterocyclic group” or “substituted condensed polycyclic aromatic group” is the “substituted” represented by Ar 1 to Ar 4 in the above general formula (1).
  • the “aryloxy group” in the “substituted aryloxy group” specifically includes phenyloxy group, tolyloxy group, biphenylyloxy group, terphenylyloxy group, naphthyloxy group, anthryloxy group, phenanthryloxy group.
  • N—Ar 8 means “substituted or unsubstituted aromatic hydrocarbon group” represented by Ar 1 to Ar 4 in the above general formula (1), “substituted or unsubstituted aromatic complex”. It means the same as “N—Ar 8 ” defined for “ring group” or “substituted or unsubstituted condensed polycyclic aromatic group”.
  • Substituted aryloxy represented by R 1 to R 8 in the structural formulas (B), (B-1), (B-2), (B-3), (B-4), and (B ′)
  • the “substituent” in the “group” is the “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group” or “substituted condensed polycycle” represented by Ar 1 to Ar 4 in the general formula (1).
  • n represents an integer of 0 to 4, and n is preferably 0, 1 or 2, and more preferably 0 or 1.
  • at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 is the structural formula (B), or at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 is the structure
  • An embodiment having the formula (B) as a substituent, or at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 is the structural formula (B), and Ar 1 , Ar 2 , Ar 3 , Ar 4
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 Or at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 is the above-described structural formula (B), or Ar 1 , Ar 2 , Ar 3 , or Ar 4 has the structural formula (B) as a substituent, or any one of Ar 1 , Ar 2 , Ar 3 , Ar 4 is the structural formula (B)
  • Ar 1 and Ar 4 have the structural formula (B-1), (B-3) or (B-4) as a substituent.
  • the embodiment or the embodiment represented by the structural formula (B-2) is more preferable.
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 in the general formula (1) include an aromatic hydrocarbon group, a condensed polycyclic aromatic group, the structural formula (B), a thienyl group, a benzothienyl group, and a dibenzofura.
  • Nyl group and dibenzothienyl group are preferable, and phenyl group, biphenylyl group, terphenylyl group, naphthyl group, phenanthryl group, fluorenyl group, the structural formula (B), thienyl group, benzothienyl group, dibenzofuranyl group, dibenzothienyl group are More preferred are a phenyl group, a biphenylyl group, a fluorenyl group, the structural formula (B), a dibenzofuranyl group, and a dibenzothienyl group.
  • Ar 5 , Ar 6 and Ar 7 in the structural formulas (B), (B-2) and (B ′) are aromatic hydrocarbon groups, condensed polycyclic aromatic groups, thienyl groups, benzothienyl groups, dibenzos A furanyl group and a dibenzothienyl group are preferable, and a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, a thienyl group, a benzothienyl group, a dibenzofuranyl group, and a dibenzothienyl group are more preferable.
  • R 1 , R 2 , R 3 , R 4 , Ar 5 , Ar 6 , Ar 7 is a linking group.
  • X represents a carbon atom or a nitrogen atom
  • Y represents a carbon atom, an oxygen atom, a sulfur atom, or a nitrogen atom.
  • Y when Y is an oxygen atom or a sulfur atom, Y has no Ar 7 linking group or substituent (Ar 7 does not exist), and when X and Y are nitrogen atoms, Any one of Ar 5 , Ar 6 , Ar 7 is a linking group or a substituent (no two of Ar 5 , Ar 6 , Ar 7 exist), X is a nitrogen atom and Y is a carbon atom In this case, any one of Ar 5 and Ar 6 is a linking group or a substituent (any of Ar 5 and Ar 6 does not exist).
  • Y when X is a nitrogen atom, Y is preferably a nitrogen atom.
  • the linking group of Ar 5 , Ar 6 or Ar 7 is Ar 1 , It is bonded to the carbon atom of Ar 2 , Ar 3 , Ar 4 (the structural formula (B) or (B ′) becomes a substituent of Ar 1 , Ar 2 , Ar 3 or Ar 4 ).
  • the structural formulas (B) and (B ′) when X is a carbon atom, Y is preferably a carbon atom, an oxygen atom, or a sulfur atom, and more preferably an oxygen atom or a sulfur atom.
  • the case where X is a nitrogen atom and Y is an oxygen atom or a sulfur atom is excluded from the present invention.
  • the arylamine compound represented by the general formula (1) that is preferably used in the organic EL device of the present invention is a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, or a capping layer of the organic EL device. It can be used as a constituent material.
  • the thickness of the capping layer is preferably in the range of 30 nm to 120 nm, and more preferably in the range of 40 nm to 80 nm.
  • the refractive index of the capping layer is 1.85 or more when the wavelength of light transmitted through the capping layer is in the range of 450 nm to 750 nm. More preferably.
  • the capping layer may be produced by laminating two or more different constituent materials.
  • the organic EL element of the present invention has a capping layer having a refractive index higher than that of the semi-transparent electrode provided outside the transparent or semi-transparent electrode, an organic EL element capable of greatly improving the light extraction efficiency is provided. can get.
  • the arylamine compound represented by the general formula (1) for the capping layer a film can be formed at a temperature of 400 ° C. or lower, so that the light emitting element is not damaged.
  • the light extraction efficiency of each color can be optimized using the fine mask, and can be suitably applied to a full color display, and a clear and bright image with good color purity can be displayed.
  • the organic EL element of the present invention uses a material for an organic EL element having a high refractive index and excellent thin film stability and durability as a material for the capping layer, compared with a conventional organic EL element, The light extraction efficiency can be greatly improved. Furthermore, it has become possible to realize an organic EL element with high efficiency and long life.
  • FIG. 3 is a diagram showing organic EL element configurations of Examples 10 to 13 and Comparative Example 1.
  • the arylamine compound represented by the general formula (1) that is suitably used in the organic EL device of the present invention is a novel compound, and these compounds can be synthesized, for example, as follows.
  • a 2-aminoarylazobenzene derivative is synthesized from a 1,2-diaminobenzene derivative and a nitroaryl derivative by a known method, and an oxidative cyclization reaction with bis (acetato-O) phenyliodine is performed.
  • a benzotriazole derivative having a group can be synthesized (see, for example, Non-Patent Document 4).
  • a bromo-substituted product of a benzotriazole derivative having an aryl group can be synthesized.
  • an arylamine compound represented by the general formula (1) of the present invention can be synthesized by performing a condensation reaction such as an Ullmann reaction or a Buchwald-Hartwig reaction between the bromo-substituted product and diarylamine. .
  • the brominated benzotriazole derivative can also be synthesized by brominating the synthesized benzotriazole derivative having an aryl group with N-bromosuccinimide or the like.
  • bromo-substituted products having different substitution positions can be obtained by changing the bromination reagent and conditions.
  • the arylamine compound represented by General formula (1) of this invention is compoundable by performing the same reaction.
  • Suzuki coupling of a boronic acid or a boronic acid ester derivative see, for example, Non-Patent Document 5 synthesized by reacting various aryl halides with pinacol borane or bis (pinacolato) diboron, for this bromo-substituted product.
  • the arylamine compound represented by the general formula (1) of the present invention can also be synthesized by performing a cross coupling reaction such as (see, for example, Non-Patent Document 6). Further, a boronic acid or a boronic acid ester (for example, see Non-Patent Document 5) derivative is synthesized from the bromo-substituted product, and a cross-coupling reaction such as Suzuki coupling with an aryl halide having various diarylamino groups (for example, The arylamine compound represented by the general formula (1) of the present invention can also be synthesized by performing Non-Patent Document 6).
  • a cross coupling reaction such as (see, for example, Non-Patent Document 6).
  • a boronic acid or a boronic acid ester for example, see Non-Patent Document 5
  • a cross-coupling reaction such as Suzuki coupling with an aryl halide having various diarylamino groups
  • a benzothiazole group, a benzothiazole group, a benzothiazole derivative, a benzoxazole derivative, or a bromo substituent of an indole derivative having a corresponding substituent, or a bromo substituent after bromination An arylamine compound represented by the general formula (1) of the present invention having a benzoxazole group or an indole group can be synthesized.
  • Tg glass transition point
  • refractive index is an index for improving the light extraction efficiency.
  • the glass transition point (Tg) was measured with a high sensitivity differential scanning calorimeter (manufactured by Bruker AXS, DSC3100S) using powder.
  • the refractive index was measured using a spectroscopic measurement device (F10-RT-UV, manufactured by Filmetrics) by preparing a thin film of 80 nm on a silicon substrate.
  • the organic EL device of the present invention for example, in the case of a light emitting device having a top emission structure, a metal anode, a hole transport layer, a light emitting layer, an electron transport layer, a translucent cathode, Containing a capping layer, having a hole injection layer between the anode and the hole transport layer, having an electron blocking layer between the hole transport layer and the light emitting layer, and between the light emitting layer and the electron transport layer And those having an electron injection layer between the electron transport layer and the cathode.
  • each layer of the organic EL element is preferably about 200 nm to 750 nm, and more preferably about 350 nm to 600 nm.
  • the film thickness of the capping layer is preferably 30 nm to 120 nm, for example, and more preferably 40 nm to 80 nm. In this case, good light extraction efficiency can be obtained. Note that the thickness of the capping layer can be changed as appropriate depending on the type of the light emitting material used for the light emitting element, the thickness of the organic EL element other than the capping layer, and the like.
  • an electrode material having a large work function such as ITO or gold is used.
  • an arylamine compound having a structure in which three or more triphenylamine structures are connected by a divalent group not containing a single bond or a hetero atom in the molecule for example, starburst Materials such as triphenylamine derivatives of various types, various triphenylamine tetramers, porphyrin compounds represented by copper phthalocyanine, acceptor heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymer materials are used. be able to.
  • These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used.
  • These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
  • N, N′-diphenyl-N, N′-di (m-tolyl) benzidine hereinafter abbreviated as TPD
  • NPD N, N′-diphenyl- N, N'-di ( ⁇ -naphthyl) benzidine
  • TAPC 1,1-bis [4- (di-4-tolylamino) phenyl] cyclohexane
  • N, N, N ′, N′-tetrabiphenylylbenzidine especially two triphenylamine structures in the molecule
  • an arylamine compound having a structure in which a single bond or a divalent group not containing a hetero atom is connected, for example, N, N, N ′, N′-tetrabiphenylylbenzidine.
  • arylamine compounds having a structure in which three or more triphenylamine structures in the molecule are linked by a divalent group not containing a single bond or a hetero atom such as various triphenylamine trimers and tetramers Is preferably used.
  • These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used.
  • These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
  • the material usually used for the layer is further P-doped with trisbromophenylamine hexachloroantimony or the structure of a benzidine derivative such as TPD.
  • TPD a benzidine derivative
  • TCTA N-carbazolyl triphenylamine
  • mCP 1,3-bis (carbazol-9-yl) benzene
  • Ad-Cz 2,2-bis (4-carbazol-9-ylphenyl) adamantane
  • Carbazole derivatives such as 9- [4- (carbazol-9-yl) phenyl] -9- [4- (triphenylsilyl) phenyl] -9H-fluorene and triarylamine structures
  • a compound having an electron-blocking action such as a compound having an electron can be used.
  • These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used.
  • These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
  • the light emitting layer of the organic EL device of the present invention metal complexes of quinolinol derivatives such as Alq 3 , various metal complexes, anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, and the like are used. be able to.
  • the light-emitting layer may be composed of a host material and a dopant material.
  • a thiazole derivative, a benzimidazole derivative, a polydialkylfluorene derivative, or the like can be used in addition to the light-emitting material.
  • quinacridone coumarin, rubrene, perylene, and derivatives thereof
  • benzopyran derivatives rhodamine derivatives, aminostyryl derivatives, and the like
  • These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used.
  • a phosphorescent material can be used as the light emitting material.
  • a phosphorescent emitter of a metal complex such as iridium or platinum can be used.
  • Green phosphorescent emitters such as Ir (ppy) 3
  • blue phosphorescent emitters such as FIrpic and FIr6, red phosphorescent emitters such as Btp 2 Ir (acac), and the like are used as host materials.
  • carbazole derivatives such as 4,4′-di (N-carbazolyl) biphenyl (CBP), TCTA, and mCP can be used.
  • p-bis (triphenylsilyl) benzene (UGH2) and 2,2 ′, 2 ′′-(1,3,5-phenylene) -tris (1-phenyl-1H-benzimidazole) ) (TPBI) or the like, and a high-performance organic EL element can be manufactured.
  • the phosphorescent light-emitting material into the host material by co-evaporation in the range of 1 to 30 weight percent with respect to the entire light-emitting layer.
  • Non-Patent Document 7 a material that emits delayed fluorescence such as CDCB derivatives such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN as a light-emitting material.
  • CDCB derivatives such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN
  • These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
  • a phenanthroline derivative such as bathocuproine (BCP) or aluminum (III) bis (2-methyl-8-quinolinato) -4-phenylphenolate (hereinafter abbreviated as BAlq).
  • BCP bathocuproine
  • BAlq aluminum (III) bis (2-methyl-8-quinolinato) -4-phenylphenolate
  • BAlq aluminum (III) bis (2-methyl-8-quinolinato) -4-phenylphenolate
  • BAlq aluminum (III) bis (2-methyl-8-quinolinato) -4-phenylphenolate
  • BAlq aluminum (III) bis (2-methyl-8-quinolinato) -4-phenylphenolate
  • BAlq aluminum (III) bis (2-methyl-8-quinolinato) -4-phenylphenolate
  • BAlq aluminum (III) bis (2-methyl-8-quinolinato) -4-phenylphenolate
  • BAlq aluminum (III) bis (2-methyl-8-quinolinato) -4-phenylphenolate
  • metal complexes of quinolinol derivatives such as Alq 3 and BAlq, various metal complexes, triazole derivatives, triazine derivatives, oxadiazole derivatives, thiadiazole derivatives, pyridoindole derivatives, carbodiimides Derivatives, quinoxaline derivatives, phenanthroline derivatives, silole derivatives, and the like can be used.
  • quinolinol derivatives such as Alq 3 and BAlq
  • various metal complexes such as Alq 3 and BAlq
  • triazole derivatives triazine derivatives
  • oxadiazole derivatives oxadiazole derivatives
  • thiadiazole derivatives pyridoindole derivatives
  • carbodiimides Derivatives quinoxaline derivatives, phenanthroline derivatives, silole derivatives, and the like
  • These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone,
  • an alkali metal salt such as lithium fluoride and cesium fluoride
  • an alkaline earth metal salt such as magnesium fluoride
  • a metal oxide such as aluminum oxide
  • a material usually used for the layer and further doped with a metal such as cesium can be used.
  • an electrode material having a low work function such as aluminum, an alloy having a lower work function such as a magnesium silver alloy, a magnesium calcium alloy, a magnesium indium alloy, an aluminum magnesium alloy, ITO, IZO or the like is used as an electrode material.
  • an arylamine compound represented by the general formula (1) may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
  • the organic EL element having the top emission structure has been described.
  • the present invention is not limited to this, and the organic EL element having the bottom emission structure or the dual emission structure that emits light from both the top and bottom directions is used.
  • organic EL elements In these cases, an electrode in a direction in which light is extracted from the light emitting element to the outside needs to be transparent or translucent.
  • the refractive index of the material constituting the capping layer is preferably larger than the refractive index of the adjacent electrode.
  • the refractive index of the material constituting the capping layer is preferably larger than the refractive index of the adjacent electrode, and the refractive index may be 1.70 or more, more preferably 1.80 or more, and 1.85. The above is particularly preferable.
  • the glass transition point was calculated
  • the compound of the present invention has a glass transition point of 100 ° C. or higher. This indicates that the thin film state is stable in the compound of the present invention.
  • a deposited film having a thickness of 80 nm was formed on a silicon substrate, and the refractive index at 633 nm was measured using a spectroscopic measurement apparatus (F10-RT-UV, manufactured by Filmetrics).
  • F10-RT-UV spectroscopic measurement apparatus
  • the comparative compounds (2-1), (2-2) and Alq 3 having the following structural formula were also measured (see, for example, Patent Document 3).
  • the compound of the present invention has a value higher than the refractive index of 1.70 to 1.81 of the comparative compounds (2-1), (2-2) and Alq 3 , The improvement of the extraction efficiency can be expected.
  • the organic EL element has a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport on a glass substrate 1 on which a reflective ITO electrode is previously formed as a metal anode 2.
  • the layer 6, the electron injection layer 7, the cathode 8, and the capping layer 9 were deposited in this order.
  • the glass substrate 1 formed with ITO having a thickness of 150 nm was subjected to ultrasonic cleaning in isopropyl alcohol for 20 minutes, and then dried on a hot plate heated to 250 ° C. for 10 minutes. Then, after performing UV ozone treatment for 2 minutes, this glass substrate with ITO was attached in a vacuum evaporation machine, and pressure was reduced to 0.001 Pa or less. Subsequently, a compound (HIM-1) having the following structural formula was formed to a thickness of 5 nm as a hole injection layer 3 so as to cover the metal anode 2. On the hole injection layer 3, the comparative compound (2-1) was formed as a hole transport layer 4 so as to have a film thickness of 70 nm.
  • compound EMD-1 NUBD370 manufactured by SFC Co., Ltd.
  • compound EMH-1 ABS113 manufactured by SFC Co., Ltd.
  • Binary vapor deposition was performed at a vapor deposition rate of 5:95, and a film thickness of 25 nm was formed.
  • lithium fluoride was formed as the electron injection layer 7 so as to have a film thickness of 0.5 nm.
  • a magnesium silver alloy was formed as a cathode 8 so as to have a film thickness of 14 nm.
  • Example 1 the compound (1-1) of Example 1 was formed as the capping layer 9 so as to have a film thickness of 60 nm.
  • the characteristic measurement was performed at normal temperature in air
  • Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the manufactured organic EL element.
  • Example 10 the organic layer was formed under the same conditions except that the compound (1-32) of Example 2 was formed to a film thickness of 60 nm instead of the compound (1-1) of Example 1 as the capping layer 9.
  • An EL element was produced. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air
  • Example 10 the organic layer was formed under the same conditions except that the compound (1-2) of Example 3 was formed to a film thickness of 60 nm instead of the compound (1-1) of Example 1 as the capping layer 9.
  • An EL element was produced. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air
  • Example 10 the organic layer was formed under the same conditions except that the compound (1-22) of Example 4 was formed to a thickness of 60 nm instead of the compound (1-1) of Example 1 as the capping layer 9.
  • An EL element was produced. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air
  • Example 1 For comparison, an organic EL device was manufactured under the same conditions as in Example 10 except that Alq 3 was formed to a thickness of 60 nm instead of the compound (1-1) of Example 1 as the capping layer 9. Produced. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air
  • the driving voltage at a current density of 10 mA / cm 2 is the device of Comparative Example 1 (4.19 V) using Alq 3 and the devices of Examples 10 to 13 (4.17 to 4.18 V). ), The luminance, light emission efficiency, and power efficiency are almost the same as those of Comparative Example 1 using Alq 3 (light emission efficiency: 5.13 cd / A, power efficiency: 3.78 lm / W). In contrast, the devices of Examples 10 to 13 (light emission efficiency: 5.31 to 5.36 cd / A, power efficiency: 3.98 to 4.06 lm / W) were all improved.
  • the arylamine compound represented by the general formula (1) suitably used in the organic EL device of the present invention has a high refractive index, can greatly improve the light extraction efficiency, and the thin film state is stable. Therefore, it is excellent as a compound for an organic EL device.
  • the use of the compound having no absorption in each of the blue, green, and red wavelength regions is particularly suitable for displaying a clear and bright image with good color purity. For example, it has become possible to develop home appliances and lighting.

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Abstract

[Problem] To provide an organic electroluminescent element that is provided with a capping layer, which has high refractive index and excellent stability and durability of a thin film, and which is configured from a material that does not have absorption in blue, green and red wavelength regions, for the purpose of improving element characteristics of the organic electroluminescent element, especially for the purpose of greatly improving the light extraction efficiency. [Solution] An organic electroluminescent element which sequentially comprises at least a positive electrode, a hole transport layer, a light emitting layer, an electron transport layer, a negative electrode and a capping layer in this order, and wherein the capping layer contains an aryl amine compound represented by general formula (1).

