JP5749870B1 - Organic electroluminescence device - Google Patents

Abstract

[PROBLEMS] To improve the device characteristics of an organic electroluminescence device, in particular, to greatly improve the light extraction efficiency, the refractive index is high, the thin film has excellent stability and durability, and blue, To provide an organic electroluminescence device comprising a capping layer composed of a material that does not absorb in the wavelength regions of green and red. 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 aryl represented by the following general formula (1). An organic electroluminescence device comprising an amine compound. [Chemical 1]

Description

  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.

  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 has a clear display.

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).

  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).

  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 above 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.

  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).

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).

  For the formation of the capping layer, it has been proposed to use a metal mask with high definition. However, 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.

When tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq ₃ ) is used as a capping layer for adjusting the refractive index (see, for example, 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.

  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.

JP-A-8-048656 Japanese Patent No. 3194657 WO2013-038627

Proceedings of the 9th meeting of the Japan Society of Applied Physics 55-61 pages (2001) Appl. Phys. Lett. , 78, 544 (2001) Appl. Phys. Lett. , 82, 466 (2003) Aust. J. et al. Chem. , 45, 371 (1992) J. et al. Org. Chem. , 60, 7508 (1995) Synth. Commun. , 11, 513 (1981) Appl. Phys. Let. 98,083302 (2011)

  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.

  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.

  That is, according to the present invention, the following organic EL elements are provided.

  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

（１）

(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 condensed polycyclic aromatic group, and n represents an integer of 0 to _4. Here, at least one of Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ is represented by the following structural formula (B). It is a monovalent group or has the monovalent group as a substituent.)

（Ｂ）

(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 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) The organic EL device according to 1), wherein the structural formula (B) is a monovalent group represented by the following structural formula (B-1).

（Ｂ−１）

(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 And a ring 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. Ar ₈ is a substituted or unsubstituted group. Represents an aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.)

  3) The organic EL device according to 1), wherein the structural formula (B) is a monovalent group represented by the following structural formula (B-2).

（Ｂ−２）

(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) The organic EL device according to 1), wherein the structural formula (B) is a monovalent group represented by the following structural formula (B-3).

（Ｂ−３）

(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 And a ring 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. Ar ₈ is a substituted or unsubstituted group. Represents an aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.)

  5) The organic EL device according to 1), wherein the structural formula (B) is a monovalent group represented by the following structural formula (B-4).

（Ｂ−４）

(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 And a ring 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. Ar ₈ is a substituted or unsubstituted group. Represents an aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.)

  6) The organic EL device according to 1), wherein the structural formula (B) is a monovalent group represented by the following structural formula (B ′).

（Ｂ’）

(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) The organic EL device according to 1), wherein n is 0 in the general formula (1).

  8) The organic EL device according to 1), wherein n is 1 in the general formula (1).

  9) The organic EL device according to 1), wherein n is 2 in the general formula (1).

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) 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) 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) 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) The method of using the compound represented by the said General formula (1) for the capping layer of an organic electroluminescent element.

“Substituted or unsubstituted aromatic hydrocarbon group”, “substituted or unsubstituted aromatic heterocyclic group” represented by Ar _{1 to} Ar ₄ in the general 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.

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.
In addition, these substituents 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” or “substituted or unsubstituted aromatic heterocycle” represented by Ar _{1 to} Ar ₄ in the general formula (1). It means the same as “N—Ar ₈ ” defined for “ring group” or “substituted or unsubstituted condensed polycyclic aromatic group”.

Represented by R _{1 to} R ₈ in the structural formulas (B), (B-1), (B-2), (B-3), (B-4), and (B ′), 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“ C2-C6 linear or branched alkenyl group ”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, and the like. 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” or “substituted or unsubstituted aromatic heterocycle” represented by Ar _{1 to} Ar ₄ in the general formula (1). It means the same as “N—Ar ₈ ” defined for “ring group” or “substituted or unsubstituted condensed polycyclic aromatic group”.

Represented by R _{1 to} R ₈ in the structural formulas (B), (B-1), (B-2), (B-3), (B-4), and (B ′), 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 " As the “substituent” in the “like or branched alkenyl 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.

Represented by R _{1 to} R ₈ in the structural formulas (B), (B-1), (B-2), (B-3), (B-4), and (B ′), “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” 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 A xyl group, a 1-adamantyloxy group, a 2-adamantyloxy group, and the like, 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” or “substituted or unsubstituted aromatic heterocycle” represented by Ar _{1 to} Ar ₄ in the general formula (1). It means the same as “N—Ar ₈ ” defined for “ring group” or “substituted or unsubstituted condensed polycyclic aromatic group”.

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 “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 shown 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.

Represented by R _{1 to} R ₈ in the structural formulas (B), (B-1), (B-2), (B-3), (B-4), and (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" condensed polycyclic aromatic group "includes" 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.

