JP2015013807A - Aromatic amine derivative and organic electroluminescent element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic EL element capable of obtaining blue luminescence, and a useful aromatic amine derivative used as the organic thin film layer of the organic EL element.SOLUTION: Provided is an aromatic amine derivative represented by formula (1). In the formula (1), Rto Rand Rto Rrespectively independently denote a hydrogen atom or a substitutional group; Rand Rdenote a substitutional group of formula (2); Lto Lrespectively independently denote a single bond, the bivalent residue of an aryl group or the like; Ardenotes a substitutional group having formula (3) having at least one of a fluorine atom, a cyano group, an alkylsilyl group or the like as a substitutional group as a partial structure; X denotes an oxygen atom or a sulfur atom; and A and B denote a 6-membered ring; and Ardenotes a substitutional group having an aryl group or the formula (3) as a partial structure or the like.

Description

  The present invention relates to an aromatic amine derivative and an organic electroluminescence device using the same.

  Organic electroluminescence elements using organic substances (hereinafter sometimes abbreviated as organic EL elements) are expected to be used as solid-state, inexpensive, large-area, full-color display elements, and many developments have been made. ing. In general, an organic EL element is composed of a light emitting layer and a pair of counter electrodes sandwiching the light emitting layer. In light emission, when an electric field is applied between both electrodes, electrons are injected from the cathode side and holes are injected from the anode side. Further, the electrons recombine with holes in the light emitting layer to generate an excited state, and energy is emitted as light when the excited state returns to the ground state.

  Conventional organic EL elements have a higher driving voltage and lower light emission luminance and light emission efficiency than inorganic light-emitting diodes. Further, the characteristic deterioration has been remarkably not put into practical use. Although recent organic EL devices have been gradually improved, further higher light emission efficiency, longer life, improved color reproducibility, and the like are required.

The performance of organic EL elements has been gradually improved by improving the light emitting material for organic EL. In particular, improving the color purity of blue organic EL elements (shortening the emission wavelength) is an important technique that leads to improved color reproducibility of displays.
As an example of the material used for the light emitting layer, Patent Document 1 discloses a light emitting material having dibenzofuran, and although blue light emission with a short wavelength is obtained, the light emission efficiency is low and further improvement has been demanded. .

  Patent Documents 4 and 5 disclose diaminopyrene derivatives. Patent Document 2 discloses a combination of an anthracene host and an arylamine. Patent Documents 3 to 5 disclose a combination of an anthracene host having a specific structure and a diaminopyrene dopant. Further, Patent Documents 6 to 8 disclose anthracene host materials.

  Although any material and any combination show improvement in light emission characteristics, it is not sufficient, and a light emitting material that exhibits high light emission efficiency and realizes further short wavelength light emission has been demanded.

  Patent Document 9 discloses that an aromatic amine derivative having an arylene group at the center and a dibenzofuran ring bonded to a nitrogen atom is used as a hole transport material, and Patent Document 10 discloses a dibenzofuran ring, a dibenzofuran ring, and a dibenzofuran ring. Although it is disclosed that an aromatic amine derivative in which a thiophene ring, a benzofuran ring, a benzothiophene ring, or the like is bonded to a nitrogen atom via an arylene group is used as a hole transport material, there is no example of using it as a light emitting material.

  Patent Documents 11 to 13 disclose aromatic amine derivatives in which an amino group is bonded to the 1-position and 6-position of pyrene. In the aromatic amine derivatives described in Patent Document 11 and Patent Document 12, a dibenzofuran ring or a dibenzothiophene ring is bonded to the nitrogen atom of the amino group. These aromatic amine derivatives are used as blue light emitting materials, but further improvement in color purity and luminous efficiency is required for practical use.

WO2006 / 128800 pamphlet WO2004 / 018588 pamphlet WO2004 / 018587 pamphlet JP 2004-204238 A WO2005 / 108348 pamphlet WO2005 / 054162 pamphlet WO2005 / 061656 pamphlet WO2002 / 038524 pamphlet JP-A-11-35532 WO2007 / 125714 pamphlet International Publication No. 2010/122810 International Publication No. 2009/084512 Korean Published Patent No. 10-2011-0076376

  An object of this invention is to provide the useful organic amine element which can obtain blue light emission, and the useful aromatic amine derivative which can be used for the organic thin film layer of the said organic EL element.