Description

有機エレクトロルミネッセンス素子Organic electroluminescence device
　本発明は、各種の表示装置に好適な自発光素子である有機エレクトロルミネッセンス素子（以下、有機ＥＬ素子と略称する）に関するものであリ、詳しくは特定のアリールアミン化合物を用いた有機ＥＬ素子に関するものであり、特に、光の取出し効率が大幅に改善された有機ＥＬ素子に関するものである。 The present invention relates to an organic electroluminescence element (hereinafter abbreviated as an organic EL element) which is a self-luminous element suitable for various display devices, and more particularly to an organic EL element using a specific arylamine compound. In particular, the present invention relates to an organic EL element in which the light extraction efficiency is greatly improved.
　有機ＥＬ素子は自己発光性素子であるため、液晶素子に比べて明るく視認性に優れ、鮮明な表示が可能であることから、活発な研究がなされてきた。 Since the organic EL element is a self-luminous element, it has been actively researched because it is brighter and more visible than a liquid crystal element and can be clearly displayed.
　１９８７年にイーストマン・コダック社のＣ．Ｗ．Ｔａｎｇらは各種の役割を各材料に分担した積層構造素子を開発することにより有機材料を用いた有機ＥＬ素子を実用的なものにした。彼らは電子を輸送することのできる蛍光体と正孔を輸送することのできる有機物とを積層し、両方の電荷を蛍光体の層の中に注入して発光させることにより、１０Ｖ以下の電圧で１０００ｃｄ／ｍ２以上の高輝度が得られるようになった（例えば、特許文献１および特許文献２参照）。 In 1987, Eastman Kodak's C.I. W. Tang et al. Have made a practical organic EL device using an organic material by developing a laminated structure device in which various roles are assigned to each material. They laminate a phosphor capable of transporting electrons and an organic substance capable of transporting holes, and inject both charges into the phosphor layer to emit light. High luminance of 1000 cd / m 2 or more can be obtained (for example, see Patent Document 1 and Patent Document 2).
　現在まで、有機ＥＬ素子の実用化のために多くの改良がなされ、積層構造の各種の役割をさらに細分化して、基板上に順次に、陽極、正孔注入層、正孔輸送層、発光層、電子輸送層、電子注入層、陰極を設けた電界発光素子において、高効率と耐久性が、底部から発光するボトムエミッション構造の発光素子によって達成されるようになってきた（例えば、非特許文献１参照）。 Up to now, many improvements have been made for practical use of organic EL devices, and the various roles of the laminated structure have been further subdivided, and sequentially on the substrate, anode, hole injection layer, hole transport layer, light emitting layer In an electroluminescent device provided with an electron transport layer, an electron injection layer, and a cathode, high efficiency and durability have been achieved by a light emitting device having a bottom emission structure that emits light from the bottom (for example, non-patent literature) 1).
　近年、高い仕事関数を持った金属を陽極に用い、上部から発光するトップエミッション構造の発光素子が用いられるようになってきた。画素回路によって発光部の面積が制限されてしまうボトムエミッション構造の発光素子とは違い、トップエミッション構造の発光素子では、発光部を広くとれるという利点がある。トップエミッション構造の発光素子では、陰極にＬｉＦ／Ａｌ／Ａｇ（例えば、非特許文献２参照）、Ｃａ／Ｍｇ（例えば、非特許文献３参照）、ＬｉＦ／ＭｇＡｇなどの半透明電極が用いられる。 In recent years, a light emitting element having a top emission structure in which a metal having a high work function is used for an anode and light is emitted from the upper part has been used. Unlike a light emitting element having a bottom emission structure in which the area of the light emitting part is limited by the pixel circuit, a light emitting element having a top emission structure has an advantage that a wide light emitting part can be obtained. In a light emitting device having a top emission structure, a semitransparent electrode such as LiF / Al / Ag (for example, see Non-Patent Document 2), Ca / Mg (for example, see Non-Patent Document 3), LiF / MgAg, or the like is used as a cathode.
　このような発光素子では、発光層で発光した光が他の膜に入射する場合に、ある角度以上で入射すると、発光層と他の膜との界面で全反射されてしまう。このため、発光した光の一部しか利用できていなかった。近年、光の取出し効率を向上させるために、屈折率の低い半透明電極の外側に、屈折率の高い「キャッピング層」を設けた発光素子が提案されている（例えば、非特許文献２および３参照）。 In such a light emitting element, when light emitted from the light emitting layer is incident on another film, if the light is incident at an angle or more, the light is totally reflected at the interface between the light emitting layer and the other film. For this reason, only a part of the emitted light was available. In recent years, in order to improve the light extraction efficiency, a light emitting element in which a “capping layer” having a high refractive index is provided outside a translucent electrode having a low refractive index has been proposed (for example, Non-Patent Documents 2 and 3). reference).
　トップエミッション構造の発光素子におけるキャッピング層の効果は、Ｉｒ（ｐｐｙ）３を発光材料に用いた発光素子において、キャッピング層がない場合は電流効率が３８ｃｄ／Ａであったものが、キャッピング層として膜厚６０ｎｍのＺｎＳｅを使用した発光素子では、６４ｃｄ／Ａと約１．７倍の効率向上が認められた。また、半透明電極とキャッピング層の透過率の極大点と効率の極大点とが必ずしも一致しないことが示されており、光の取出し効率の最大点は干渉効果によって決められることが示されている（例えば、非特許文献３参照）。 The effect of the capping layer in the light emitting device having the top emission structure is that a light emitting device using Ir (ppy) 3 as a light emitting material has a current efficiency of 38 cd / A when there is no capping layer. In the light emitting device using ZnSe having a thickness of 60 nm, an efficiency improvement of about 1.7 times as 64 cd / A was recognized. In addition, it is shown that the maximum point of transmittance and the maximum point of efficiency of the translucent electrode and the capping layer do not necessarily coincide with each other, and the maximum point of light extraction efficiency is determined by the interference effect. (For example, refer nonpatent literature 3).
　キャッピング層の形成には、精細度の高いメタルマスクを用いることが提案されているが、かかるメタルマスクでは、熱による歪みによって位置合わせ精度が悪くなるという問題点があった。すなわち、ＺｎＳｅは、融点が１１００℃以上と高く（例えば、非特許文献３参照）、精細度の高いマスクでは正確な位置に蒸着することができない。無機物の多くは蒸着温度が高く、精細度の高いマスクの使用には適さず、発光素子そのものにもダメージを与える可能性がある。さらに、スパッタ法による成膜では、発光素子にダメージを与えてしまうため、無機物を構成材料とするキャッピング層は使用することができない。 It has been proposed to use a metal mask with high definition for the formation of the capping layer, but such a metal mask has a problem that the alignment accuracy is deteriorated due to thermal distortion. That is, ZnSe has a high melting point of 1100 ° C. or higher (see, for example, Non-Patent Document 3), and cannot be deposited at an accurate position with a high-definition mask. Many inorganic substances have high deposition temperatures and are not suitable for use with high-definition masks, and may damage the light-emitting elements themselves. Further, in the film formation by the sputtering method, the light emitting element is damaged, and therefore a capping layer containing an inorganic material cannot be used.
　屈折率を調整するキャッピング層として、トリス（８－ヒドロキシキノリン）アルミニウム（以後、Ａｌｑ３と略称する）を使用する場合（例えば、非特許文献２参照）、Ａｌｑ３は緑の発光材料または電子輸送材料として一般的に使用される有機ＥＬ材料として知られているが、青色発光素子に使用される４５０ｎｍ付近に弱い吸収を持つ。そのために、青色発光素子の場合、色純度の低下と、光の取出し効率がともに低下するという問題点もあった。 When tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq 3 ) is used as a capping layer for adjusting the refractive index (for example, see Non-Patent Document 2), Alq 3 is a green light-emitting material or electron transport. Although known as an organic EL material generally used as a material, it has weak absorption in the vicinity of 450 nm used for a blue light emitting element. Therefore, in the case of a blue light emitting element, there is a problem that both the color purity is lowered and the light extraction efficiency is lowered.
　有機ＥＬ素子の素子特性を改善させるために、特に、光の取出し効率を大幅に改善させるために、キャッピング層の材料として、屈折率が高く、薄膜の安定性や耐久性に優れた材料が求められている。 In order to improve the device characteristics of organic EL devices, especially in order to greatly improve the light extraction efficiency, a material with a high refractive index and excellent thin film stability and durability is required as a material for the capping layer. It has been.
特開平８－０４８６５６号公報JP-A-8-048656 特許第３１９４６５７号公報Japanese Patent No. 3194657 ＷＯ２０１３－０３８６２７号WO2013-038627
　本発明の目的は、有機ＥＬ素子の素子特性を改善させるために、特に、光の取出し効率を大幅に改善させるために、屈折率が高く、薄膜の安定性や耐久性に優れているとともに、青、緑および赤それぞれの波長領域において吸収を持たない材料から構成されるキャッピング層を備えた有機ＥＬ素子を提供することにある。 The object of the present invention is to improve the device characteristics of the organic EL device, in particular, to greatly improve the light extraction efficiency, and has a high refractive index and excellent thin film stability and durability. An object of the present invention is to provide an organic EL device having a capping layer made of a material that does not absorb in the wavelength regions of blue, green and red.
　本発明に適したキャッピング層の材料における物理的な特性としては、（１）屈折率が高いこと、（２）蒸着が可能で熱分解しないこと、（３）薄膜状態が安定であること、（４）ガラス転移温度が高いことをあげることができる。また、本発明に適した素子の物理的な特性としては、（１）光の取出し効率が高いこと、（２）色純度の低下がないこと、（３）経時変化することなく光を透過すること、（４）長寿命であることをあげることができる。 The physical properties of the capping layer material suitable for the present invention include (1) high refractive index, (2) vapor deposition and no thermal decomposition, (3) stable thin film state, 4) The glass transition temperature is high. The physical characteristics of the element suitable for the present invention include (1) high light extraction efficiency, (2) no decrease in color purity, and (3) light transmission without change over time. (4) Long life can be mentioned.
　本発明者らは上記の目的を達成するために、アリールアミン系材料が薄膜の安定性や耐久性に優れていることに着目して、屈折率が高い特定のアリールアミン化合物を選別し、キャッピング層を構成する材料として用いた有機ＥＬ素子を作製し、素子の特性評価を鋭意行った結果、本発明を完成するに至った。 In order to achieve the above object, the present inventors selected a specific arylamine compound having a high refractive index and capped the arylamine material, focusing on the excellent stability and durability of the thin film. As a result of producing an organic EL element used as a material constituting the layer and intensively evaluating the characteristics of the element, the present invention was completed.
　すなわち、本発明によれば、以下の有機ＥＬ素子が提供される。 That is, according to the present invention, the following organic EL elements are provided.
　１）少なくとも陽極電極、正孔輸送層、発光層、電子輸送層、陰極電極およびキャッピング層をこの順に有する有機エレクトロルミネッセンス素子において、前記キャッピング層が下記一般式（１）で表されるアリールアミン化合物を含む、有機ＥＬ素子。 1) In an organic electroluminescence device having at least an anode electrode, a hole transport layer, a light emitting layer, an electron transport layer, a cathode electrode and a capping layer in this order, the capping layer is an arylamine compound represented by the following general formula (1) An organic EL element including
Figure JPOXMLDOC01-appb-C000001
 　　　　　　　　　　　　　　　　　　　　　　　　　（１）
Figure JPOXMLDOC01-appb-C000001
 (1)
　（式中、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４は相互に同一でも異なってもよく、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基を表し、ｎは０～４の整数を表す。ここで、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４の少なくとも１つは、下記構造式（Ｂ）で示される１価基であるか、もしくは、該１価基を置換基として有するものとする。） (In the formula, Ar 1 , Ar 2 , Ar 3 and Ar 4 may be the same or different from each other, and are substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted aromatic heterocyclic groups, substituted or unsubstituted Represents a substituted fused polycyclic aromatic group, and n represents an integer of 0 to 4. Here, at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 is represented by the following structural formula (B) It is a monovalent group or has the monovalent group as a substituent.)
Figure JPOXMLDOC01-appb-C000002
 　　　　　　　　　　　　　　　　　　　　　　　　　（Ｂ）
Figure JPOXMLDOC01-appb-C000002
 (B)
　（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は相互に同一でも異なってもよく、連結基、もしくは水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキル基、置換基を有していてもよい炭素原子数２ないし６の直鎖状もしくは分岐状のアルケニル基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキルオキシ基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、または置換もしくは無置換のアリールオキシ基であって、単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成していてもよい。Ｘは炭素原子または窒素原子を表し、Ｙは炭素原子、酸素原子、硫黄原子、または窒素原子を表し、Ａｒ５は置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基、もしくは連結基を表し、Ａｒ６、Ａｒ７は相互に同一でも異なってもよく、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基、もしくは連結基であって、Ｙが酸素原子もしくは硫黄原子である場合、ＹはＡｒ７を有さないものとし、ＸおよびＹが窒素原子である場合、Ａｒ５、Ａｒ６、Ａｒ７のいずれかひとつが置換基、もしくは連結基であるものとし、Ｘが窒素原子かつＹが炭素原子である場合、ＸはＡｒ６を有さないものとする。Ａｒ８は置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表す。ただし、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ａｒ５、Ａｒ６、Ａｒ７のいずれか１つのみが連結基であるものとし、Ｘが窒素原子、かつＹが酸素原子もしくは硫黄原子である場合を除く。なお、Ａｒ６、Ａｒ６、Ａｒ７は相互に同一でも異なってもよい。） (In the formula, R 1 , R 2 , R 3 and R 4 may be the same or different from each other, and may be a linking group, or a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group, substituent. A linear or branched alkyl group having 1 to 6 carbon atoms which may have a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or a substituent. A linear or branched alkenyl group having 2 to 6 carbon atoms, a linear or branched alkyloxy group having 1 to 6 carbon atoms which may have a substituent, and a substituent; C5-C10 cycloalkyloxy group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensed polycyclic aromatic which may have Group, or substituted or unsubstituted A substituted aryloxy group which may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom or N—Ar 8 , wherein X is a carbon atom; Or a nitrogen atom, Y represents a carbon atom, an oxygen atom, a sulfur atom, or a nitrogen atom, and Ar 5 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted atom Alternatively, it represents an unsubstituted condensed polycyclic aromatic group or a linking group, and Ar 6 and Ar 7 may be the same or different from each other, and are a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic group A heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a linking group, where Y is an oxygen atom or a sulfur atom, Y shall not have Ar 7 and X and Y may be nitrogen If a child, Ar 5, one of Ar 6, Ar 7 is assumed to be a substituent or linking group, if X is a nitrogen atom and Y is carbon atom, X has no Ar 6 Ar 8 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, provided that R 1 , R Only one of 2 , R 3 , R 4 , Ar 5 , Ar 6 , Ar 7 is a linking group, except when X is a nitrogen atom and Y is an oxygen atom or a sulfur atom. , Ar 6 , Ar 6 , Ar 7 may be the same or different from each other.
　２）前記構造式（Ｂ）が下記構造式（Ｂ－１）で示される１価基である、上記１）記載の有機ＥＬ素子。 2) The organic EL device according to 1), wherein the structural formula (B) is a monovalent group represented by the following structural formula (B-1).
Figure JPOXMLDOC01-appb-C000003
 　　　　　　　　　　　　　　　　　　　　　　　　　（Ｂ－１）
Figure JPOXMLDOC01-appb-C000003
 (B-1)
　（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は相互に同一でも異なってもよく、水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキル基、置換基を有していてもよい炭素原子数２ないし６の直鎖状もしくは分岐状のアルケニル基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキルオキシ基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、または置換もしくは無置換のアリールオキシ基であって、単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成してもよい。Ａｒ８は置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表す。） (In the formula, R 1 , R 2 , R 3 and R 4 may be the same or different from each other and have a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group or substituent. An optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, and an optionally substituted carbon A linear or branched alkenyl group having 2 to 6 atoms, an optionally substituted linear or branched alkyloxy group having 1 to 6 carbon atoms, or a substituent. A cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted group Or unsubstituted aryloxy A sheet group, a single bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom or N-Ar 8 .Ar 8 may be bonded to each other to form a ring through the substituted or unsubstituted Represents an aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.)
　３）前記構造式（Ｂ）が下記構造式（Ｂ－２）で示される１価基である、上記１）記載の有機ＥＬ素子。 3) The organic EL device according to 1) above, wherein the structural formula (B) is a monovalent group represented by the following structural formula (B-2).
Figure JPOXMLDOC01-appb-C000004
 　　　　　　　　　　　　　　　　　　　　　　　　　（Ｂ－２）
Figure JPOXMLDOC01-appb-C000004
 (B-2)
　（式中、Ｒ１、Ｒ３、Ｒ４は相互に同一でも異なってもよく、水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキル基、置換基を有していてもよい炭素原子数２ないし６の直鎖状もしくは分岐状のアルケニル基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキルオキシ基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、または置換もしくは無置換のアリールオキシ基であって、Ｒ３とＲ４は単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成してもよい。Ａｒ６、Ａｒ８は相互に同一でも異なってもよく、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表す。） (In the formula, R 1 , R 3 and R 4 may be the same or different from each other, and may have a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group or substituent. A linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, and an optionally substituted carbon atom 2 1 to 6 linear or branched alkenyl groups, optionally having a straight chain or branched alkyloxy group having 1 to 6 carbon atoms, and optionally having a substituent. A cycloalkyloxy group having 5 to 10 atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted group In the aryloxy group It, R 3 and R 4 is a single bond, a substituted or unsubstituted methylene group, an oxygen atom, through a sulfur atom or N-Ar 8 may be bonded to each other to form a ring .Ar 6, Ar 8 May be the same or different from each other, and each represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.
　４）前記構造式（Ｂ）が下記構造式（Ｂ－３）で示される１価基である、上記１）記載の有機ＥＬ素子。 4) The organic EL device according to 1) above, wherein the structural formula (B) is a monovalent group represented by the following structural formula (B-3).
Figure JPOXMLDOC01-appb-C000005
 　　　　　　　　　　　　　　　　　　　　　　　　　（Ｂ－３）
Figure JPOXMLDOC01-appb-C000005
 (B-3)
　（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は相互に同一でも異なってもよく、水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキル基、置換基を有していてもよい炭素原子数２ないし６の直鎖状もしくは分岐状のアルケニル基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキルオキシ基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、または置換もしくは無置換のアリールオキシ基であって、単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成してもよい。Ａｒ８は置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表す。） (In the formula, R 1 , R 2 , R 3 and R 4 may be the same or different from each other and have a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group or substituent. An optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, and an optionally substituted carbon A linear or branched alkenyl group having 2 to 6 atoms, an optionally substituted linear or branched alkyloxy group having 1 to 6 carbon atoms, or a substituent. A cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted group Or unsubstituted aryloxy A sheet group, a single bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom or N-Ar 8 .Ar 8 may be bonded to each other to form a ring through the substituted or unsubstituted Represents an aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.)
　５）前記構造式（Ｂ）が下記構造式（Ｂ－４）で示される１価基である、上記１）記載の有機ＥＬ素子。 5) The organic EL device according to 1) above, wherein the structural formula (B) is a monovalent group represented by the following structural formula (B-4).
Figure JPOXMLDOC01-appb-C000006
 　　　　　　　　　　　　　　　　　　　　　　　　　（Ｂ－４）
Figure JPOXMLDOC01-appb-C000006
 (B-4)
　（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は相互に同一でも異なってもよく、水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキル基、置換基を有していてもよい炭素原子数２ないし６の直鎖状もしくは分岐状のアルケニル基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキルオキシ基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、または置換もしくは無置換のアリールオキシ基であって、単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成してもよい。Ａｒ８は置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表す。） (In the formula, R 1 , R 2 , R 3 and R 4 may be the same or different from each other and have a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group or substituent. An optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, and an optionally substituted carbon A linear or branched alkenyl group having 2 to 6 atoms, an optionally substituted linear or branched alkyloxy group having 1 to 6 carbon atoms, or a substituent. A cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted group Or unsubstituted aryloxy A sheet group, a single bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom or N-Ar 8 .Ar 8 may be bonded to each other to form a ring through the substituted or unsubstituted Represents an aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.)
　６）前記構造式（Ｂ）が下記構造式（Ｂ’）で示される１価基である、上記１）記載の有機ＥＬ素子。 6) The organic EL device according to 1), wherein the structural formula (B) is a monovalent group represented by the following structural formula (B ′).