The “substituted aromatic” represented by R _{1 to} R ₈ in the structural formulas (B), (B-1), (B-2), (B-3), (B-4), and (B ′) As the “substituent” in the “hydrocarbon group”, “substituted aromatic heterocyclic group” or “substituted condensed polycyclic aromatic group”, “substitution” 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 the same I can give you something.

Represented by R _{1 to} R ₈ in the structural formulas (B), (B-1), (B-2), (B-3), (B-4), and (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” or “substituted or unsubstituted aromatic heterocycle” represented by Ar _{1 to} Ar ₄ in the general formula (1). 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 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.

“Substituted or unsubstituted aromatic hydrocarbon group” represented by Ar ₅ , Ar ₆ , Ar ₇ in structural formulas (B), (B-2), and (B ′), “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 polycycle” 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.

A “substituted aromatic hydrocarbon group”, “substituted aromatic heterocyclic group” or “represented by Ar ₅ , Ar ₆ , Ar ₇ in Structural Formulas (B), (B-2), (B ′)” 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.

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). It is more preferable that the structural formula (B) is used as the substituent, and Ar ₁ and Ar ₄ have the structural formula (B-1), (B-3) or (B-4) as a substituent. The aspect which is an aspect or the said 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.

  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.

  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.

  In the organic EL device of the present invention, the capping layer preferably has a refractive index of 1.85 or more in a wavelength range of 450 nm to 750 nm of light transmitted through the capping layer. More preferably.

  In the organic EL device of the present invention, the capping layer may be produced by laminating two or more different constituent materials.

  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.

  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.

1 is a ¹ H-NMR chart of a compound (1-1) of Example 1 of the present invention. ^{1 is} a ¹ H-NMR chart of a compound (1-32) of Inventive Example 2. FIG. It is a ¹ H-NMR chart of the compound (1-2) of Invention Example 3. FIG. 3 is a ¹ H-NMR chart of the compound (1-22) of Invention Example 4. ^{1 is} a ¹ H-NMR chart of a compound (1-23) of Inventive Example 5. FIG. FIG. 6 is a ¹ H-NMR chart of the compound (1-25) of Invention Example 6. It is the figure which showed the organic EL element structure of Examples 10-13 and the comparative example 1. FIG.

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. .
Also, brominated benzotriazole derivatives can be synthesized by brominating the synthesized benzotriazole derivatives 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.

  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.

（１−１）

(1-1)

（１−２）

(1-2)

（１−３）

(1-3)

（１−４）

(1-4)

（１−５）

(1-5)

（１−６）

(1-6)

（１−７）

(1-7)

（１−８）

(1-8)

（１−９）

(1-9)

（１−１０）

(1-10)

（１−１１）

(1-11)

（１−１２）

(1-12)

（１−１３）

(1-13)

（１−１４）

(1-14)

（１−１５）

(1-15)

（１−１６）

(1-16)

（１−１７）

(1-17)

（１−１８）

(1-18)

（１−１９）

(1-19)

（１−２０）

(1-20)

（１−２１）

(1-21)

（１−２２）

(1-22)

（１−２３）

(1-23)

（１−２４）

(1-24)

（１−２５）

(1-25)

（１−２６）

(1-26)

（１−２７）

(1-27)

（１−２８）

(1-28)

（１−２９）

(1-29)

（１−３０）

(1-30)

（１−３１）

(1-31)

（１−３２）

(1-32)

（１−３３）

(1-33)

（１−３４）

(1-34)

（１−３５）

(1-35)

（１−３６）

(1-36)

（１−３７）

(1-37)

（１−３８）

(1-38)

（１−３９）

(1-39)

（１−４０）

(1-40)

（１−４１）

(1-41)

（１−４２）

(1-42)

（１−４３）

(1-43)

（１−４４）

(1-44)

（１−４５）

(1-45)

（１−４６）

(1-46)

（１−４７）

(1-47)

（１−４８）

(1-48)

（１−４９）

(1-49)

（１−５０）

(1-50)

（１−５１）

(1-51)

（１−５２）

(1-52)

（１−５３）

(1-53)

（１−５４）

(1-54)

（１−５５）

(1-55)

（１−５６）

(1-56)

  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. 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.

  The glass transition point (Tg) was measured with a high-sensitive differential scanning calorimeter (Bruker AXS, DSC3100S) using powder.

  The refractive index was measured using a spectrophotometer (F10-RT-UV, manufactured by Filmetrics) by preparing a thin film of 80 nm on a silicon substrate.

  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 film 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. Further, the film thickness of the capping layer is preferably, for example, 30 nm to 120 nm, 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.

  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.

  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.

  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 containing no hetero atom is connected, for example, N, N, N ′, N′-tetrabiphenylylbenzidine and the like. 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.

  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.

  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.

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.

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) or 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.