Figure JPOXMLDOC01-appb-C000007
 　　　　　　　　　　　　　　　　　　　　　　　　　（Ｂ’）
Figure JPOXMLDOC01-appb-C000007
 (B ')
　（式中、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８は相互に同一でも異なってもよく、連結基、もしくは水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキル基、置換基を有していてもよい炭素原子数２ないし６の直鎖状もしくは分岐状のアルケニル基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキルオキシ基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、または置換もしくは無置換のアリールオキシ基であって、単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成していてもよい。Ｘは炭素原子または窒素原子を表し、Ｙは炭素原子、酸素原子、硫黄原子、または窒素原子を表し、Ａｒ５は置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基、もしくは連結基を表し、Ａｒ６、Ａｒ７は相互に同一でも異なってもよく、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基、もしくは連結基であって、Ｙが酸素原子もしくは硫黄原子である場合、ＹはＡｒ７を有さないものとし、ＸおよびＹが窒素原子である場合、Ａｒ５、Ａｒ６、Ａｒ７のいずれかひとつが置換基、もしくは連結基であるものとし、Ｘが窒素原子かつＹが炭素原子である場合、ＸはＡｒ６を有さないものとする。Ａｒ８は置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表す。ただし、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ａｒ５、Ａｒ６、Ａｒ７のいずれか１つのみが連結基であるものとし、Ｘが窒素原子、かつＹが酸素原子もしくは硫黄原子である場合を除く。） (In the formula, R 3 , R 4 , R 5 , R 6 , R 7 and R 8 may be the same or different from each other, and may be a linking group, or a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group. , A nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched alkyl having 1 to 6 carbon atoms which may have a substituent Oxy group, optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted A fused polycyclic aromatic group, or A substituted or unsubstituted aryloxy group, a single bond, a substituted or unsubstituted methylene group, an oxygen atom, through a sulfur atom or N-Ar 8 may be bonded to each other to form a ring .X Represents a carbon atom or a nitrogen atom, Y represents a carbon atom, an oxygen atom, a sulfur atom, or a nitrogen atom, Ar 5 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group Or a substituted or unsubstituted condensed polycyclic aromatic group or a linking group, and Ar 6 and Ar 7 may be the same or different from each other, and are substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted Or a substituted or unsubstituted condensed polycyclic aromatic group or a linking group, and Y is an oxygen atom or sulfur atom, Y does not have Ar 7 , And Y is a nitrogen atom, any one of Ar 5 , Ar 6 and Ar 7 is a substituent or a linking group, and when X is a nitrogen atom and Y is a carbon atom, X is Ar 6. Ar 8 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, provided that Only one of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , Ar 5 , Ar 6 , Ar 7 is a linking group, X is a nitrogen atom, and Y is an oxygen atom Or except for the case of sulfur atoms.)
　７）前記一般式（１）において、ｎが０である、上記１）記載の有機ＥＬ素子。 7) The organic EL device according to 1), wherein n is 0 in the general formula (1).
　８）前記一般式（１）において、ｎが１である、上記１）記載の有機ＥＬ素子。 8) The organic EL device according to 1), wherein n is 1 in the general formula (1).
　９）前記一般式（１）において、ｎが２である、上記１）記載の有機ＥＬ素子。 9) The organic EL device according to 1), wherein n is 2 in the general formula (1).
　１０）前記一般式（１）において、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４のいずれか２つが、前記構造式（Ｂ）で示される１価基であるか、もしくは該１価基を置換基として有するものである、上記１）記載の有機ＥＬ素子。 10) In the general formula (1), any two of Ar 1 , Ar 2 , Ar 3 , Ar 4 are a monovalent group represented by the structural formula (B), or substituted for the monovalent group The organic EL device according to 1), which is a group.
　１１）前記一般式（１）において、Ａｒ１およびＡｒ４が、前記構造式（Ｂ）で示される１価基であるか、もしくは該１価基を置換基として有するものである、上記１）記載の有機ＥＬ素子。 11) In the general formula (1), Ar 1 and Ar 4 are the monovalent group represented by the structural formula (B), or have the monovalent group as a substituent. The organic EL element of description.
　１２）前記キャッピング層の厚さが、３０ｎｍ～１２０ｎｍの範囲内である、上記１）記載の有機ＥＬ素子。 12) The organic EL device according to 1) above, wherein the thickness of the capping layer is in the range of 30 nm to 120 nm.
　１３）前記キャッピング層の屈折率が、該キャッピング層を透過する光の波長が４５０ｎｍ～７５０ｎｍの範囲内において、１．８５以上である、上記１）記載の有機ＥＬ素子。 13) The organic EL device according to 1), wherein the refractive index of the capping layer is 1.85 or more when the wavelength of light transmitted through the capping layer is in the range of 450 nm to 750 nm.
　１４）前記一般式（１）で表される化合物を有機エレクトロルミネッセンス素子のキャッピング層に用いる方法。 14) A method of using the compound represented by the general formula (1) for a capping layer of an organic electroluminescence element.
　一般式（１）中のＡｒ１～Ａｒ４で表される「置換もしくは無置換の芳香族炭化水素基」、「置換もしくは無置換の芳香族複素環基」または「置換もしくは無置換の縮合多環芳香族基」における「芳香族炭化水素基」、「芳香族複素環基」または「縮合多環芳香族基」としては、具体的に、フェニル基、ビフェニリル基、ターフェニリル基、ナフチル基、アントリル基、フェナントリル基、フルオレニル基、インデニル基、ピレニル基、ペリレニル基、フルオランテニル基、トリフェニレニル基、ピリジル基、フリル基、ピロリル基、チエニル基、キノリル基、イソキノリル基、ベンゾフラニル基、ベンゾチエニル基、インドリル基、カルバゾリル基、ベンゾトリアゾリル基、ベンゾオキサゾリル基、ベンゾチアゾリル基、キノキサリル基、ベンゾイミダゾリル基、ピラゾリル基、ジベンゾフラニル基、ジベンゾチエニル基、およびカルボリニル基などをあげることができる。また、Ａｒ１とＡｒ２、もしくはＡｒ３とＡｒ４は単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成していてもよい。ここで、「Ｎ－Ａｒ８」の「Ｎ」は窒素原子を表し、「Ａｒ８」は「置換もしくは無置換の芳香族炭化水素基」、「置換もしくは無置換の芳香族複素環基」または「置換もしくは無置換の縮合多環芳香族基」であって、前記例示した基と同様の基をあげることができ、これらの基が有していてよい置換基も、同様に下記に例示した置換基をあげることができる。 “Substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” represented by Ar 1 to Ar 4 in formula (1), or “substituted or unsubstituted condensed hydrocarbon group” Specific examples of the “aromatic hydrocarbon group”, “aromatic heterocyclic group” or “condensed polycyclic aromatic group” in the “ring aromatic group” include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthryl group. Group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyridyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, Indolyl group, carbazolyl group, benzotriazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group Benzimidazolyl group, a pyrazolyl group, and a dibenzofuranyl group, dibenzothienyl group, and carbolinyl group and the like. Ar 1 and Ar 2 , or Ar 3 and Ar 4 may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or N—Ar 8 to form a ring. Good. Here, “N” in “N—Ar 8 ” represents a nitrogen atom, and “Ar 8 ” represents “substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” or Examples of the “substituted or unsubstituted condensed polycyclic aromatic group” include the same groups as those exemplified above, and the substituents that these groups may have are also exemplified below. Substituents can be mentioned.
　一般式（１）中のＡｒ１～Ａｒ４で表される「置換芳香族炭化水素基」、「置換芳香族複素環基」または「置換縮合多環芳香族基」における「置換基」としては、具体的に、重水素原子、トリフルオロメチル基、シアノ基、ニトロ基；フッ素原子、塩素原子、臭素原子、ヨウ素原子などのハロゲン原子；メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｎ－ヘキシル基などの炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基；メチルオキシ基、エチルオキシ基、プロピルオキシ基などの炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基；アリル基などのアルケニル基；ベンジル基、ナフチルメチル基、フェネチル基などのアラルキル基；フェニルオキシ基、トリルオキシ基などのアリールオキシ基；ベンジルオキシ基、フェネチルオキシ基などのアリールアルキルオキシ基；フェニル基、ビフェニリル基、ターフェニリル基、ナフチル基、アントラセニル基、フェナントリル基、フルオレニル基、インデニル基、ピレニル基、ペリレニル基、フルオランテニル基、トリフェニレニル基などの芳香族炭化水素基もしくは縮合多環芳香族基；ピリジル基、フリル基、チエニル基、ピロリル基、キノリル基、イソキノリル基、ベンゾフラニル基、ベンゾチエニル基、インドリル基、カルバゾリル基、ベンゾトリアゾリル基、ベンゾオキサゾリル基、ベンゾチアゾリル基、キノキサリル基、ベンゾイミダゾリル基、ピラゾリル基、ジベンゾフラニル基、ジベンゾチエニル基、カルボリニル基などの芳香族複素環基；スチリル基、ナフチルビニル基などのアリールビニル基；アセチル基、ベンゾイル基などのアシル基；ジメチルアミノ基、ジエチルアミノ基などのジアルキルアミノ基；ジフェニルアミノ基、ジナフチルアミノ基などの芳香族炭化水素基もしくは縮合多環芳香族基で置換されたジ置換アミノ基；ジベンジルアミノ基、ジフェネチルアミノ基などのジアラルキルアミノ基；ジピリジルアミノ基、ジチエニルアミノ基などの芳香族複素環基で置換されたジ置換アミノ基；ジアリルアミノ基などのジアルケニルアミノ基；アルキル基、芳香族炭化水素基、縮合多環芳香族基、アラルキル基、芳香族複素環基またはアルケニル基から選択される置換基で置換されたジ置換アミノ基のような基をあげることができ、これらの置換基は、さらに前記例示した置換基が置換していてもよい。
　また、これらの置換基同士が単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成していてもよい。ここで、「Ｎ－Ａｒ８」は、上記一般式（１）中のＡｒ１～Ａｒ４で表される「置換もしくは無置換の芳香族炭化水素基」、「置換もしくは無置換の芳香族複素環基」または「置換もしくは無置換の縮合多環芳香族基」に関して規定した「Ｎ－Ａｒ８」と同じものを意味する。 As the “substituent” in the “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group” or “substituted condensed polycyclic aromatic group” represented by Ar 1 to Ar 4 in the general formula (1), Specifically, deuterium atom, trifluoromethyl group, cyano group, nitro group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, a linear or branched alkyl group having 1 to 6 carbon atoms such as n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group; methyloxy group A linear or branched alkyloxy group having 1 to 6 carbon atoms such as ethyloxy group and propyloxy group; alkenyl group such as allyl group; benzyl group and naphthylmethyl Group, aralkyl group such as phenethyl group; aryloxy group such as phenyloxy group and tolyloxy group; arylalkyloxy group such as benzyloxy group and phenethyloxy group; phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group; pyridyl group, furyl group, thienyl group, pyrrolyl group, quinolyl group Group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzotriazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuran Aromatic group such as thiol group, dibenzothienyl group and carbolinyl group; aryl vinyl group such as styryl group and naphthyl vinyl group; acyl group such as acetyl group and benzoyl group; dialkylamino group such as dimethylamino group and diethylamino group A disubstituted amino group substituted with an aromatic hydrocarbon group such as a diphenylamino group or a dinaphthylamino group or a condensed polycyclic aromatic group; a diaralkylamino group such as a dibenzylamino group or a diphenethylamino group; Group, disubstituted amino group substituted by aromatic heterocyclic group such as dithienylamino group; dialkenylamino group such as diallylamino group; alkyl group, aromatic hydrocarbon group, condensed polycyclic aromatic group, aralkyl group A disubstituted amino group substituted with a substituent selected from an aromatic heterocyclic group or an alkenyl group Such a group can be enumerated, and these substituents may be further substituted with the substituents exemplified above.
These substituents may be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom or N—Ar 8 to form a ring. Here, “N—Ar 8 ” means “substituted or unsubstituted aromatic hydrocarbon group” represented by Ar 1 to Ar 4 in the above general formula (1), “substituted or unsubstituted aromatic complex”. It means the same as “N—Ar 8 ” defined for “ring group” or “substituted or unsubstituted condensed polycyclic aromatic group”.
　構造式（Ｂ）、（Ｂ－１）、（Ｂ－２）、（Ｂ－３）、（Ｂ－４）、（Ｂ’）中のＲ１～Ｒ８で表される、「置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基」、「置換基を有していてもよい炭素原子数５ないし１０のシクロアルキル基」または「置換基を有していてもよい炭素原子数２ないし６の直鎖状もしくは分岐状のアルケニル基」における「炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基」、「炭素原子数５ないし１０のシクロアルキル基」または「炭素原子数２ないし６の直鎖状もしくは分岐状のアルケニル基」としては、具体的に、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｎ－ヘキシル基、シクロペンチル基、シクロヘキシル基、１－アダマンチル基、２－アダマンチル基、ビニル基、アリル基、イソプロペニル基および２－ブテニル基などをあげることができ、これらの基同士が単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成していてもよい。ここで、「Ｎ－Ａｒ８」は、上記一般式（１）中のＡｒ１～Ａｒ４で表される「置換もしくは無置換の芳香族炭化水素基」、「置換もしくは無置換の芳香族複素環基」または「置換もしくは無置換の縮合多環芳香族基」に関して規定した「Ｎ－Ａｒ８」と同じものを意味する。 In the structural formulas (B), (B-1), (B-2), (B-3), (B-4), and (B ′), “substituents” are represented by R 1 to R 8. A linear or branched alkyl group having 1 to 6 carbon atoms which may have ", a" cycloalkyl group having 5 to 10 carbon atoms which may have a substituent "or" a substituent. “Straight or branched alkenyl group having 2 to 6 carbon atoms” which may have “straight or branched alkyl group having 1 to 6 carbon atoms”, “5 to 10 carbon atoms” Specific examples of the cycloalkyl group or the linear or branched alkenyl group having 2 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Isobutyl group, tert-butyl group, n-pentyl group, isopentyl group , Neopentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-adamantyl group, vinyl group, allyl group, isopropenyl group and 2-butenyl group. May be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom or N—Ar 8 to form a ring. Here, “N—Ar 8 ” means “substituted or unsubstituted aromatic hydrocarbon group” represented by Ar 1 to Ar 4 in the above general formula (1), “substituted or unsubstituted aromatic complex”. It means the same as “N—Ar 8 ” defined for “ring group” or “substituted or unsubstituted condensed polycyclic aromatic group”.
　構造式（Ｂ）、（Ｂ－１）、（Ｂ－２）、（Ｂ－３）、（Ｂ－４）、（Ｂ’）中のＲ１～Ｒ８で表される、「置換基を有する炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基」、「置換基を有する炭素原子数５ないし１０のシクロアルキル基」または「置換基を有する炭素原子数２ないし６の直鎖状もしくは分岐状のアルケニル基」における「置換基」としては、上記一般式（１）中のＡｒ１～Ａｒ４で表される「置換芳香族炭化水素基」、「置換芳香族複素環基」または「置換縮合多環芳香族基」における「置換基」に関して示したものと同様のものをあげることができ、とりうる態様も、同様のものをあげることができる。 In the structural formulas (B), (B-1), (B-2), (B-3), (B-4), and (B ′), “substituents” are represented by R 1 to R 8. Having a straight or branched alkyl group having 1 to 6 carbon atoms "," a cycloalkyl group having 5 to 10 carbon atoms having a substituent "or" straight chain having 2 to 6 carbon atoms having a substituent " The “substituent” in the “like or branched alkenyl group” is the “substituted aromatic hydrocarbon group” or “substituted aromatic heterocyclic group” represented by Ar 1 to Ar 4 in the general formula (1). Or the thing similar to what was shown regarding the "substituent" in a "substituted condensed polycyclic aromatic group" can be mention | raise | lifted, and the aspect which can be taken can also mention the same thing.
　構造式（Ｂ）、（Ｂ－１）、（Ｂ－２）、（Ｂ－３）、（Ｂ－４）、（Ｂ’）中のＲ１～Ｒ８で表される、「置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基」または「置換基を有していてもよい炭素原子数５ないし１０のシクロアルキルオキシ基」における「炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基」または「炭素原子数５ないし１０のシクロアルキルオキシ基」としては、具体的に、メチルオキシ基、エチルオキシ基、ｎ－プロピルオキシ基、イソプロピルオキシ基、ｎ－ブチルオキシ基、ｔｅｒｔ－ブチルオキシ基、ｎ－ペンチルオキシ基、ｎ－ヘキシルオキシ基、シクロペンチルオキシ基、シクロヘキシルオキシ基、シクロヘプチルオキシ基、シクロオクチルオキシ基、１－アダマンチルオキシ基および２－アダマンチルオキシ基などをあげることができ、これらの基同士が単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成していてもよい。ここで、「Ｎ－Ａｒ８」は、上記一般式（１）中のＡｒ１～Ａｒ４で表される「置換もしくは無置換の芳香族炭化水素基」、「置換もしくは無置換の芳香族複素環基」または「置換もしくは無置換の縮合多環芳香族基」に関して規定した「Ｎ－Ａｒ８」と同じものを意味する。 In the structural formulas (B), (B-1), (B-2), (B-3), (B-4), and (B ′), “substituents” are represented by R 1 to R 8. “Carbon in 1 to 6 linear or branched alkyloxy group which may have” or “carbonoxy in 5 to 10 cycloalkyloxy group which may have a substituent” Specific examples of the “linear or branched alkyloxy group having 1 to 6 atoms” or “cycloalkyloxy group having 5 to 10 carbon atoms” specifically include a methyloxy group, an ethyloxy group, and an n-propyloxy group. Isopropyloxy group, n-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctylo group And a 1-adamantyloxy group, a 2-adamantyloxy group, etc., and these groups are bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or N—Ar 8. They may be bonded to each other to form a ring. Here, “N—Ar 8 ” means “substituted or unsubstituted aromatic hydrocarbon group” represented by Ar 1 to Ar 4 in the above general formula (1), “substituted or unsubstituted aromatic complex”. It means the same as “N—Ar 8 ” defined for “ring group” or “substituted or unsubstituted condensed polycyclic aromatic group”.
　構造式（Ｂ）、（Ｂ－１）、（Ｂ－２）、（Ｂ－３）、（Ｂ－４）、（Ｂ’）中のＲ１～Ｒ８で表される、「置換基を有する炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基」または「置換基を有する炭素原子数５ないし１０のシクロアルキルオキシ基」における「置換基」としては、上記一般式（１）中のＡｒ１～Ａｒ４で表される「置換芳香族炭化水素基」、「置換芳香族複素環基」または「置換縮合多環芳香族基」における「置換基」に関して示したものと同様のものをあげることができ、とりうる態様も、同様のものをあげることができる。 In the structural formulas (B), (B-1), (B-2), (B-3), (B-4), and (B ′), “substituents” are represented by R 1 to R 8. The “substituent” in the “straight-chain or branched alkyloxy group having 1 to 6 carbon atoms” or “cycloalkyloxy group having 5 to 10 carbon atoms having a substituent” includes the above general formula (1 The same as that described for the “substituent” in the “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group” or “substituted condensed polycyclic aromatic group” represented by Ar 1 to Ar 4 in FIG. Examples of possible modes can also be given.
　構造式（Ｂ）、（Ｂ－１）、（Ｂ－２）、（Ｂ－３）、（Ｂ－４）、（Ｂ’）中のＲ１～Ｒ８で表される、「置換もしくは無置換の芳香族炭化水素基」、「置換もしくは無置換の芳香族複素環基」または「置換もしくは無置換の縮合多環芳香族基」における「芳香族炭化水素基」、「芳香族複素環基」または「縮合多環芳香族基」としては、上記一般式（１）中のＡｒ１～Ａｒ４で表される「置換もしくは無置換の芳香族炭化水素基」、「置換もしくは無置換の芳香族複素環基」または「置換もしくは無置換の縮合多環芳香族基」における「芳香族炭化水素基」、「芳香族複素環基」または「縮合多環芳香族基」に関して示したものと同様のものをあげることができ、とりうる態様も、同様のものをあげることができる。 Represented by R 1 to R 8 in the structural formulas (B), (B-1), (B-2), (B-3), (B-4), (B ′), "Aromatic hydrocarbon group", "Aromatic heterocyclic group" in "Substituted aromatic hydrocarbon group", "Substituted or unsubstituted aromatic heterocyclic group" or "Substituted or unsubstituted condensed polycyclic aromatic group" Or a “condensed polycyclic aromatic group” is a “substituted or unsubstituted aromatic hydrocarbon group” represented by Ar 1 to Ar 4 in the general formula (1), “substituted or unsubstituted aromatic group” The same as those shown for the “aromatic hydrocarbon group”, “aromatic heterocyclic group” or “fused polycyclic aromatic group” in the “aromatic heterocyclic group” or “substituted or unsubstituted condensed polycyclic aromatic group” Examples of possible modes can also be given.
　構造式（Ｂ）、（Ｂ－１）、（Ｂ－２）、（Ｂ－３）、（Ｂ－４）、（Ｂ’）中のＲ１～Ｒ８で表される、「置換芳香族炭化水素基」、「置換芳香族複素環基」または「置換縮合多環芳香族基」における「置換基」としては、上記一般式（１）中のＡｒ１～Ａｒ４で表される「置換芳香族炭化水素基」、「置換芳香族複素環基」または「置換縮合多環芳香族基」における「置換基」に関して示したものと同様のものをあげることができ、とりうる態様も、同様のものをあげることができる。 The “substituted aromatic” represented by R 1 to R 8 in the structural formulas (B), (B-1), (B-2), (B-3), (B-4), (B ′) The “substituent” in the “hydrocarbon group”, “substituted aromatic heterocyclic group” or “substituted condensed polycyclic aromatic group” is the “substituted” represented by Ar 1 to Ar 4 in the above general formula (1). The same thing as what was shown regarding "substituent" in "aromatic hydrocarbon group", "substituted aromatic heterocyclic group" or "substituted condensed polycyclic aromatic group" can be mention | raise | lifted, and the aspect which can be taken is also the same I can give you something.
　構造式（Ｂ）、（Ｂ－１）、（Ｂ－２）、（Ｂ－３）、（Ｂ－４）、（Ｂ’）中のＲ１～Ｒ８で表される、「置換もしくは無置換のアリールオキシ基」における「アリールオキシ基」としては、具体的に、フェニルオキシ基、トリルオキシ基、ビフェニリルオキシ基、ターフェニリルオキシ基、ナフチルオキシ基、アントリルオキシ基、フェナントリルオキシ基、フルオレニルオキシ基、インデニルオキシ基、ピレニルオキシ基、ペリレニルオキシ基などをあげることができ、これらの基同士が単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成していてもよい。ここで、「Ｎ－Ａｒ８」は、上記一般式（１）中のＡｒ１～Ａｒ４で表される「置換もしくは無置換の芳香族炭化水素基」、「置換もしくは無置換の芳香族複素環基」または「置換もしくは無置換の縮合多環芳香族基」に関して規定した「Ｎ－Ａｒ８」と同じものを意味する。 Represented by R 1 to R 8 in the structural formulas (B), (B-1), (B-2), (B-3), (B-4), (B ′), The “aryloxy group” in the “substituted aryloxy group” specifically includes phenyloxy group, tolyloxy group, biphenylyloxy group, terphenylyloxy group, naphthyloxy group, anthryloxy group, phenanthryloxy group. Group, fluorenyloxy group, indenyloxy group, pyrenyloxy group, perylenyloxy group, etc., and these groups are single bond, substituted or unsubstituted methylene group, oxygen atom, sulfur atom or N-Ar. 8 may be bonded to each other via 8 to form a ring. Here, “N—Ar 8 ” means “substituted or unsubstituted aromatic hydrocarbon group” represented by Ar 1 to Ar 4 in the above general formula (1), “substituted or unsubstituted aromatic complex”. It means the same as “N—Ar 8 ” defined for “ring group” or “substituted or unsubstituted condensed polycyclic aromatic group”.
　構造式（Ｂ）、（Ｂ－１）、（Ｂ－２）、（Ｂ－３）、（Ｂ－４）、（Ｂ’）中のＲ１～Ｒ８で表される、「置換アリールオキシ基」における「置換基」としては、上記一般式（１）中のＡｒ１～Ａｒ４で表される「置換芳香族炭化水素基」、「置換芳香族複素環基」または「置換縮合多環芳香族基」における「置換基」に関して示したものと同様のものをあげることができ、とりうる態様も、同様のものをあげることができる。 “Substituted aryloxy” represented by R 1 to R 8 in the structural formulas (B), (B-1), (B-2), (B-3), (B-4), and (B ′) The “substituent” in the “group” is the “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group” or “substituted condensed polycycle” represented by Ar 1 to Ar 4 in the general formula (1). The thing similar to what was shown regarding the "substituent" in an "aromatic group" can be mention | raise | lifted, and the aspect which can be taken can also mention the same thing.
　構造式（Ｂ）、（Ｂ－２）、（Ｂ’）中のＡｒ５、Ａｒ６、Ａｒ７で表される、「置換もしくは無置換の芳香族炭化水素基」、「置換もしくは無置換の芳香族複素環基」または「置換もしくは無置換の縮合多環芳香族基」における「芳香族炭化水素基」、「芳香族複素環基」または「縮合多環芳香族基」としては、上記一般式（１）中のＡｒ１～Ａｒ４で表される「置換もしくは無置換の芳香族炭化水素基」、「置換もしくは無置換の芳香族複素環基」または「置換もしくは無置換の縮合多環芳香族基」における「芳香族炭化水素基」、「芳香族複素環基」または「縮合多環芳香族基」に関して示したものと同様のものをあげることができ、とりうる態様も、同様のものをあげることができる。 Represented by Ar 5 , Ar 6 , Ar 7 in the structural formulas (B), (B-2), (B ′), “substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted As the “aromatic hydrocarbon group”, “aromatic heterocyclic group” or “fused polycyclic aromatic group” in the “aromatic heterocyclic group” or “substituted or unsubstituted condensed polycyclic aromatic group”, the above-mentioned general “Substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” or “substituted or unsubstituted condensed polycyclic ring” represented by Ar 1 to Ar 4 in formula (1) Examples of the "aromatic hydrocarbon group", "aromatic heterocyclic group" or "condensed polycyclic aromatic group" in the "aromatic group" can be the same, and possible embodiments are also the same. I can give you something.
　構造式（Ｂ）、（Ｂ－２）、（Ｂ’）中のＡｒ５、Ａｒ６、Ａｒ７で表される、「置換芳香族炭化水素基」、「置換芳香族複素環基」または「置換縮合多環芳香族基」における「置換基」としては、上記一般式（１）中のＡｒ１～Ａｒ４で表される「置換芳香族炭化水素基」、「置換芳香族複素環基」または「置換縮合多環芳香族基」における「置換基」に関して示したものと同様のものをあげることができ、とりうる態様も、同様のものをあげることができる。 In the structural formulas (B), (B-2), and (B ′), represented by Ar 5 , Ar 6 , Ar 7 , “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group” or “ As the “substituent” in the “substituted condensed polycyclic aromatic group”, “substituted aromatic hydrocarbon group” and “substituted aromatic heterocyclic group” represented by Ar 1 to Ar 4 in the above general formula (1) Or the thing similar to what was shown regarding the "substituent" in a "substituted condensed polycyclic aromatic group" can be mention | raise | lifted, and the aspect which can be taken can also mention the same thing.
　一般式（１）において、ｎは０～４の整数を表し、ｎは０、１または２であることが好ましく、０または１であることがより好ましい。
　一般式（１）において、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４の少なくとも１つが前記構造式（Ｂ）である態様か、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４の少なくとも１つが前記構造式（Ｂ）をその置換基として有する態様、もしくは、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４の少なくとも１つが前記構造式（Ｂ）であり、かつＡｒ１、Ａｒ２、Ａｒ３、Ａｒ４の少なくとも１つが前記構造式（Ｂ）をその置換基として有する態様であるものとし、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４のいずれか２つが前記構造式（Ｂ）である態様か、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４のいずれか２つが前記構造式（Ｂ）をその置換基として有する態様、もしくは、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４のいずれか１つが前記構造式（Ｂ）であり、かつ前記構造式（Ｂ）ではないＡｒ１、Ａｒ２、Ａｒ３、Ａｒ４のいずれか１つが前記構造式（Ｂ）をその置換基として有する態様であることが好ましく、Ａｒ１およびＡｒ４が前記構造式（Ｂ）である態様か、Ａｒ１およびＡｒ４が前記構造式（Ｂ）をその置換基として有する態様、もしくは、Ａｒ１が前記構造式（Ｂ）であり、Ａｒ４が前記構造式（Ｂ）をその置換基として有する態様であることがより好ましく、Ａｒ１およびＡｒ４が前記構造式（Ｂ－１）、（Ｂ－３）または（Ｂ－４）を置換基として有する態様、もしくは、前記構造式（Ｂ－２）である態様がより好ましい。
　一般式（１）中のＡｒ１、Ａｒ２、Ａｒ３、Ａｒ４としては、芳香族炭化水素基、縮合多環芳香族基、前記構造式（Ｂ）、チエニル基、ベンゾチエニル基、ジベンゾフラニル基、ジベンゾチエニル基が好ましく、フェニル基、ビフェニリル基、ターフェニリル基、ナフチル基、フェナントリル基、フルオレニル基、前記構造式（Ｂ）、チエニル基、ベンゾチエニル基、ジベンゾフラニル基、ジベンゾチエニル基がより好ましく、フェニル基、ビフェニリル基、フルオレニル基、前記構造式（Ｂ）、ジベンゾフラニル基、ジベンゾチエニル基が特に好ましい。
　構造式（Ｂ）、（Ｂ－２）、（Ｂ’）中のＡｒ５、Ａｒ６、Ａｒ７としては、芳香族炭化水素基、縮合多環芳香族基、チエニル基、ベンゾチエニル基、ジベンゾフラニル基、ジベンゾチエニル基が好ましく、フェニル基、ビフェニリル基、ターフェニリル基、ナフチル基、フェナントリル基、フルオレニル基、チエニル基、ベンゾチエニル基、ジベンゾフラニル基、ジベンゾチエニル基がより好ましい。
　一般式（１）において、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ａｒ５、Ａｒ６、Ａｒ７のいずれか１つのみが連結基であるものとする。
　構造式（Ｂ）、（Ｂ’）において、Ｘは炭素原子または窒素原子を表し、Ｙは炭素原子、酸素原子、硫黄原子、または窒素原子を表す。ここで、Ｙが酸素原子、もしくは硫黄原子である場合、ＹはＡｒ７の連結基、もしくは置換基を有さない（Ａｒ７が存在しない）ものとし、ＸおよびＹが窒素原子である場合、Ａｒ５、Ａｒ６、Ａｒ７のいずれかひとつが連結基、もしくは置換基である（Ａｒ５、Ａｒ６、Ａｒ７のいずれかふたつが存在しない）ものとし、Ｘが窒素原子かつＹが炭素原子である場合、Ａｒ５、Ａｒ６のいずれかが連結基、もしくは置換基である（Ａｒ５、Ａｒ６のいずれかが存在しない）ものとする。
　構造式（Ｂ）、（Ｂ’）において、Ｘが窒素原子である場合、Ｙは窒素原子であることが好ましく、この場合において、Ａｒ５、Ａｒ６もしくはＡｒ７の連結基は、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４の炭素原子と結合する（構造式（Ｂ）もしくは（Ｂ’）が、Ａｒ１、Ａｒ２、Ａｒ３もしくはＡｒ４の置換基となる）のが、化合物の安定性の観点から好ましい。
　構造式（Ｂ）、（Ｂ’）において、Ｘが炭素原子である場合、Ｙは炭素原子、酸素原子、または硫黄原子であることが好ましく、酸素原子、または硫黄原子であることがより好ましい。
　構造式（Ｂ）、（Ｂ’）において、Ｘが窒素原子、かつＹが酸素原子もしくは硫黄原子である場合は本発明から除かれる。 In the general formula (1), n represents an integer of 0 to 4, and n is preferably 0, 1 or 2, and more preferably 0 or 1.
In the general formula (1), at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 is the structural formula (B), or at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 is the structure An embodiment having the formula (B) as a substituent, or at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 is the structural formula (B), and Ar 1 , Ar 2 , Ar 3 , Ar 4 Or at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 is the above-described structural formula (B), or Ar 1 , Ar 2 , Ar 3 , or Ar 4 has the structural formula (B) as a substituent, or any one of Ar 1 , Ar 2 , Ar 3 , Ar 4 is the structural formula (B) In addition, it is preferable that any one of Ar 1 , Ar 2 , Ar 3 , Ar 4 which is not the structural formula (B) has the structural formula (B) as a substituent, Ar 1 and Ar 4 Is the structural formula (B), Ar 1 and Ar 4 have the structural formula (B) as a substituent, or Ar 1 is the structural formula (B), and Ar 4 is the above-described structural formula (B). More preferred is an embodiment having the structural formula (B) as a substituent, and Ar 1 and Ar 4 have the structural formula (B-1), (B-3) or (B-4) as a substituent. The embodiment or the embodiment represented by the structural formula (B-2) is more preferable.
Ar 1 , Ar 2 , Ar 3 , Ar 4 in the general formula (1) include an aromatic hydrocarbon group, a condensed polycyclic aromatic group, the structural formula (B), a thienyl group, a benzothienyl group, and a dibenzofura. Nyl group and dibenzothienyl group are preferable, and phenyl group, biphenylyl group, terphenylyl group, naphthyl group, phenanthryl group, fluorenyl group, the structural formula (B), thienyl group, benzothienyl group, dibenzofuranyl group, dibenzothienyl group are More preferred are a phenyl group, a biphenylyl group, a fluorenyl group, the structural formula (B), a dibenzofuranyl group, and a dibenzothienyl group.
Ar 5 , Ar 6 and Ar 7 in the structural formulas (B), (B-2) and (B ′) are aromatic hydrocarbon groups, condensed polycyclic aromatic groups, thienyl groups, benzothienyl groups, dibenzos A furanyl group and a dibenzothienyl group are preferable, and a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, a thienyl group, a benzothienyl group, a dibenzofuranyl group, and a dibenzothienyl group are more preferable.
In the general formula (1), only one of R 1 , R 2 , R 3 , R 4 , Ar 5 , Ar 6 , Ar 7 is a linking group.
In the structural formulas (B) and (B ′), X represents a carbon atom or a nitrogen atom, and Y represents a carbon atom, an oxygen atom, a sulfur atom, or a nitrogen atom. Here, when Y is an oxygen atom or a sulfur atom, Y has no Ar 7 linking group or substituent (Ar 7 does not exist), and when X and Y are nitrogen atoms, Any one of Ar 5 , Ar 6 , Ar 7 is a linking group or a substituent (no two of Ar 5 , Ar 6 , Ar 7 exist), X is a nitrogen atom and Y is a carbon atom In this case, any one of Ar 5 and Ar 6 is a linking group or a substituent (any of Ar 5 and Ar 6 does not exist).
In the structural formulas (B) and (B ′), when X is a nitrogen atom, Y is preferably a nitrogen atom. In this case, the linking group of Ar 5 , Ar 6 or Ar 7 is Ar 1 , It is bonded to the carbon atom of Ar 2 , Ar 3 , Ar 4 (the structural formula (B) or (B ′) becomes a substituent of Ar 1 , Ar 2 , Ar 3 or Ar 4 ). From the viewpoint of sex.
In the structural formulas (B) and (B ′), when X is a carbon atom, Y is preferably a carbon atom, an oxygen atom, or a sulfur atom, and more preferably an oxygen atom or a sulfur atom.
In the structural formulas (B) and (B ′), the case where X is a nitrogen atom and Y is an oxygen atom or a sulfur atom is excluded from the present invention.
　本発明の有機ＥＬ素子に好適に用いられる、前記一般式（１）で表されるアリールアミン化合物は、有機ＥＬ素子の正孔注入層、正孔輸送層、発光層、電子阻止層またはキャッピング層の構成材料として使用することができる。 The arylamine compound represented by the general formula (1) that is preferably used in the organic EL device of the present invention is a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, or a capping layer of the organic EL device. It can be used as a constituent material.
　また、本発明の有機ＥＬ素子において、前記キャッピング層の厚さは、３０ｎｍ～１２０ｎｍの範囲であることが好ましく、４０ｎｍ～８０ｎｍの範囲であることがより好ましい。 In the organic EL device of the present invention, the thickness of the capping layer is preferably in the range of 30 nm to 120 nm, and more preferably in the range of 40 nm to 80 nm.
　また、本発明の有機ＥＬ素子において、前記キャッピング層を透過する光の波長が４５０ｎｍ～７５０ｎｍの範囲内における、該キャッピング層の屈折率が１．８５以上であることが好ましく、１．９０以上であることがより好ましい。 In the organic EL device of the present invention, it is preferable that the refractive index of the capping layer is 1.85 or more when the wavelength of light transmitted through the capping layer is in the range of 450 nm to 750 nm. More preferably.
　また、本発明の有機ＥＬ素子において、前記キャッピング層を２種以上の異なる構成材料を積層することによって作製してもよい。 In the organic EL device of the present invention, the capping layer may be produced by laminating two or more different constituent materials.
　本発明の有機ＥＬ素子は、透明または半透明電極の外側に設けた、半透明電極よりも屈折率の高いキャッピング層を有するため、光の取出し効率を大幅に向上することができる有機ＥＬ素子が得られる。また、キャッピング層に、前記一般式（１）で表されるアリールアミン化合物を使用することによって、４００℃以下の温度で成膜することができるので、発光素子にダメージを与えることなく、また高精細マスクを用いて各色の光の取出し効率を最適化することができるとともに、フルカラーディスプレイに好適に適用でき、色純度がよく鮮明で明るい画像を表示することができる。 Since the organic EL element of the present invention has a capping layer having a refractive index higher than that of the semi-transparent electrode provided outside the transparent or semi-transparent electrode, an organic EL element capable of greatly improving the light extraction efficiency is provided. can get. In addition, by using the arylamine compound represented by the general formula (1) for the capping layer, a film can be formed at a temperature of 400 ° C. or lower, so that the light emitting element is not damaged. The light extraction efficiency of each color can be optimized using the fine mask, and can be suitably applied to a full color display, and a clear and bright image with good color purity can be displayed.
　本発明の有機ＥＬ素子は、キャッピング層の材料として、屈折率が高く、薄膜の安定性や耐久性に優れた有機ＥＬ素子用の材料を用いているため、従来の有機ＥＬ素子に比べて、光の取出し効率を大幅に向上することができる。さらに、高効率、長寿命の有機ＥＬ素子を実現することが可能となった。 Since the organic EL element of the present invention uses a material for an organic EL element having a high refractive index and excellent thin film stability and durability as a material for the capping layer, compared with a conventional organic EL element, The light extraction efficiency can be greatly improved. Furthermore, it has become possible to realize an organic EL element with high efficiency and long life.
本発明実施例１の化合物（１－１）の１Ｈ－ＮＭＲチャート図である。1 is a 1 H-NMR chart of a compound (1-1) of Inventive Example 1. FIG. 本発明実施例２の化合物（１－３２）の１Ｈ－ＮＭＲチャート図である。3 is a 1 H-NMR chart of the compound (1-32) of Invention Example 2. FIG. 本発明実施例３の化合物（１－２）の１Ｈ－ＮＭＲチャート図である。FIG. 3 is a 1 H-NMR chart of the compound (1-2) of Invention Example 3. 本発明実施例４の化合物（１－２２）の１Ｈ－ＮＭＲチャート図である。FIG. 2 is a 1 H-NMR chart of the compound (1-22) of Invention Example 4. 本発明実施例５の化合物（１－２３）の１Ｈ－ＮＭＲチャート図である。 1 is a 1 H-NMR chart of a compound (1-23) of Inventive Example 5. FIG. 本発明実施例６の化合物（１－２５）の１Ｈ－ＮＭＲチャート図である。FIG. 6 is a 1 H-NMR chart of the compound (1-25) of Invention Example 6. 実施例１０～１３、比較例１の有機ＥＬ素子構成を示した図である。FIG. 3 is a diagram showing organic EL element configurations of Examples 10 to 13 and Comparative Example 1.