  In order to avoid concentration quenching, the host material of the phosphorescent light emitting material is preferably doped by co-evaporation in the range of 1 to 30 weight percent with respect to the entire light emitting layer.

  In addition, a material that emits delayed fluorescence such as CDCB derivatives such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN can be used as the light-emitting material (see, for example, Non-Patent Document 7).

  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.

  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.

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.

  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.

  Further, 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.

  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.

  As the capping layer of the organic EL device of the present invention, the arylamine compound represented by the general formula (1) 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.

  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.

  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.

  Embodiments of the present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples.

<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))>
In a reaction vessel purged with nitrogen, 4.2 g of 2- (4-bromophenyl) -2H-benzo [1,2,3] triazole, 2.3 g of N, N′-diphenylbenzidine, 2.0 g of tert-butoxy sodium, 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, the column was purified by column chromatography (carrier: NH silica gel, eluent: toluene / n-hexane), and further dispersed and washed with 100 ml of n-hexane to obtain 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.

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′-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))>
In a reaction vessel purged with nitrogen, 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.

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′-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 and 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%).

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), 7.9-7.92 (4H), 7.72-7.58 (7H), 7.50-7.12 (23H).

<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 instead of {4- (2H-benzo [1,2,3] triazol-2-yl) phenyl} phenylamine. , N, N′-bis {4- (benzoxazol-2-yl) phenyl} -N, N′-diphenyl-4,4 ″ -diamino-1,1 ′ : 12.4 g (yield 47%) of a yellow powder of 4 ′, 1 ″ -terphenyl (compound (1-22)).

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′-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 performed 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.

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′-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%).

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′-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 for 3 hours with stirring. After cooling to room temperature and collecting the precipitate by filtration, N, N′-bis {4- (benzothiazole-2) is obtained by repeating crystallization purification using a mixed solvent of 1,2-dichlorobenzene / methanol. -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.

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

  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.

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 formulas were also measured (for example, see 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

（２−１）

(2-1)

（２−２）

(2-2)

Thus compounds of the invention are comparative compounds (2-1), (2-2) and has a refractive index from 1.70 to 1.81 greater than the Alq _3, the light in the large organic EL element The improvement of the extraction efficiency can be expected.

  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.

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 the 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, as the electron transport layer 6, a compound (ETM-1) having the following structural formula and a compound (ETM-2) having the following structural formula are deposited at an evaporation rate ratio of (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.

（ＨＩＭ−１）

(HIM-1)

（ＥＴＭ−１）

(ETM-1)

（ＥＴＭ−２）

(ETM-2)

  In Example 10, except that the compound (1-32) of Example 2 was formed so as to have a film thickness of 60 nm instead of the compound (1-1) of Example 1 as the capping layer 9, it was organic under the same conditions. 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.

  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.

  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 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.

[Comparative Example 1]
For comparison, in Example 10, an organic EL device was formed under the same conditions 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.

As shown in Table 1, the driving voltage at a current density of 10 mA / cm ² was 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 the external quantum efficiency, it was confirmed that the elements of Examples 10 to 13 (11.41 to 11.93%) significantly improved with respect 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.

  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.

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 (9)

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.

(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 condensed polycyclic aromatic group, and n represents an integer of 0 to _4. Here, at least one of Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ represents the following structural formula (B-1), (It is assumed that it is a monovalent group represented by either (B-2) or (B ′), or has the monovalent group as a substituent.)

(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 And a ring 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. Ar ₈ is a substituted or unsubstituted group. Represents an aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.)

(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.

(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.)   The organic electroluminescent element according to claim 1, wherein n is 0 in the general formula (1).   The organic electroluminescent element according to claim 1, wherein n is 1 in the general formula (1).   The organic electroluminescent element according to claim 1, wherein n is 2 in the general formula (1). In the general formula (1), any _{two of} Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ are represented by any one of the structural formulas (B-1), (B-2), and (B ′). The organic electroluminescent element according to claim 1, which is a monovalent group or has a monovalent group as a substituent. In the general formula (1), Ar ₁ and Ar ₄ are monovalent groups represented by any one of the structural formulas (B-1), (B-2), and (B ′), or the 1 The organic electroluminescent element of Claim 1 which has a valence group as a substituent.   The organic electroluminescence device according to claim 1, wherein the thickness of the capping layer is within a range of 30 nm to 120 nm.   The organic electroluminescent element 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. The method of using the arylamine compound represented by following General formula (1) for the capping layer of an organic electroluminescent element.

(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 condensed polycyclic aromatic group, and n represents an integer of 0 to _4. Here, at least one of Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ represents the following structural formula (B-1), (It is assumed that it is a monovalent group represented by either (B-2) or (B ′), or has the monovalent group as a substituent.)

(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 And a ring 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. Ar ₈ is a substituted or unsubstituted group. Represents an aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.)

(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.

(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.)

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