　本発明の有機ＥＬ素子に好適に用いられる、前記一般式（１）で表されるアリールアミン化合物は新規な化合物であり、これらの化合物は例えば、以下のように合成できる。例えば、１，２－ジアミノベンゼン誘導体とニトロアリール誘導体より、既知の方法によって、２－アミノアリールアゾベンゼン誘導体を合成し、ビス（アセタト－Ｏ）フェニルイオジンによる酸化的環化反応を行うことによってアリール基を有するベンゾトリアゾール誘導体を合成することができる（例えば、非特許文献４参照）。
　ここでハロゲン原子、例えばブロモ原子を置換基として有する、１，２－ジアミノベンゼン誘導体もしくはニトロアリール誘導体を用いることによって、アリール基を有するベンゾトリアゾール誘導体のブロモ置換体を合成することができる。続いて、このブロモ置換体とジアリールアミンとのウルマン反応、ブッフバルド・ハートウィッグ反応などによる縮合反応を行うことによって、本発明の一般式（１）で表されるアリールアミン化合物を合成することができる。
　また、前記合成したアリール基を有するベンゾトリアゾール誘導体に対して、Ｎ－ブロモコハク酸イミドなどによるブロモ化を行うことによっても、ブロモ化されたベンゾトリアゾール誘導体を合成することができる。ここで、ブロモ化の試薬、条件を変更することによって、置換位置の異なるブロモ置換体を得ることができる。そして、同様の反応を行うことによって、本発明の一般式（１）で表されるアリールアミン化合物を合成することができる。
　また、このブロモ置換体に対し、種々のアリールハライドとピナコールボランやビス（ピナコラート）ジボロンとの反応で合成されたボロン酸またはボロン酸エステル誘導体（例えば、非特許文献５参照）とをＳｕｚｕｋｉカップリングなどのクロスカップリング反応（例えば、非特許文献６参照）を行うことによっても、本発明の一般式（１）で表されるアリールアミン化合物を合成することができる。
　また、前記ブロモ置換体からボロン酸またはボロン酸エステル（例えば、非特許文献５参照）誘導体を合成し、種々のジアリールアミノ基を有するアリールハライドとのＳｕｚｕｋｉカップリングなどのクロスカップリング反応（例えば、非特許文献６参照）を行うことによっても、本発明の一般式（１）で表されるアリールアミン化合物を合成することができる。
　ここで、相当する置換基を有するベンゾチアゾール誘導体、ベンゾオキサゾール誘導体、もしくはインドール誘導体のブロモ置換体、もしくはブロモ化を行った後のブロモ置換体に対し、同様の反応を行うことによって、ベンゾチアゾール基、ベンゾオキサゾール基、もしくはインドール基を有する本発明の一般式（１）で表されるアリールアミン化合物を合成することができる。 The arylamine compound represented by the general formula (1) that is suitably used in the organic EL device of the present invention is a novel compound, and these compounds can be synthesized, for example, as follows. For example, a 2-aminoarylazobenzene derivative is synthesized from a 1,2-diaminobenzene derivative and a nitroaryl derivative by a known method, and an oxidative cyclization reaction with bis (acetato-O) phenyliodine is performed. A benzotriazole derivative having a group can be synthesized (see, for example, Non-Patent Document 4).
Here, by using a 1,2-diaminobenzene derivative or nitroaryl derivative having a halogen atom, for example, a bromo atom as a substituent, a bromo-substituted product of a benzotriazole derivative having an aryl group can be synthesized. Subsequently, an arylamine compound represented by the general formula (1) of the present invention can be synthesized by performing a condensation reaction such as an Ullmann reaction or a Buchwald-Hartwig reaction between the bromo-substituted product and diarylamine. .
The brominated benzotriazole derivative can also be synthesized by brominating the synthesized benzotriazole derivative having an aryl group with N-bromosuccinimide or the like. Here, bromo-substituted products having different substitution positions can be obtained by changing the bromination reagent and conditions. And the arylamine compound represented by General formula (1) of this invention is compoundable by performing the same reaction.
In addition, Suzuki coupling of a boronic acid or a boronic acid ester derivative (see, for example, Non-Patent Document 5) synthesized by reacting various aryl halides with pinacol borane or bis (pinacolato) diboron, for this bromo-substituted product. The arylamine compound represented by the general formula (1) of the present invention can also be synthesized by performing a cross coupling reaction such as (see, for example, Non-Patent Document 6).
Further, a boronic acid or a boronic acid ester (for example, see Non-Patent Document 5) derivative is synthesized from the bromo-substituted product, and a cross-coupling reaction such as Suzuki coupling with an aryl halide having various diarylamino groups (for example, The arylamine compound represented by the general formula (1) of the present invention can also be synthesized by performing Non-Patent Document 6).
Here, a benzothiazole group, a benzothiazole group, a benzothiazole derivative, a benzoxazole derivative, or a bromo substituent of an indole derivative having a corresponding substituent, or a bromo substituent after bromination, An arylamine compound represented by the general formula (1) of the present invention having a benzoxazole group or an indole group can be synthesized.
　本発明の有機ＥＬ素子に好適に用いられる、前記一般式（１）で表されるアリールアミン化合物の中で、特に好ましい化合物の具体例を以下に示すが、これらの化合物に限定されるものではない。 Specific examples of particularly preferred compounds among the arylamine compounds represented by the general formula (1) that are preferably used in the organic EL device of the present invention are shown below, but are not limited to these compounds. Absent.
Figure JPOXMLDOC01-appb-C000008
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Figure JPOXMLDOC01-appb-C000008
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Figure JPOXMLDOC01-appb-C000009
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Figure JPOXMLDOC01-appb-C000009
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Figure JPOXMLDOC01-appb-C000010
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Figure JPOXMLDOC01-appb-C000010
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Figure JPOXMLDOC01-appb-C000011
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Figure JPOXMLDOC01-appb-C000011
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Figure JPOXMLDOC01-appb-C000012
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Figure JPOXMLDOC01-appb-C000012
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Figure JPOXMLDOC01-appb-C000013
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Figure JPOXMLDOC01-appb-C000013
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Figure JPOXMLDOC01-appb-C000014
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Figure JPOXMLDOC01-appb-C000014
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Figure JPOXMLDOC01-appb-C000015
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Figure JPOXMLDOC01-appb-C000015
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Figure JPOXMLDOC01-appb-C000016
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Figure JPOXMLDOC01-appb-C000016
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Figure JPOXMLDOC01-appb-C000017
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Figure JPOXMLDOC01-appb-C000017
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Figure JPOXMLDOC01-appb-C000018
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Figure JPOXMLDOC01-appb-C000018
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Figure JPOXMLDOC01-appb-C000019
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Figure JPOXMLDOC01-appb-C000019
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Figure JPOXMLDOC01-appb-C000020
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Figure JPOXMLDOC01-appb-C000020
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Figure JPOXMLDOC01-appb-C000021
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Figure JPOXMLDOC01-appb-C000021
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Figure JPOXMLDOC01-appb-C000022
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Figure JPOXMLDOC01-appb-C000022
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Figure JPOXMLDOC01-appb-C000023
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Figure JPOXMLDOC01-appb-C000023
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Figure JPOXMLDOC01-appb-C000024
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Figure JPOXMLDOC01-appb-C000024
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Figure JPOXMLDOC01-appb-C000025
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Figure JPOXMLDOC01-appb-C000025
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Figure JPOXMLDOC01-appb-C000026
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Figure JPOXMLDOC01-appb-C000026
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Figure JPOXMLDOC01-appb-C000027
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Figure JPOXMLDOC01-appb-C000027
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Figure JPOXMLDOC01-appb-C000028
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Figure JPOXMLDOC01-appb-C000028
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Figure JPOXMLDOC01-appb-C000029
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Figure JPOXMLDOC01-appb-C000029
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Figure JPOXMLDOC01-appb-C000030
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Figure JPOXMLDOC01-appb-C000030
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Figure JPOXMLDOC01-appb-C000031
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Figure JPOXMLDOC01-appb-C000031
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Figure JPOXMLDOC01-appb-C000032
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Figure JPOXMLDOC01-appb-C000032
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Figure JPOXMLDOC01-appb-C000033
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Figure JPOXMLDOC01-appb-C000033
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Figure JPOXMLDOC01-appb-C000034
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Figure JPOXMLDOC01-appb-C000034
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Figure JPOXMLDOC01-appb-C000035
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Figure JPOXMLDOC01-appb-C000035
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Figure JPOXMLDOC01-appb-C000036
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Figure JPOXMLDOC01-appb-C000036
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Figure JPOXMLDOC01-appb-C000037
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Figure JPOXMLDOC01-appb-C000037
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Figure JPOXMLDOC01-appb-C000038
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Figure JPOXMLDOC01-appb-C000038
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Figure JPOXMLDOC01-appb-C000039
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Figure JPOXMLDOC01-appb-C000039
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Figure JPOXMLDOC01-appb-C000040
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Figure JPOXMLDOC01-appb-C000040
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Figure JPOXMLDOC01-appb-C000041
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Figure JPOXMLDOC01-appb-C000041
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Figure JPOXMLDOC01-appb-C000042
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Figure JPOXMLDOC01-appb-C000042
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Figure JPOXMLDOC01-appb-C000043
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Figure JPOXMLDOC01-appb-C000043
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Figure JPOXMLDOC01-appb-C000044
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Figure JPOXMLDOC01-appb-C000045
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Figure JPOXMLDOC01-appb-C000045
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Figure JPOXMLDOC01-appb-C000046
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Figure JPOXMLDOC01-appb-C000046
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Figure JPOXMLDOC01-appb-C000047
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Figure JPOXMLDOC01-appb-C000047
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Figure JPOXMLDOC01-appb-C000048
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Figure JPOXMLDOC01-appb-C000048
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Figure JPOXMLDOC01-appb-C000049
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Figure JPOXMLDOC01-appb-C000049
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Figure JPOXMLDOC01-appb-C000050
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Figure JPOXMLDOC01-appb-C000050
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Figure JPOXMLDOC01-appb-C000051
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Figure JPOXMLDOC01-appb-C000051
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Figure JPOXMLDOC01-appb-C000052
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Figure JPOXMLDOC01-appb-C000052
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Figure JPOXMLDOC01-appb-C000053
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Figure JPOXMLDOC01-appb-C000053
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Figure JPOXMLDOC01-appb-C000054
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Figure JPOXMLDOC01-appb-C000054
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Figure JPOXMLDOC01-appb-C000055
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Figure JPOXMLDOC01-appb-C000055
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Figure JPOXMLDOC01-appb-C000056
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Figure JPOXMLDOC01-appb-C000056
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Figure JPOXMLDOC01-appb-C000057
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Figure JPOXMLDOC01-appb-C000057
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Figure JPOXMLDOC01-appb-C000058
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Figure JPOXMLDOC01-appb-C000058
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Figure JPOXMLDOC01-appb-C000059
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Figure JPOXMLDOC01-appb-C000059
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Figure JPOXMLDOC01-appb-C000060
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Figure JPOXMLDOC01-appb-C000060
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Figure JPOXMLDOC01-appb-C000061
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Figure JPOXMLDOC01-appb-C000061
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Figure JPOXMLDOC01-appb-C000062
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Figure JPOXMLDOC01-appb-C000062
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Figure JPOXMLDOC01-appb-C000063
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Figure JPOXMLDOC01-appb-C000063
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　これらの化合物の精製はカラムクロマトグラフによる精製、シリカゲル、活性炭、活性白土などによる吸着精製、溶媒による再結晶や晶析法などによって行い、最終的には、昇華精製などによる精製を行った。物性値として、ガラス転移点（Ｔｇ）と屈折率の測定を行った。ガラス転移点（Ｔｇ）は薄膜状態の安定性の指標となるものであり、屈折率は光の取出し効率の向上に関する指標となるものである。 These compounds were purified by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, etc., recrystallization or crystallization using a solvent, and finally purification by sublimation purification or the like. As a physical property value, a glass transition point (Tg) and a refractive index were measured. The glass transition point (Tg) is an index of the stability of the thin film state, and the refractive index is an index for improving the light extraction efficiency.
　ガラス転移点（Ｔｇ）は、粉体を用いて高感度示差走査熱量計（ブルカー・エイエックスエス製、ＤＳＣ３１００Ｓ）によって測定した。 The glass transition point (Tg) was measured with a high sensitivity differential scanning calorimeter (manufactured by Bruker AXS, DSC3100S) using powder.
　屈折率は、シリコン基板の上に８０ｎｍの薄膜を作製して、分光測定装置（フィルメトリクス社製、Ｆ１０－ＲＴ－ＵＶ）を用いて測定した。 The refractive index was measured using a spectroscopic measurement device (F10-RT-UV, manufactured by Filmetrics) by preparing a thin film of 80 nm on a silicon substrate.
　本発明の有機ＥＬ素子の構造としては、例えば、トップエミッション構造の発光素子の場合、ガラス基板上に順次に、金属からなる陽極、正孔輸送層、発光層、電子輸送層、半透明陰極およびキャッピング層からなるもの、また、陽極と正孔輸送層の間に正孔注入層を有するもの、正孔輸送層と発光層の間に電子阻止層を有するもの、発光層と電子輸送層の間に正孔阻止層を有するもの、電子輸送層と陰極の間に電子注入層を有するものがあげられる。これらの多層構造においては有機層を何層か省略あるいは兼ねることが可能であり、例えば正孔輸送層と電子阻止層を兼ねた構成、電子輸送層と正孔阻止層を兼ねた構成とすることもできる。有機ＥＬ素子の各層の膜厚の合計は、２００ｎｍ～７５０ｎｍ程度が好ましく、３５０ｎｍ～６００ｎｍ程度がより好ましい。また、キャッピング層の膜厚は、例えば、３０ｎｍ～１２０ｎｍが好ましく、４０ｎｍ～８０ｎｍがより好ましい。この場合、良好な光の取出し効率が得られる。なお、キャッピング層の膜厚は、発光素子に使用する発光材料の種類、キャッピング層以外の有機ＥＬ素子の厚さなどに応じて、適宜変更することができる。 As the structure of the organic EL device of the present invention, for example, in the case of a light emitting device having a top emission structure, a metal anode, a hole transport layer, a light emitting layer, an electron transport layer, a translucent cathode, Containing a capping layer, having a hole injection layer between the anode and the hole transport layer, having an electron blocking layer between the hole transport layer and the light emitting layer, and between the light emitting layer and the electron transport layer And those having an electron injection layer between the electron transport layer and the cathode. In these multilayer structures, several organic layers can be omitted or doubled, for example, a structure that serves as both a hole transport layer and an electron blocking layer, and a structure that serves as both an electron transport layer and a hole blocking layer. You can also. The total thickness of each layer of the organic EL element is preferably about 200 nm to 750 nm, and more preferably about 350 nm to 600 nm. The film thickness of the capping layer is preferably 30 nm to 120 nm, for example, and more preferably 40 nm to 80 nm. In this case, good light extraction efficiency can be obtained. Note that the thickness of the capping layer can be changed as appropriate depending on the type of the light emitting material used for the light emitting element, the thickness of the organic EL element other than the capping layer, and the like.
　本発明の有機ＥＬ素子の陽極としては、ＩＴＯや金のような仕事関数の大きな電極材料が用いられる。 As the anode of the organic EL element of the present invention, an electrode material having a large work function such as ITO or gold is used.
　本発明の有機ＥＬ素子の正孔注入層として、分子中にトリフェニルアミン構造を３個以上、単結合またはヘテロ原子を含まない２価基で連結した構造を有するアリールアミン化合物、例えば、スターバースト型のトリフェニルアミン誘導体、種々のトリフェニルアミン４量体などの材料や銅フタロシアニンに代表されるポルフィリン化合物、ヘキサシアノアザトリフェニレンのようなアクセプター性の複素環化合物や塗布型の高分子材料などを用いることができる。これらは、単独で成膜してもよいが、他の材料とともに混合して成膜した単層として使用してもよく、単独で成膜した層同士、混合して成膜した層同士、または単独で成膜した層と混合して成膜した層の積層構造としてもよい。これらの材料は蒸着法の他、スピンコート法やインクジェット法などの公知の方法によって薄膜形成を行うことができる。 As the hole injection layer of the organic EL device of the present invention, an arylamine compound having a structure in which three or more triphenylamine structures are connected by a divalent group not containing a single bond or a hetero atom in the molecule, for example, starburst Materials such as triphenylamine derivatives of various types, various triphenylamine tetramers, porphyrin compounds represented by copper phthalocyanine, acceptor heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymer materials are used. be able to. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
　本発明の有機ＥＬ素子の正孔輸送層として、例えば、Ｎ，Ｎ’－ジフェニル－Ｎ，Ｎ’－ジ（ｍ－トリル）ベンジジン（以後、ＴＰＤと略称する）、Ｎ，Ｎ’－ジフェニル－Ｎ，Ｎ’－ジ（α－ナフチル）ベンジジン（ＮＰＤ）や１，１－ビス［４－（ジ－４－トリルアミノ）フェニル］シクロヘキサン（ＴＡＰＣ）、特に、分子中にトリフェニルアミン構造を２個、単結合またはヘテロ原子を含まない２価基で連結した構造を有するアリールアミン化合物、例えば、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラビフェニリルベンジジンなどを用いるのが好ましい。また、分子中にトリフェニルアミン構造を３個以上、単結合またはヘテロ原子を含まない２価基で連結した構造を有するアリールアミン化合物、例えば、種々のトリフェニルアミン３量体および４量体などを用いるのが好ましい。これらは、単独で成膜してもよいが、他の材料とともに混合して成膜した単層として使用してもよく、単独で成膜した層同士、混合して成膜した層同士、または単独で成膜した層と混合して成膜した層の積層構造としてもよい。これらの材料は蒸着法の他、スピンコート法やインクジェット法などの公知の方法によって薄膜形成を行うことができる。 As the hole transport layer of the organic EL device of the present invention, for example, N, N′-diphenyl-N, N′-di (m-tolyl) benzidine (hereinafter abbreviated as TPD), N, N′-diphenyl- N, N'-di (α-naphthyl) benzidine (NPD) and 1,1-bis [4- (di-4-tolylamino) phenyl] cyclohexane (TAPC), especially two triphenylamine structures in the molecule It is preferable to use an arylamine compound having a structure in which a single bond or a divalent group not containing a hetero atom is connected, for example, N, N, N ′, N′-tetrabiphenylylbenzidine. In addition, arylamine compounds having a structure in which three or more triphenylamine structures in the molecule are linked by a divalent group not containing a single bond or a hetero atom, such as various triphenylamine trimers and tetramers Is preferably used. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
　また、正孔注入層あるいは正孔輸送層において、該層に通常使用される材料に対し、さらにトリスブロモフェニルアミンヘキサクロルアンチモンなどをＰドーピングしたものや、ＴＰＤなどのベンジジン誘導体の構造をその部分構造に有する高分子化合物などを用いることができる。 Further, in the hole injection layer or the hole transport layer, the material usually used for the layer is further P-doped with trisbromophenylamine hexachloroantimony or the structure of a benzidine derivative such as TPD. A high molecular compound having a structure can be used.
　本発明の有機ＥＬ素子の電子阻止層として、４，４’，４’’－トリ（Ｎ－カルバゾリル）トリフェニルアミン（以後、ＴＣＴＡと略称する）、９，９－ビス［４－（カルバゾール－９－イル）フェニル］フルオレン、１，３－ビス（カルバゾール－９－イル）ベンゼン（以後、ｍＣＰと略称する）、２，２－ビス（４－カルバゾール－９－イルフェニル）アダマンタン（Ａｄ－Ｃｚ）などのカルバゾール誘導体、９－［４－（カルバゾール－９－イル）フェニル］－９－［４－（トリフェニルシリル）フェニル］－９Ｈ－フルオレンに代表されるトリフェニルシリル基とトリアリールアミン構造を有する化合物などの電子阻止作用を有する化合物を用いることができる。これらは、単独で成膜してもよいが、他の材料とともに混合して成膜した単層として使用してもよく、単独で成膜した層同士、混合して成膜した層同士、または単独で成膜した層と混合して成膜した層の積層構造としてもよい。これらの材料は蒸着法の他、スピンコート法やインクジェット法などの公知の方法によって薄膜形成を行うことができる。 As an electron blocking layer of the organic EL device of the present invention, 4,4 ′, 4 ″ -tri (N-carbazolyl) triphenylamine (hereinafter abbreviated as TCTA), 9,9-bis [4- (carbazole- 9-yl) phenyl] fluorene, 1,3-bis (carbazol-9-yl) benzene (hereinafter abbreviated as mCP), 2,2-bis (4-carbazol-9-ylphenyl) adamantane (Ad-Cz) ), Carbazole derivatives such as 9- [4- (carbazol-9-yl) phenyl] -9- [4- (triphenylsilyl) phenyl] -9H-fluorene and triarylamine structures A compound having an electron-blocking action such as a compound having an electron can be used. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
　本発明の有機ＥＬ素子の発光層として、Ａｌｑ３をはじめとするキノリノール誘導体の金属錯体、各種の金属錯体、アントラセン誘導体、ビススチリルベンゼン誘導体、ピレン誘導体、オキサゾール誘導体、ポリパラフェニレンビニレン誘導体などを用いることができる。また、発光層をホスト材料とドーパント材料とで構成してもよく、ホスト材料として、前記発光材料に加え、チアゾール誘導体、ベンズイミダゾール誘導体、ポリジアルキルフルオレン誘導体などを用いることができる。またドーパント材料としては、キナクリドン、クマリン、ルブレン、ペリレンおよびそれらの誘導体、ベンゾピラン誘導体、ローダミン誘導体、アミノスチリル誘導体などを用いることができる。これらは、単独で成膜してもよいが、他の材料とともに混合して成膜した単層として使用してもよく、単独で成膜した層同士、混合して成膜した層同士、または単独で成膜した層と混合して成膜した層の積層構造としてもよい。 As the light emitting layer of the organic EL device of the present invention, metal complexes of quinolinol derivatives such as Alq 3 , various metal complexes, anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, and the like are used. be able to. The light-emitting layer may be composed of a host material and a dopant material. As the host material, a thiazole derivative, a benzimidazole derivative, a polydialkylfluorene derivative, or the like can be used in addition to the light-emitting material. As the dopant material, quinacridone, coumarin, rubrene, perylene, and derivatives thereof, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, and the like can be used. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used.
　また、発光材料として燐光発光材料を使用することも可能である。燐光発光体としては、イリジウムや白金などの金属錯体の燐光発光体を使用することができる。Ｉｒ（ｐｐｙ）３などの緑色の燐光発光体、ＦＩｒｐｉｃ、ＦＩｒ６などの青色の燐光発光体、Ｂｔｐ２Ｉｒ（ａｃａｃ）などの赤色の燐光発光体などが用いられ、このときのホスト材料としては正孔注入・輸送性のホスト材料として４，４’－ジ（Ｎ－カルバゾリル）ビフェニル（ＣＢＰ）やＴＣＴＡ、ｍＣＰなどのカルバゾール誘導体などを用いることができる。電子輸送性のホスト材料として、ｐ－ビス（トリフェニルシリル）ベンゼン（ＵＧＨ２）や２，２’，２’’－（１，３，５－フェニレン）－トリス（１－フェニル－１Ｈ－ベンズイミダゾール）（ＴＰＢＩ）などを用いることができ、高性能の有機ＥＬ素子を作製することができる。 In addition, a phosphorescent material can be used as the light emitting material. As the phosphorescent emitter, a phosphorescent emitter of a metal complex such as iridium or platinum can be used. Green phosphorescent emitters such as Ir (ppy) 3 , blue phosphorescent emitters such as FIrpic and FIr6, red phosphorescent emitters such as Btp 2 Ir (acac), and the like are used as host materials. As the hole injecting / transporting host material, carbazole derivatives such as 4,4′-di (N-carbazolyl) biphenyl (CBP), TCTA, and mCP can be used. As an electron transporting host material, p-bis (triphenylsilyl) benzene (UGH2) and 2,2 ′, 2 ″-(1,3,5-phenylene) -tris (1-phenyl-1H-benzimidazole) ) (TPBI) or the like, and a high-performance organic EL element can be manufactured.
　燐光性の発光材料のホスト材料へのドープは濃度消光を避けるため、発光層全体に対して１～３０重量パーセントの範囲で、共蒸着によってドープすることが好ましい。 In order to avoid concentration quenching, it is preferable to dope the phosphorescent light-emitting material into the host material by co-evaporation in the range of 1 to 30 weight percent with respect to the entire light-emitting layer.
　また、発光材料としてＰＩＣ－ＴＲＺ、ＣＣ２ＴＡ、ＰＸＺ－ＴＲＺ、４ＣｚＩＰＮなどのＣＤＣＢ誘導体などの遅延蛍光を放射する材料を使用することも可能である（例えば、非特許文献７参照）。 Moreover, it is also possible to use a material that emits delayed fluorescence such as CDCB derivatives such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN as a light-emitting material (see, for example, Non-Patent Document 7).
　これらの材料は蒸着法の他、スピンコート法やインクジェット法などの公知の方法によって薄膜形成を行うことができる。 These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
　本発明の有機ＥＬ素子の正孔阻止層として、バソクプロイン（ＢＣＰ）などのフェナントロリン誘導体や、アルミニウム（III）ビス（２－メチル－８－キノリナート）－４－フェニルフェノレート（以後、ＢＡｌｑと略称する）などのキノリノール誘導体の金属錯体、各種の希土類錯体、トリアゾール誘導体、トリアジン誘導体、オキサジアゾール誘導体など、正孔阻止作用を有する化合物を用いることができる。これらの材料は電子輸送層の材料を兼ねてもよい。これらは、単独で成膜してもよいが、他の材料とともに混合して成膜した単層として使用してもよく、単独で成膜した層同士、混合して成膜した層同士、または単独で成膜した層と混合して成膜した層の積層構造としてもよい。これらの材料は蒸着法の他、スピンコート法やインクジェット法などの公知の方法によって薄膜形成を行うことができる。 As a hole blocking layer of the organic EL device of the present invention, a phenanthroline derivative such as bathocuproine (BCP) or aluminum (III) bis (2-methyl-8-quinolinato) -4-phenylphenolate (hereinafter abbreviated as BAlq). ) And other quinolinol derivative metal complexes, various rare earth complexes, triazole derivatives, triazine derivatives, oxadiazole derivatives, and the like can be used. These materials may also serve as the material for the electron transport layer. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
　本発明の有機ＥＬ素子の電子輸送層として、Ａｌｑ３、ＢＡｌｑをはじめとするキノリノール誘導体の金属錯体、各種金属錯体、トリアゾール誘導体、トリアジン誘導体、オキサジアゾール誘導体、チアジアゾール誘導体、ピリドインドール誘導体、カルボジイミド誘導体、キノキサリン誘導体、フェナントロリン誘導体、シロール誘導体などを用いることができる。これらは、単独で成膜してもよいが、他の材料とともに混合して成膜した単層として使用してもよく、単独で成膜した層同士、混合して成膜した層同士、または単独で成膜した層と混合して成膜した層の積層構造としてもよい。これらの材料は蒸着法の他、スピンコート法やインクジェット法などの公知の方法によって薄膜形成を行うことができる。 As an electron transport layer of the organic EL device of the present invention, metal complexes of quinolinol derivatives such as Alq 3 and BAlq, various metal complexes, triazole derivatives, triazine derivatives, oxadiazole derivatives, thiadiazole derivatives, pyridoindole derivatives, carbodiimides Derivatives, quinoxaline derivatives, phenanthroline derivatives, silole derivatives, and the like can be used. These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
　本発明の有機ＥＬ素子の電子注入層として、フッ化リチウム、フッ化セシウムなどのアルカリ金属塩、フッ化マグネシウムなどのアルカリ土類金属塩、酸化アルミニウムなどの金属酸化物などを用いることができるが、電子輸送層と陰極の好ましい選択においては、これを省略することができる。 As the electron injection layer of the organic EL device of the present invention, an alkali metal salt such as lithium fluoride and cesium fluoride, an alkaline earth metal salt such as magnesium fluoride, and a metal oxide such as aluminum oxide can be used. In the preferred selection of the electron transport layer and the cathode, this can be omitted.
　さらに、電子注入層あるいは電子輸送層において、該層に通常使用される材料に対し、さらにセシウムなどの金属をＮドーピングしたものを用いることができる。 Furthermore, in the electron injecting layer or the electron transporting layer, a material usually used for the layer and further doped with a metal such as cesium can be used.
　本発明の有機ＥＬ素子の半透明陰極として、アルミニウムのような仕事関数の低い電極材料や、マグネシウム銀合金、マグネシウムカルシウム合金、マグネシウムインジウム合金、アルミニウムマグネシウム合金のような、より仕事関数の低い合金やＩＴＯ、ＩＺＯなどが電極材料として用いられる。 As a semitransparent cathode of the organic EL device of the present invention, an electrode material having a low work function such as aluminum, an alloy having a lower work function such as a magnesium silver alloy, a magnesium calcium alloy, a magnesium indium alloy, an aluminum magnesium alloy, ITO, IZO or the like is used as an electrode material.
　本発明の有機ＥＬ素子のキャッピング層として、前記一般式（１）で表されるアリールアミン化合物などを用いるのが好ましい。これらは、単独で成膜してもよいが、他の材料とともに混合して成膜した単層として使用してもよく、単独で成膜した層同士、混合して成膜した層同士、または単独で成膜した層と混合して成膜した層の積層構造としてもよい。これらの材料は蒸着法の他、スピンコート法やインクジェット法などの公知の方法によって薄膜形成を行うことができる。 For the capping layer of the organic EL device of the present invention, it is preferable to use an arylamine compound represented by the general formula (1). These may be formed alone, but may be used as a single layer formed by mixing with other materials, layers formed alone, mixed layers formed, or A stacked structure of layers formed by mixing with a layer formed alone may be used. These materials can be formed into a thin film by a known method such as a spin coating method or an ink jet method in addition to a vapor deposition method.
　なお、上記では、トップエミッション構造の有機ＥＬ素子について説明したが、本発明はこれに限定されるものではなく、ボトムエミッション構造の有機ＥＬ素子や、上部および底部の両方向から発光するデュアルエミッション構造の有機ＥＬ素子についても、同様に適用することができる。これらの場合、光が発光素子から外部に取出される方向にある電極は、透明又は半透明である必要がある。 In the above description, the organic EL element having the top emission structure has been described. However, the present invention is not limited to this, and the organic EL element having the bottom emission structure or the dual emission structure that emits light from both the top and bottom directions is used. The same applies to organic EL elements. In these cases, an electrode in a direction in which light is extracted from the light emitting element to the outside needs to be transparent or translucent.
　キャッピング層を構成する材料の屈折率は、隣接する電極の屈折率よりも大きいことが好ましい。すなわち、キャッピング層によって、有機ＥＬ素子における光の取出し効率は向上するが、その効果は、キャッピング層と、キャッピング層に接している材料との界面での反射率が大きい方が、光干渉の効果が大きいために有効である。そのため、キャッピング層を構成する材料の屈折率は、隣接する電極の屈折率よりも大きい方が好ましく、屈折率が１．７０以上であればよいが、１．８０以上がより好ましく、１．８５以上であることが特に好ましい。 The refractive index of the material constituting the capping layer is preferably larger than the refractive index of the adjacent electrode. In other words, the light extraction efficiency of the organic EL element is improved by the capping layer, but the effect is that the higher the reflectance at the interface between the capping layer and the material in contact with the capping layer, the more effective the light interference. Is effective because of its large size. Therefore, the refractive index of the material constituting the capping layer is preferably larger than the refractive index of the adjacent electrode, and the refractive index may be 1.70 or more, more preferably 1.80 or more, and 1.85. The above is particularly preferable.
　以下、本発明の実施の形態について、実施例により具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, embodiments of the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.
　＜Ｎ，Ｎ’－ビス｛４－（２Ｈ－ベンゾ［１，２，３］トリアゾール－２－イル）フェニル｝－Ｎ，Ｎ’－ジフェニル－４，４’－ジアミノ－１，１’－ビフェニル（化合物（１－１））の合成＞
　窒素置換した反応容器に、２－（４－ブロモフェニル）－２Ｈ－ベンゾ［１，２，３］トリアゾール４．２ｇ、Ｎ，Ｎ’－ジフェニルベンジジン２．３ｇ、ｔｅｒｔ－ブトキシナトリウム２．０ｇ、トルエン５０ｍｌを加え、３０分間超音波を照射しながら窒素ガスを通気した。酢酸パラジウム６２．０ｍｇ、トリ－ｔｅｒｔ－ブチルホスフィン０．２ｍｌを加えて加熱し、９１℃で５時間攪拌した。室温まで冷却した後、トルエン５０ｍｌを加え、抽出操作を行うことによって有機層を採取した。有機層を濃縮した後、カラムクロマトグラフ（担体：ＮＨシリカゲル、溶離液：トルエン／ｎ－ヘキサン）によって精製し、さらに、ｎ－ヘキサン１００ｍｌを用いた分散洗浄を行うことによって、Ｎ，Ｎ’－ビス｛４－（２Ｈ－ベンゾ［１，２，３］トリアゾール－２－イル）フェニル｝－Ｎ，Ｎ’－ジフェニル－４，４’－ジアミノ－１，１’－ビフェニル（化合物（１－１））の黄色粉体３．３ｇ（収率６６％）を得た。 <N, N′-bis {4- (2H-benzo [1,2,3] triazol-2-yl) phenyl} -N, N′-diphenyl-4,4′-diamino-1,1′-biphenyl Synthesis of (Compound (1-1))>
Into a nitrogen-substituted reaction vessel, 4.2 g of 2- (4-bromophenyl) -2H-benzo [1,2,3] triazole, 2.3 g of N, N′-diphenylbenzidine, 2.0 g of sodium tert-butoxy, 50 ml of toluene was added, and nitrogen gas was bubbled while irradiating ultrasonic waves for 30 minutes. 62.0 mg of palladium acetate and 0.2 ml of tri-tert-butylphosphine were added and heated, followed by stirring at 91 ° C. for 5 hours. After cooling to room temperature, 50 ml of toluene was added, and an organic layer was collected by performing an extraction operation. After concentrating the organic layer, it is purified by column chromatography (carrier: NH silica gel, eluent: toluene / n-hexane), and further dispersed and washed with 100 ml of n-hexane, whereby N, N′- Bis {4- (2H-benzo [1,2,3] triazol-2-yl) phenyl} -N, N′-diphenyl-4,4′-diamino-1,1′-biphenyl (compound (1-1 )) Yellow powder 3.3g (yield 66%) was obtained.
　得られた黄色粉体についてＮＭＲを使用して構造を同定した。
　１Ｈ－ＮＭＲ（ＴＨＦ－ｄ８）で以下の３４個の水素のシグナルを検出した。
　δ（ｐｐｍ）＝８．２６（４Ｈ）、７．８９（４Ｈ）、７．６０（４Ｈ）、７．３９（４Ｈ）、７．３３（４Ｈ）、７．２４（４Ｈ）、７．２１（８Ｈ）、７．１０（２Ｈ）。 The structure of the obtained yellow powder was identified using NMR.
The following 34 hydrogen signals were detected by 1 H-NMR (THF-d 8 ).
δ (ppm) = 8.26 (4H), 7.89 (4H), 7.60 (4H), 7.39 (4H), 7.33 (4H), 7.24 (4H), 7.21 (8H), 7.10 (2H).
　＜Ｎ，Ｎ’－ビス（２－フェニル－２Ｈ－ベンゾ［１，２，３］トリアゾール－５－イル）－Ｎ，Ｎ’－ジフェニル－４，４’－ジアミノ－１，１’－ビフェニル（化合物（１－３２））の合成＞
　窒素置換した反応容器に、５－ブロモ－２－フェニル－２Ｈ－ベンゾ［１，２，３］トリアゾール４．１ｇ、Ｎ，Ｎ’－ジフェニルベンジジン２．３ｇ、ｔｅｒｔ－ブトキシナトリウム２．０ｇ、トルエン５０ｍｌを加え、３０分間超音波を照射しながら窒素ガスを通気した。酢酸パラジウム６２．０ｍｇ、トリ－ｔｅｒｔ－ブチルホスフィン０．２ｍｌを加えて加熱し、９１℃で３．５時間攪拌した。室温まで冷却した後、トルエン５０ｍｌを加え、抽出操作を行うことによって有機層を採取した。有機層を濃縮した後、カラムクロマトグラフ（担体：シリカゲル、溶離液：トルエン／ｎ－ヘキサン）によって精製した。さらに、ＴＨＦ２５ｍｌを加えて溶解した後、メタノール１００ｍｌを滴下することによって晶析精製し、Ｎ，Ｎ’－ビス（２－フェニル－２Ｈ－ベンゾ［１，２，３］トリアゾール－５－イル）－Ｎ，Ｎ’－ジフェニル－４，４’－ジアミノ－１，１’－ビフェニル（化合物（１－３２））の黄褐色粉体４．０ｇ（収率：８０％）を得た。 <N, N′-bis (2-phenyl-2H-benzo [1,2,3] triazol-5-yl) -N, N′-diphenyl-4,4′-diamino-1,1′-biphenyl ( Synthesis of Compound (1-32))>
Into a nitrogen-substituted reaction vessel, 4.1 g of 5-bromo-2-phenyl-2H-benzo [1,2,3] triazole, 2.3 g of N, N′-diphenylbenzidine, 2.0 g of tert-butoxy sodium, toluene 50 ml was added and nitrogen gas was aerated while irradiating ultrasonic waves for 30 minutes. 62.0 mg of palladium acetate and 0.2 ml of tri-tert-butylphosphine were added and heated, followed by stirring at 91 ° C. for 3.5 hours. After cooling to room temperature, 50 ml of toluene was added, and an organic layer was collected by performing an extraction operation. The organic layer was concentrated and then purified by column chromatography (carrier: silica gel, eluent: toluene / n-hexane). Further, 25 ml of THF was added and dissolved, and then purified by crystallization by dropwise addition of 100 ml of methanol, and N, N′-bis (2-phenyl-2H-benzo [1,2,3] triazol-5-yl)- 4.0 g (yield: 80%) of a tan powder of N, N′-diphenyl-4,4′-diamino-1,1′-biphenyl (compound (1-32)) was obtained.
　得られた黄褐色粉体についてＮＭＲを使用して構造を同定した。
　１Ｈ－ＮＭＲ（ＴＨＦ－ｄ８）で以下の３４個の水素のシグナルを検出した。
　δ（ｐｐｍ）＝８．３２（４Ｈ）、７．８１（２Ｈ）、７．５９（４Ｈ）、７．５４（４Ｈ）、７．４３（２Ｈ）、７．４０（２Ｈ）、７．３２（４Ｈ）、７．２８（２Ｈ）、７．２０（４Ｈ）、７．１８（４Ｈ）、７．０９（２Ｈ）。 The structure of the resulting tan powder was identified using NMR.
The following 34 hydrogen signals were detected by 1 H-NMR (THF-d 8 ).
δ (ppm) = 8.32 (4H), 7.81 (2H), 7.59 (4H), 7.54 (4H), 7.43 (2H), 7.40 (2H), 7.32 (4H), 7.28 (2H), 7.20 (4H), 7.18 (4H), 7.09 (2H).
　＜Ｎ，Ｎ’－ビス｛４－（２Ｈ－ベンゾ［１，２，３］トリアゾール－２－イル）フェニル｝－Ｎ，Ｎ’－ジフェニル－４，４’’－ジアミノ－１，１’：４’，１’’－ターフェニル（化合物（１－２））の合成＞
　窒素置換した反応容器に、４，４’’－ジヨード－１，１’：４’，１’’－ターフェニル１４．０ｇ、｛４－（２Ｈ－ベンゾ［１，２，３］トリアゾール－２－イル）フェニル｝フェニルアミン１８．３ｇ、炭酸カリウム１３．２ｇ、銅粉０．３ｇ、亜硫酸水素ナトリウム０．９ｇ、３，５－ジ－ｔｅｒｔ－ブチルサリチル酸０．７ｇ、ドデシルベンゼン３０ｍｌを加えて加熱し、２１０℃で４４時間撹拌した。室温まで放冷した後、トルエン５０ｍｌを加え、析出物をろ過によって採取した。析出物に１，２－ジクロロベンゼン２３０ｍｌを加え、加熱することによって溶解し、熱時ろ過によって不溶物を除去した。ろ液を濃縮し、１，２－ジクロロベンゼンを用いた晶析精製を行った後、メタノールを用いた分散洗浄を行うことによって、Ｎ，Ｎ’－ビス｛４－（２Ｈ－ベンゾ［１，２，３］トリアゾール－２－イル）フェニル｝－Ｎ，Ｎ’－ジフェニル－４，４’’－ジアミノ－１，１’：４’，１’’－ターフェニル（化合物（１－２））の黄色粉体２２．２ｇ（収率９６％）を得た。 <N, N′-bis {4- (2H-benzo [1,2,3] triazol-2-yl) phenyl} -N, N′-diphenyl-4,4 ″ -diamino-1,1 ′: Synthesis of 4 ′, 1 ″ -terphenyl (compound (1-2))>
In a nitrogen-substituted reaction vessel, 14.0 g of 4,4 ″ -diiodo-1,1 ′: 4 ′, 1 ″ -terphenyl, {4- (2H-benzo [1,2,3] triazole-2 -Yl) phenyl} phenylamine 18.3 g, potassium carbonate 13.2 g, copper powder 0.3 g, sodium hydrogen sulfite 0.9 g, 3,5-di-tert-butylsalicylic acid 0.7 g, dodecylbenzene 30 ml were added. Heated and stirred at 210 ° C. for 44 hours. After cooling to room temperature, 50 ml of toluene was added, and the precipitate was collected by filtration. To the precipitate, 230 ml of 1,2-dichlorobenzene was added and dissolved by heating, and insoluble matters were removed by hot filtration. The filtrate was concentrated, purified by crystallization using 1,2-dichlorobenzene, and then dispersed and washed with methanol, whereby N, N′-bis {4- (2H-benzo [1, 2,3] triazol-2-yl) phenyl} -N, N′-diphenyl-4,4 ″ -diamino-1,1 ′: 4 ′, 1 ″ -terphenyl (compound (1-2)) Of yellow powder was obtained (yield 96%).
　得られた黄色粉体についてＮＭＲを使用して構造を同定した。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）で以下の３８個の水素のシグナルを検出した。
　δ（ｐｐｍ）＝８．２４（４Ｈ）、７．９９－７．９２（４Ｈ）、７．７２－７．５８（７Ｈ）、７．５０－７．１２（２３Ｈ）。 The structure of the obtained yellow powder was identified using NMR.
The following 38 hydrogen signals were detected by 1 H-NMR (CDCl 3 ).
δ (ppm) = 8.24 (4H), 7.99-7.92 (4H), 7.72-7.58 (7H), 7.50-7.12 (23H).
　＜Ｎ，Ｎ’－ビス｛４－（ベンゾオキサゾール－２－イル）フェニル｝－Ｎ，Ｎ’－ジフェニル－４，４’’－ジアミノ－１，１’：４’，１’’－ターフェニル（化合物（１－２２））の合成＞
　実施例３において、｛４－（２Ｈ－ベンゾ［１，２，３］トリアゾール－２－イル）フェニル｝フェニルアミンに代えて、｛４－（ベンゾオキサゾール－２－イル）フェニル｝フェニルアミンを用い、同様の条件で反応を行うことによって、Ｎ，Ｎ’－ビス｛４－（ベンゾオキサゾール－２－イル）フェニル｝－Ｎ，Ｎ’－ジフェニル－４，４’’－ジアミノ－１，１’：４’，１’’－ターフェニル（化合物（１－２２））の黄色粉体１２．４ｇ（収率４７％）を得た。 <N, N′-bis {4- (benzoxazol-2-yl) phenyl} -N, N′-diphenyl-4,4 ″ -diamino-1,1 ′: 4 ′, 1 ″ -terphenyl Synthesis of (Compound (1-22))>
In Example 3, {4- (benzoxazol-2-yl) phenyl} phenylamine was used in place of {4- (2H-benzo [1,2,3] triazol-2-yl) phenyl} phenylamine By conducting the reaction under the same conditions, N, N′-bis {4- (benzoxazol-2-yl) phenyl} -N, N′-diphenyl-4,4 ″ -diamino-1,1 ′ : 12.4 g (yield 47%) of 4 ′, 1 ″ -terphenyl (compound (1-22)) as a yellow powder.
　得られた黄色粉体についてＮＭＲを使用して構造を同定した。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）で以下の３８個の水素のシグナルを検出した。
　δ（ｐｐｍ）＝８．１３（４Ｈ）、７．８０－７．５５（１１Ｈ）、７．５０－７．１６（２３Ｈ）。 The structure of the obtained yellow powder was identified using NMR.
The following 38 hydrogen signals were detected by 1 H-NMR (CDCl 3 ).
δ (ppm) = 8.13 (4H), 7.80-7.55 (11H), 7.50-7.16 (23H).
　＜Ｎ，Ｎ’－ビス｛４－（ベンゾオキサゾール－２－イル）フェニル｝－Ｎ，Ｎ’－ジフェニル－４，４’－ジアミノ－１，１’－ビフェニル（化合物（１－２３））の合成＞
　実施例１において、２－（４－ブロモフェニル）－２Ｈ－ベンゾ［１，２，３］トリアゾールに代えて、２－（４－ブロモフェニル）－ベンゾオキサゾールを用い、同様の条件で反応を行うことによって、Ｎ，Ｎ’－ビス｛４－（ベンゾオキサゾール－２－イル）フェニル｝－Ｎ，Ｎ’－ジフェニル－４，４’－ジアミノ－１，１’－ビフェニル（化合物（１－２３））の淡黄色粉体８．８ｇ（収率５４％）を得た。 <N, N′-bis {4- (benzoxazol-2-yl) phenyl} -N, N′-diphenyl-4,4′-diamino-1,1′-biphenyl (compound (1-23)) Synthesis>
In Example 1, instead of 2- (4-bromophenyl) -2H-benzo [1,2,3] triazole, 2- (4-bromophenyl) -benzoxazole is used and the reaction is carried out under the same conditions. N, N′-bis {4- (benzoxazol-2-yl) phenyl} -N, N′-diphenyl-4,4′-diamino-1,1′-biphenyl (compound (1-23) 8.8 g (yield 54%) was obtained.
　得られた淡黄色粉体についてＮＭＲを使用して構造を同定した。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）で以下の３４個の水素のシグナルを検出した。
　δ（ｐｐｍ）＝８．１２（４Ｈ）、７．８０－７．７２（２Ｈ）、７．６０－７．５３（５Ｈ）、７．４１－７．１４（２３Ｈ）。 The structure of the obtained pale yellow powder was identified using NMR.
The following 34 hydrogen signals were detected by 1 H-NMR (CDCl 3 ).
δ (ppm) = 8.12 (4H), 7.80-7.72 (2H), 7.60-7.53 (5H), 7.41-7.14 (23H).
　＜Ｎ，Ｎ’－ビス｛４－（ベンゾチアゾール－２－イル）フェニル｝－Ｎ，Ｎ’－ジフェニル－４，４’－ジアミノ－１，１’－ビフェニル（化合物（１－２５））の合成＞
　実施例１において、２－（４－ブロモフェニル）－２Ｈ－ベンゾ［１，２，３］トリアゾールに代えて、２－（４－ブロモフェニル）－ベンゾチアゾールを用い、同様の条件で反応を行うことによって、Ｎ，Ｎ’－ビス｛４－（ベンゾチアゾール－２－イル）フェニル｝－Ｎ，Ｎ’－ジフェニル－４，４’－ジアミノ－１，１’－ビフェニル（化合物（１－２５））の淡黄色粉体９．３ｇ（収率６２％）を得た。 <N, N′-bis {4- (benzothiazol-2-yl) phenyl} -N, N′-diphenyl-4,4′-diamino-1,1′-biphenyl (compound (1-25)) Synthesis>
In Example 1, instead of 2- (4-bromophenyl) -2H-benzo [1,2,3] triazole, 2- (4-bromophenyl) -benzothiazole is used and the reaction is performed under the same conditions. N, N′-bis {4- (benzothiazol-2-yl) phenyl} -N, N′-diphenyl-4,4′-diamino-1,1′-biphenyl (compound (1-25) 9.3 g (yield 62%).
　得られた淡黄色粉体についてＮＭＲを使用して構造を同定した。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）で以下の３４個の水素のシグナルを検出した。
　δ（ｐｐｍ）＝８．１０－７．８８（８Ｈ）、７．６０－７．１３（２６Ｈ）。 The structure of the obtained pale yellow powder was identified using NMR.
The following 34 hydrogen signals were detected by 1 H-NMR (CDCl 3 ).
δ (ppm) = 8.10-7.88 (8H), 7.60-7.13 (26H).
　＜Ｎ，Ｎ’－ビス｛４－（ベンゾチアゾール－２－イル）フェニル｝－Ｎ，Ｎ’－ジフェニル－４，４’’－ジアミノ－１，１’：４’，１’’－ターフェニル（化合物（１－２７））の合成＞
　窒素置換した反応容器に、Ｎ－｛４－（ベンゾチアゾール－２－イル）フェニル｝フェニルアミン９．３ｇ、４，４’’－ジヨード－１，１’：４’，１’’－ターフェニル７．１ｇ、ｔｅｒｔ－ブトキシナトリウム４．６ｇ、トルエン１４０ｍｌを加え、３０分間超音波を照射しながら窒素を通気した。酢酸パラジウム０．２０ｇ、ｔｅｒｔ－ブチルホスフィンの５０％（ｖ／ｖ）トルエン溶液０．５ｇを加えて加熱し、攪拌しながら３時間加熱還流した。室温まで冷却し、ろ過によって析出物を採取した後、１，２－ジクロロベンゼン／メタノールの混合溶媒を用いた晶析精製を繰り返すことによって、Ｎ，Ｎ’－ビス｛４－（ベンゾチアゾール－２－イル）フェニル｝－Ｎ，Ｎ’－ジフェニル－４，４’’－ジアミノ－１，１’：４’，１’’－ターフェニル（化合物（１－２７））の緑色粉体７．０ｇ（収率５８％）を得た。 <N, N′-bis {4- (benzothiazol-2-yl) phenyl} -N, N′-diphenyl-4,4 ″ -diamino-1,1 ′: 4 ′, 1 ″ -terphenyl Synthesis of (Compound (1-27))
In a reaction vessel purged with nitrogen, 9.3 g of N- {4- (benzothiazol-2-yl) phenyl} phenylamine, 4,4 ″ -diiodo-1,1 ′: 4 ′, 1 ″ -terphenyl 7.1 g, 4.6 g of tert-butoxy sodium, and 140 ml of toluene were added, and nitrogen was bubbled while irradiating ultrasonic waves for 30 minutes. 0.20 g of palladium acetate and 0.5 g of a 50% (v / v) toluene solution of tert-butylphosphine were added and heated, and the mixture was heated to reflux with stirring for 3 hours. After cooling to room temperature and collecting the precipitate by filtration, crystallization purification using a mixed solvent of 1,2-dichlorobenzene / methanol is repeated to obtain N, N′-bis {4- (benzothiazole-2 -Yl) phenyl} -N, N′-diphenyl-4,4 ″ -diamino-1,1 ′: 7.0 g of green powder of 4 ′, 1 ″ -terphenyl (compound (1-27)) (Yield 58%) was obtained.
　本発明の化合物について、高感度示差走査熱量計（ブルカー・エイエックスエス製、ＤＳＣ３１００Ｓ）によってガラス転移点を求めた。
　　　　　　　　　　　　　　　　　ガラス転移点
　　例示化合物（１－１）　　　　　　１２５℃
　　例示化合物（１－３２）　　　　　１１０℃
　　例示化合物（１－２）　　　　　　１３５℃
　　例示化合物（１－２２）　　　　　１３７℃
　　例示化合物（１－２３）　　　　　１２８℃
　　例示化合物（１－２５）　　　　　１２７℃
　　例示化合物（１－２７）　　　　　１３７℃ About the compound of this invention, the glass transition point was calculated | required with the high sensitivity differential scanning calorimeter (The product made by Bruker AXS, DSC3100S).
Glass transition point Exemplary compound (1-1) 125 ° C
Exemplary Compound (1-32) 110 ° C.
Exemplary Compound (1-2) 135 ° C
Exemplary Compound (1-22) 137 ° C
Exemplary Compound (1-23) 128 ° C
Exemplary Compound (1-25) 127 ° C.
Exemplary Compound (1-27) 137 ° C
　本発明の化合物は１００℃以上のガラス転移点を有している。このことは、本発明の化合物において薄膜状態が安定であることを示すものである。 The compound of the present invention has a glass transition point of 100 ° C. or higher. This indicates that the thin film state is stable in the compound of the present invention.
　本発明の化合物を用いて、シリコン基板の上に膜厚８０ｎｍの蒸着膜を作製して、分光測定装置（フィルメトリクス社製、Ｆ１０－ＲＴ－ＵＶ）を用いて６３３ｎｍにおける屈折率を測定した。比較のために、下記構造式の比較化合物（２－１）、（２－２）およびＡｌｑ３についても測定した（例えば、特許文献３参照）。
　　　　　　　　　　　　　　　　　　 　屈折率
　　例示化合物（１－１）　　　　　　　１．９０
　　例示化合物（１－３２）　　　　　　１．９０
　　例示化合物（１－２）　　　　　　　１．９０
　　例示化合物（１－２２）　　　　　　１．８９
　　例示化合物（１－２３）　　　　　　１．９３
　　例示化合物（１－２５）　　　　　　１．９３
　　例示化合物（１－２７）　　　　　　１．９１
　　比較化合物（２－１）　　　　　　　１．８１
　　比較化合物（２－２）　　　　　　　１．８０
　　比較化合物（Ａｌｑ３）　　　　　　 １．７０ Using the compound of the present invention, a deposited film having a thickness of 80 nm was formed on a silicon substrate, and the refractive index at 633 nm was measured using a spectroscopic measurement apparatus (F10-RT-UV, manufactured by Filmetrics). For comparison, the comparative compounds (2-1), (2-2) and Alq 3 having the following structural formula were also measured (see, for example, Patent Document 3).
Refractive index Exemplary compound (1-1) 1.90
Exemplary Compound (1-32) 1.90
Exemplary Compound (1-2) 1.90
Exemplary Compound (1-22) 1.89
Exemplary Compound (1-23) 1.93
Exemplary Compound (1-25) 1.93
Exemplary Compound (1-27) 1.91
Comparative compound (2-1) 1.81
Comparative compound (2-2) 1.80
Comparative compound (Alq 3 )   1.70
Figure JPOXMLDOC01-appb-C000064
 　　　　　　　　　　　　　　　　　　　　　　　　　（２－１）
Figure JPOXMLDOC01-appb-C000064
 (2-1)
Figure JPOXMLDOC01-appb-C000065
 　　　　　　　　　　　　　　　　　　　　　　　　　（２－２）
Figure JPOXMLDOC01-appb-C000065
 (2-2)
　このように本発明の化合物は比較化合物（２－１）、（２－２）およびＡｌｑ３の屈折率１．７０～１．８１より大きい値を有しており、大きな有機ＥＬ素子における光の取出し効率の向上が期待できる。 As described above, the compound of the present invention has a value higher than the refractive index of 1.70 to 1.81 of the comparative compounds (2-1), (2-2) and Alq 3 , The improvement of the extraction efficiency can be expected.
　有機ＥＬ素子は、図７に示すように、ガラス基板１上に金属陽極２として反射ＩＴＯ電極をあらかじめ形成したものの上に、正孔注入層３、正孔輸送層４、発光層５、電子輸送層６、電子注入層７、陰極８、キャッピング層９の順に蒸着して作製した。 As shown in FIG. 7, the organic EL element has a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport on a glass substrate 1 on which a reflective ITO electrode is previously formed as a metal anode 2. The layer 6, the electron injection layer 7, the cathode 8, and the capping layer 9 were deposited in this order.
　具体的には、膜厚１５０ｎｍのＩＴＯを成膜したガラス基板１をイソプロピルアルコール中にて超音波洗浄を２０分間行った後、２５０℃に加熱したホットプレート上にて１０分間乾燥を行った。その後、ＵＶオゾン処理を２分間行った後、このＩＴＯ付きガラス基板を真空蒸着機内に取り付け、０．００１Ｐａ以下まで減圧した。続いて、金属陽極２を覆うように正孔注入層３として、下記構造式の化合物（ＨＩＭ－１）を膜厚５ｎｍとなるように形成した。この正孔注入層３の上に、正孔輸送層４として前記比較化合物（２－１）を膜厚７０ｎｍとなるように形成した。この正孔輸送層４の上に、発光層５として化合物ＥＭＤ－１（ＳＦＣ株式会社製ＮＵＢＤ３７０）と化合物ＥＭＨ－１（ＳＦＣ株式会社製ＡＢＨ１１３）を、蒸着速度比がＥＭＤ－１：ＥＭＨ－１＝５：９５となる蒸着速度で二元蒸着を行い、膜厚２５ｎｍとなるように形成した。この発光層５の上に、電子輸送層６として下記構造式の化合物（ＥＴＭ－１）と下記構造式の化合物（ＥＴＭ－２）を、蒸着速度比が（ＥＴＭ－１）：（ＥＴＭ－２）＝５０：５０となる蒸着速度で二元蒸着を行い、膜厚３０ｎｍとなるように形成した。この電子輸送層６の上に、電子注入層７としてフッ化リチウムを膜厚０．５ｎｍとなるように形成した。この電子注入層７の上に、陰極８としてマグネシウム銀合金を膜厚１４ｎｍとなるように形成した。最後に、キャッピング層９として実施例１の化合物（１－１）を膜厚６０ｎｍとなるように形成した。作製した有機ＥＬ素子について、大気中、常温で特性測定を行った。
　作製した有機ＥＬ素子に直流電圧を印加した発光特性の測定結果を表１にまとめて示した。 Specifically, the glass substrate 1 formed with ITO having a thickness of 150 nm was subjected to ultrasonic cleaning in isopropyl alcohol for 20 minutes, and then dried on a hot plate heated to 250 ° C. for 10 minutes. Then, after performing UV ozone treatment for 2 minutes, this glass substrate with ITO was attached in a vacuum evaporation machine, and pressure was reduced to 0.001 Pa or less. Subsequently, a compound (HIM-1) having the following structural formula was formed to a thickness of 5 nm as a hole injection layer 3 so as to cover the metal anode 2. On the hole injection layer 3, the comparative compound (2-1) was formed as a hole transport layer 4 so as to have a film thickness of 70 nm. On this hole transport layer 4, compound EMD-1 (NUBD370 manufactured by SFC Co., Ltd.) and compound EMH-1 (ABH113 manufactured by SFC Co., Ltd.) are used as the light emitting layer 5, and the deposition rate ratio is EMD-1: EMH-1. Binary vapor deposition was performed at a vapor deposition rate of 5:95, and a film thickness of 25 nm was formed. On this light emitting layer 5, a compound (ETM-1) having the following structural formula and a compound (ETM-2) having the following structural formula are formed as the electron transporting layer 6, and the deposition rate ratio is (ETM-1) :( ETM-2) ) = 50: 50, binary deposition was performed at a deposition rate of 30:50 to form a film thickness of 30 nm. On the electron transport layer 6, lithium fluoride was formed as the electron injection layer 7 so as to have a film thickness of 0.5 nm. On the electron injection layer 7, a magnesium silver alloy was formed as a cathode 8 so as to have a film thickness of 14 nm. Finally, the compound (1-1) of Example 1 was formed as the capping layer 9 so as to have a film thickness of 60 nm. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere.
Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the manufactured organic EL element.
Figure JPOXMLDOC01-appb-C000066
 　　　　　　　　　　　　　　　　　　　　　　　　　（ＨＩＭ－１）
Figure JPOXMLDOC01-appb-C000066
 (HIM-1)
Figure JPOXMLDOC01-appb-C000067
 　　　　　　　　　　　　　　　　　　　　　　　　　（ＥＴＭ－１）
Figure JPOXMLDOC01-appb-C000067
 (ETM-1)
Figure JPOXMLDOC01-appb-C000068
 　　　　　　　　　　　　　　　　　　　　　　　　　（ＥＴＭ－２）
Figure JPOXMLDOC01-appb-C000068
 (ETM-2)
　実施例１０において、キャッピング層９として実施例１の化合物（１－１）に代えて実施例２の化合物（１－３２）を膜厚６０ｎｍとなるように形成した以外は、同様の条件で有機ＥＬ素子を作製した。作製した有機ＥＬ素子について、大気中、常温で特性測定を行った。作製した有機ＥＬ素子に直流電圧を印加した発光特性の測定結果を表１にまとめて示した。 In Example 10, the organic layer was formed under the same conditions except that the compound (1-32) of Example 2 was formed to a film thickness of 60 nm instead of the compound (1-1) of Example 1 as the capping layer 9. An EL element was produced. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere. Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the manufactured organic EL element.
　実施例１０において、キャッピング層９として実施例１の化合物（１－１）に代えて実施例３の化合物（１－２）を膜厚６０ｎｍとなるように形成した以外は、同様の条件で有機ＥＬ素子を作製した。作製した有機ＥＬ素子について、大気中、常温で特性測定を行った。作製した有機ＥＬ素子に直流電圧を印加した発光特性の測定結果を表１にまとめて示した。 In Example 10, the organic layer was formed under the same conditions except that the compound (1-2) of Example 3 was formed to a film thickness of 60 nm instead of the compound (1-1) of Example 1 as the capping layer 9. An EL element was produced. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere. Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the manufactured organic EL element.
　実施例１０において、キャッピング層９として実施例１の化合物（１－１）に代えて実施例４の化合物（１－２２）を膜厚６０ｎｍとなるように形成した以外は、同様の条件で有機ＥＬ素子を作製した。作製した有機ＥＬ素子について、大気中、常温で特性測定を行った。作製した有機ＥＬ素子に直流電圧を印加した発光特性の測定結果を表１にまとめて示した。 In Example 10, the organic layer was formed under the same conditions except that the compound (1-22) of Example 4 was formed to a thickness of 60 nm instead of the compound (1-1) of Example 1 as the capping layer 9. An EL element was produced. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere. Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the manufactured organic EL element.
［比較例１］
　比較のために、実施例１０において、キャッピング層９として実施例１の化合物（１－１）に代えてＡｌｑ３を膜厚６０ｎｍとなるように形成した以外は、同様の条件で有機ＥＬ素子を作製した。作製した有機ＥＬ素子について、大気中、常温で特性測定を行った。作製した有機ＥＬ素子に直流電圧を印加した発光特性の測定結果を表１にまとめて示した。 [Comparative Example 1]
For comparison, an organic EL device was manufactured under the same conditions as in Example 10 except that Alq 3 was formed to a thickness of 60 nm instead of the compound (1-1) of Example 1 as the capping layer 9. Produced. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air | atmosphere. Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the manufactured organic EL element.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、電流密度１０ｍＡ／ｃｍ２時における駆動電圧は、Ａｌｑ３を用いた比較例１の素子（４．１９Ｖ）と実施例１０～１３の素子（４．１７～４．１８Ｖ）ではほぼ同等であるのに対し、輝度、発光効率、電力効率においては、Ａｌｑ３を用いた比較例１の素子（発光効率：５．１３ｃｄ／Ａ、電力効率：３．７８ｌｍ／Ｗ）に対し実施例１０～１３の素子（発光効率：５．３１～５．３６ｃｄ／Ａ、電力効率：３．９８～４．０６ｌｍ／Ｗ）はいずれも向上した。特に外部量子効率では、比較例１の素子（１０．７２％）に対し実施例１０～１３の素子（１１．４１～１１．９３％）は、大幅な向上が確認できた。このことは、キャッピング層に屈折率の高い、本発明の有機ＥＬ素子に好適に用いられる材料を含むことにより、光の取出し効率を大幅に改善できることを示している。 As shown in Table 1, the driving voltage at a current density of 10 mA / cm 2 is the device of Comparative Example 1 (4.19 V) using Alq 3 and the devices of Examples 10 to 13 (4.17 to 4.18 V). ), The luminance, light emission efficiency, and power efficiency are almost the same as those of Comparative Example 1 using Alq 3 (light emission efficiency: 5.13 cd / A, power efficiency: 3.78 lm / W). In contrast, the devices of Examples 10 to 13 (light emission efficiency: 5.31 to 5.36 cd / A, power efficiency: 3.98 to 4.06 lm / W) were all improved. In particular, in terms of external quantum efficiency, it was confirmed that the elements of Examples 10 to 13 (11.41 to 11.93%) significantly improved compared to the element of Comparative Example 1 (10.72%). This indicates that the light extraction efficiency can be significantly improved by including a material having a high refractive index suitable for the organic EL device of the present invention in the capping layer.
　以上のように、本発明の有機ＥＬ素子に好適に用いられる、一般式（１）で表されるアリールアミン化合物は、屈折率が高く、光の取出し効率を大幅に改善でき、薄膜状態が安定であるため、有機ＥＬ素子用の化合物として優れている。該化合物を用いて有機ＥＬ素子を作製することにより、高い効率を得ることができるとともに、耐久性を改善させることができる。また、青、緑および赤それぞれの波長領域において吸収を持たない該化合物を用いることにより、色純度がよく鮮明で明るい画像を表示したい場合に、特に好適である。例えば、家庭電化製品や照明の用途への展開が可能となった。 As described above, the arylamine compound represented by the general formula (1) suitably used in the organic EL device of the present invention has a high refractive index, can greatly improve the light extraction efficiency, and the thin film state is stable. Therefore, it is excellent as a compound for an organic EL device. By producing an organic EL device using the compound, high efficiency can be obtained and durability can be improved. In addition, the use of the compound having no absorption in each of the blue, green, and red wavelength regions is particularly suitable for displaying a clear and bright image with good color purity. For example, it has become possible to develop home appliances and lighting.
　１　　ガラス基板
　２　　金属陽極
　３　　正孔注入層
　４　　正孔輸送層
　５　　発光層
　６　　電子輸送層
　７　　電子注入層
　８　　陰極
　９　　キャッピング層 DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Metal anode 3 Hole injection layer 4 Hole transport layer 5 Light emitting layer 6 Electron transport layer 7 Electron injection layer 8 Cathode 9 Capping layer

Claims (14)

  1. 　少なくとも陽極電極、正孔輸送層、発光層、電子輸送層、陰極電極およびキャッピング層をこの順に有する有機エレクトロルミネッセンス素子において、前記キャッピング層が下記一般式（１）で表されるアリールアミン化合物を含む、有機エレクトロルミネッセンス素子。
    Figure JPOXMLDOC01-appb-C000069
     　　　　　　　　　　　　　　　　　　　　　　　　　（１）
    　（式中、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４は相互に同一でも異なってもよく、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基を表し、ｎは０～４の整数を表す。ここで、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４の少なくとも１つは、下記構造式（Ｂ）で示される１価基であるか、もしくは、該１価基を置換基として有するものとする。）
    Figure JPOXMLDOC01-appb-C000070
     　　　　　　　　　　　　　　　　　　　　　　　　　（Ｂ）
    　（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は相互に同一でも異なってもよく、連結基、もしくは水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキル基、置換基を有していてもよい炭素原子数２ないし６の直鎖状もしくは分岐状のアルケニル基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキルオキシ基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、または置換もしくは無置換のアリールオキシ基であって、単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成していてもよい。Ｘは炭素原子または窒素原子を表し、Ｙは炭素原子、酸素原子、硫黄原子、または窒素原子を表し、Ａｒ５は置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基、もしくは連結基を表し、Ａｒ６、Ａｒ７は相互に同一でも異なってもよく、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基、もしくは連結基であって、Ｙが酸素原子もしくは硫黄原子である場合、ＹはＡｒ７を有さないものとし、ＸおよびＹが窒素原子である場合、Ａｒ５、Ａｒ６、Ａｒ７のいずれかひとつが置換基、もしくは連結基であるものとし、Ｘが窒素原子かつＹが炭素原子である場合、ＸはＡｒ６を有さないものとする。Ａｒ８は置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表す。ただし、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ａｒ５、Ａｒ６、Ａｒ７のいずれか１つのみが連結基であるものとし、Ｘが窒素原子、かつＹが酸素原子もしくは硫黄原子である場合を除く。）     In an organic electroluminescence device having at least an anode electrode, a hole transport layer, a light emitting layer, an electron transport layer, a cathode electrode, and a capping layer in this order, the capping layer contains an arylamine compound represented by the following general formula (1) Organic electroluminescence device.
    Figure JPOXMLDOC01-appb-C000069
     (1)
    (In the formula, Ar 1 , Ar 2 , Ar 3 and Ar 4 may be the same or different from each other, and are substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted aromatic heterocyclic groups, substituted or unsubstituted Represents a substituted fused polycyclic aromatic group, and n represents an integer of 0 to 4. Here, at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 is represented by the following structural formula (B) It is a monovalent group or has the monovalent group as a substituent.)
    Figure JPOXMLDOC01-appb-C000070
     (B)
    (In the formula, R 1 , R 2 , R 3 and R 4 may be the same or different from each other, and may be a linking group, or a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group, substituent. A linear or branched alkyl group having 1 to 6 carbon atoms which may have a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, or a substituent. A linear or branched alkenyl group having 2 to 6 carbon atoms, a linear or branched alkyloxy group having 1 to 6 carbon atoms which may have a substituent, and a substituent; C5-C10 cycloalkyloxy group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensed polycyclic aromatic which may have Group, or substituted or unsubstituted A substituted aryloxy group which may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom or N—Ar 8 , wherein X is a carbon atom; Or a nitrogen atom, Y represents a carbon atom, an oxygen atom, a sulfur atom, or a nitrogen atom, and Ar 5 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted atom Alternatively, it represents an unsubstituted condensed polycyclic aromatic group or a linking group, and Ar 6 and Ar 7 may be the same or different from each other, and are a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic group A heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a linking group, where Y is an oxygen atom or a sulfur atom, Y shall not have Ar 7 and X and Y may be nitrogen If a child, Ar 5, one of Ar 6, Ar 7 is assumed to be a substituent or linking group, if X is a nitrogen atom and Y is carbon atom, X has no Ar 6 Ar 8 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, provided that R 1 , R 2 , R 3 , R 4 , Ar 5 , Ar 6 , Ar 7 are only linking groups, except when X is a nitrogen atom and Y is an oxygen atom or a sulfur atom.)
  2. 　前記構造式（Ｂ）が下記構造式（Ｂ－１）で示される１価基である、請求項１記載の有機エレクトロルミネッセンス素子。
    Figure JPOXMLDOC01-appb-C000071
     　　　　　　　　　　　　　　　　　　　　　　　　　（Ｂ－１）
    　（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は相互に同一でも異なってもよく、水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキル基、置換基を有していてもよい炭素原子数２ないし６の直鎖状もしくは分岐状のアルケニル基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキルオキシ基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、または置換もしくは無置換のアリールオキシ基であって、単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成してもよい。Ａｒ８は置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表す。）     The organic electroluminescence device according to claim 1, wherein the structural formula (B) is a monovalent group represented by the following structural formula (B-1).
    Figure JPOXMLDOC01-appb-C000071
     (B-1)
    (In the formula, R 1 , R 2 , R 3 and R 4 may be the same or different from each other and have a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group or substituent. An optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, and an optionally substituted carbon A linear or branched alkenyl group having 2 to 6 atoms, an optionally substituted linear or branched alkyloxy group having 1 to 6 carbon atoms, or a substituent. A cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted group Or unsubstituted aryloxy A sheet group, a single bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom or N-Ar 8 .Ar 8 may be bonded to each other to form a ring through the substituted or unsubstituted Represents an aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.)
  3. 　前記構造式（Ｂ）が下記構造式（Ｂ－２）で示される１価基である、請求項１記載の有機エレクトロルミネッセンス素子。
    Figure JPOXMLDOC01-appb-C000072
     　　　　　　　　　　　　　　　　　　　　　　　　　（Ｂ－２）
    　（式中、Ｒ１、Ｒ３、Ｒ４は相互に同一でも異なってもよく、水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキル基、置換基を有していてもよい炭素原子数２ないし６の直鎖状もしくは分岐状のアルケニル基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキルオキシ基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、または置換もしくは無置換のアリールオキシ基であって、Ｒ３とＲ４は単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成してもよい。Ａｒ６、Ａｒ８は相互に同一でも異なってもよく、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表す。）     The organic electroluminescence device according to claim 1, wherein the structural formula (B) is a monovalent group represented by the following structural formula (B-2).
    Figure JPOXMLDOC01-appb-C000072
     (B-2)
    (In the formula, R 1 , R 3 and R 4 may be the same or different from each other, and may have a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group or substituent. A linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, and an optionally substituted carbon atom 2 1 to 6 linear or branched alkenyl groups, optionally having a straight chain or branched alkyloxy group having 1 to 6 carbon atoms, and optionally having a substituent. A cycloalkyloxy group having 5 to 10 atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted or unsubstituted group In the aryloxy group It, R 3 and R 4 is a single bond, a substituted or unsubstituted methylene group, an oxygen atom, through a sulfur atom or N-Ar 8 may be bonded to each other to form a ring .Ar 6, Ar 8 May be the same or different from each other, and each represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.
  4. 　前記構造式（Ｂ）が下記構造式（Ｂ－３）で示される１価基である、請求項１記載の有機エレクトロルミネッセンス素子。
    Figure JPOXMLDOC01-appb-C000073
     　　　　　　　　　　　　　　　　　　　　　　　　　（Ｂ－３）
    　（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は相互に同一でも異なってもよく、水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキル基、置換基を有していてもよい炭素原子数２ないし６の直鎖状もしくは分岐状のアルケニル基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキルオキシ基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、または置換もしくは無置換のアリールオキシ基であって、単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成してもよい。Ａｒ８は置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表す。）     The organic electroluminescence device according to claim 1, wherein the structural formula (B) is a monovalent group represented by the following structural formula (B-3).
    Figure JPOXMLDOC01-appb-C000073
     (B-3)
    (In the formula, R 1 , R 2 , R 3 and R 4 may be the same or different from each other and have a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group or substituent. An optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, and an optionally substituted carbon A linear or branched alkenyl group having 2 to 6 atoms, an optionally substituted linear or branched alkyloxy group having 1 to 6 carbon atoms, or a substituent. A cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted group Or unsubstituted aryloxy A sheet group, a single bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom or N-Ar 8 .Ar 8 may be bonded to each other to form a ring through the substituted or unsubstituted Represents an aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.)
  5. 　前記構造式（Ｂ）が下記構造式（Ｂ－４）で示される１価基である、請求項１記載の有機エレクトロルミネッセンス素子。
    Figure JPOXMLDOC01-appb-C000074
     　　　　　　　　　　　　　　　　　　　　　　　　　（Ｂ－４）
    　（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は相互に同一でも異なってもよく、水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキル基、置換基を有していてもよい炭素原子数２ないし６の直鎖状もしくは分岐状のアルケニル基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキルオキシ基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、または置換もしくは無置換のアリールオキシ基であって、単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成してもよい。Ａｒ８は置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表す。）     The organic electroluminescence device according to claim 1, wherein the structural formula (B) is a monovalent group represented by the following structural formula (B-4).
    Figure JPOXMLDOC01-appb-C000074
     (B-4)
    (In the formula, R 1 , R 2 , R 3 and R 4 may be the same or different from each other and have a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group or substituent. An optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 5 to 10 carbon atoms, and an optionally substituted carbon A linear or branched alkenyl group having 2 to 6 atoms, an optionally substituted linear or branched alkyloxy group having 1 to 6 carbon atoms, or a substituent. A cycloalkyloxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, or a substituted group Or unsubstituted aryloxy A sheet group, a single bond, a substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom or N-Ar 8 .Ar 8 may be bonded to each other to form a ring through the substituted or unsubstituted Represents an aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.)
  6. 　前記構造式（Ｂ）が下記構造式（Ｂ’）で示される１価基である、請求項１記載の有機エレクトロルミネッセンス素子。
    Figure JPOXMLDOC01-appb-C000075
     　　　　　　　　　　　　　　　　　　　　　　　　　（Ｂ’）
    　（式中、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８は相互に同一でも異なってもよく、連結基、もしくは水素原子、重水素原子、フッ素原子、塩素原子、シアノ基、ニトロ基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキル基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキル基、置換基を有していてもよい炭素原子数２ないし６の直鎖状もしくは分岐状のアルケニル基、置換基を有していてもよい炭素原子数１ないし６の直鎖状もしくは分岐状のアルキルオキシ基、置換基を有していてもよい炭素原子数５ないし１０のシクロアルキルオキシ基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、置換もしくは無置換の縮合多環芳香族基、または置換もしくは無置換のアリールオキシ基であって、単結合、置換もしくは無置換のメチレン基、酸素原子、硫黄原子またはＮ－Ａｒ８を介して互いに結合して環を形成していてもよい。Ｘは炭素原子または窒素原子を表し、Ｙは炭素原子、酸素原子、硫黄原子、または窒素原子を表し、Ａｒ５は置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基、もしくは連結基を表し、Ａｒ６、Ａｒ７は相互に同一でも異なってもよく、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基、もしくは連結基であって、Ｙが酸素原子もしくは硫黄原子である場合、ＹはＡｒ７を有さないものとし、ＸおよびＹが窒素原子である場合、Ａｒ５、Ａｒ６、Ａｒ７のいずれかひとつが置換基、もしくは連結基であるものとし、Ｘが窒素原子かつＹが炭素原子である場合、ＸはＡｒ６を有さないものとする。Ａｒ８は置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基、または置換もしくは無置換の縮合多環芳香族基を表す。ただし、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ａｒ５、Ａｒ６、Ａｒ７のいずれか１つのみが連結基であるものとし、Ｘが窒素原子、かつＹが酸素原子もしくは硫黄原子である場合を除く。）     The organic electroluminescence device according to claim 1, wherein the structural formula (B) is a monovalent group represented by the following structural formula (B ').
    Figure JPOXMLDOC01-appb-C000075
     (B ')
    (In the formula, R 3 , R 4 , R 5 , R 6 , R 7 and R 8 may be the same or different from each other, and may be a linking group, or a hydrogen atom, deuterium atom, fluorine atom, chlorine atom, cyano group. , A nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a linear or branched alkyl having 1 to 6 carbon atoms which may have a substituent Oxy group, optionally substituted cycloalkyloxy group having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted A fused polycyclic aromatic group, or A substituted or unsubstituted aryloxy group, a single bond, a substituted or unsubstituted methylene group, an oxygen atom, through a sulfur atom or N-Ar 8 may be bonded to each other to form a ring .X Represents a carbon atom or a nitrogen atom, Y represents a carbon atom, an oxygen atom, a sulfur atom, or a nitrogen atom, Ar 5 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group Or a substituted or unsubstituted condensed polycyclic aromatic group or a linking group, and Ar 6 and Ar 7 may be the same or different from each other, and are substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted Or a substituted or unsubstituted condensed polycyclic aromatic group or a linking group, and Y is an oxygen atom or sulfur atom, Y does not have Ar 7 , And Y is a nitrogen atom, any one of Ar 5 , Ar 6 and Ar 7 is a substituent or a linking group, and when X is a nitrogen atom and Y is a carbon atom, X is Ar 6. Ar 8 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, provided that Only one of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , Ar 5 , Ar 6 , Ar 7 is a linking group, X is a nitrogen atom, and Y is an oxygen atom Or except for the case of sulfur atoms.)
  7. 　前記一般式（１）において、ｎが０である、請求項１記載の有機エレクトロルミネッセンス素子。 The organic electroluminescent device according to claim 1, wherein n is 0 in the general formula (1).
  8. 　前記一般式（１）において、ｎが１である、請求項１記載の有機エレクトロルミネッセンス素子。 The organic electroluminescent element according to claim 1, wherein n is 1 in the general formula (1).
  9. 　前記一般式（１）において、ｎが２である、請求項１記載の有機エレクトロルミネッセンス素子。 The organic electroluminescent element according to claim 1, wherein n is 2 in the general formula (1).
  10. 　前記一般式（１）において、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４のいずれか２つが、前記構造式（Ｂ）で示される１価基であるか、もしくは該１価基を置換基として有するものである、請求項１記載の有機エレクトロルミネッセンス素子。 In the general formula (1), any two of Ar 1 , Ar 2 , Ar 3 , Ar 4 are the monovalent group represented by the structural formula (B), or the monovalent group is used as a substituent. The organic electroluminescent element according to claim 1, which is provided.
  11. 　前記一般式（１）において、Ａｒ１およびＡｒ４が、前記構造式（Ｂ）で示される１価基であるか、もしくは該１価基を置換基として有するものである、請求項１記載の有機エレクトロルミネッセンス素子。 In the general formula (1), Ar 1 and Ar 4 are the structural formula (B) or a monovalent represented by, or those having as substituents the monovalent, according to claim 1, wherein Organic electroluminescence device.
  12. 　前記キャッピング層の厚さが、３０ｎｍ～１２０ｎｍの範囲内である、請求項１記載の有機エレクトロルミネッセンス素子。 The organic electroluminescence device according to claim 1, wherein the thickness of the capping layer is in the range of 30 nm to 120 nm.
  13. 　前記キャッピング層の屈折率が、該キャッピング層を透過する光の波長が４５０ｎｍ～７５０ｎｍの範囲内において、１．８５以上である、請求項１記載の有機エレクトロルミネッセンス素子。 The organic electroluminescence device according to claim 1, wherein the refractive index of the capping layer is 1.85 or more when the wavelength of light transmitted through the capping layer is in the range of 450 nm to 750 nm.
  14. 　前記一般式（１）で表される化合物を有機エレクトロルミネッセンス素子のキャッピング層に用いる方法。 A method of using the compound represented by the general formula (1) for a capping layer of an organic electroluminescence element.
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