  According to the present invention, the following aromatic amine derivative and organic EL device are provided.

[1] An aromatic amine derivative represented by the following general formula (1).

(In the general formula (1), R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently
Hydrogen atom,
Deuterium atom,
Halogen atoms,
A cyano group,
A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms;
A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms,
A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms,
A substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms,
A substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms,
A substituted or unsubstituted arylsilyl group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted trifluoroalkyl group having 1 to 20 carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms,
A substituted or unsubstituted aralkyl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms.
However, in the general formula (1), R ₁ and R ₆ are represented by the following general formula (2). )

(In the general formula (2), L ₁ , L ₂ and L ₃ are each independently
Single bond,
It is a divalent residue of a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a divalent residue of a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms.
In the general formula (2), Ar ₁ is a substituent having the following general formula (3) as a partial structure. )

(In the general formula (3), X represents an oxygen atom or a sulfur atom. In the general formula (3), A and B represent a 6-membered ring. The 6-membered ring represented by A and B. In addition, another ring may be condensed.
The substituent having the general formula (3) as a partial structure is
Fluorine atom,
A cyano group,
A substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms,
It has at least one substituent selected from a substituted or unsubstituted arylsilyl group having 6 to 30 ring carbon atoms and a substituted or unsubstituted trifluoroalkyl group having 1 to 20 carbon atoms.
In the general formula (2), Ar ₂ is
Fluorine atom,
A cyano group,
A substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms,
6 or more ring-forming carbon atoms having at least one substituent selected from a substituted or unsubstituted arylsilyl group having 6 to 30 ring carbon atoms and a substituted or unsubstituted trifluoroalkyl group having 1 to 20 carbon atoms An aryl group of -30, a heterocyclic group having 5-30 ring-forming atoms, or a substituent having the general formula (3) as a partial structure. )

[2] In the aromatic amine derivative according to [1],
The aromatic amine derivative, wherein the substituent having the general formula (3) as a partial structure is a monovalent residue of the following general formula (4).

(In the general formula (4), X represents an oxygen atom or a sulfur atom.
In the general formula (4), R ₁₁ to R ₁₈ are each independently
Hydrogen atom,
Deuterium atom,
Halogen atoms,
A cyano group,
A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms;
A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms,
A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms,
A substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms,
A substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms,
A substituted or unsubstituted arylsilyl group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms,
A substituted or unsubstituted aralkyl group having 6 to 30 ring carbon atoms,
It is a substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted trifluoroalkyl group having 1 to 20 carbon atoms.
In the general formula (4), at least one of R ₁₁ to R ₁₈ is
Fluorine atom,
A cyano group,
A substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms,
It is a substituted or unsubstituted arylsilyl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted trifluoroalkyl group having 1 to 20 carbon atoms.
However, in the general formula (2), when Ar ₁ is a monovalent residue of the general formula (4), one of R ₁₁ to R ₁₈ is bonded to L ₁ . And when Ar ₂ is a monovalent residue of the general formula (4), one of R ₁₁ to R ₁₈ is a single bond that binds to L ₂ . is there.
In the general formula _(4), among the combinations of _{R 11} and _{R 12, R 12} and _{R 13, R 13} and _{R 14, R 15} and _{R 16, R 16} and _{R 17} and _{R 17} and _{R 18,} at least one One or a combination may form a saturated or unsaturated ring. )

[3] The aromatic amine derivative according to [2], wherein at least one of R ₁₁ to R ₁₈ in the general formula (4) is a fluorine atom.

[4] The aromatic amine derivative according to [2], wherein at least one of R ₁₁ to R ₁₈ in the general formula (4) is a cyano group.

[5] The aromatic amine derivative according to [2], wherein at least one of R ₁₁ to R ₁₈ in the general formula (4) is a substituted or unsubstituted alkyl silyl group having 3 to 30 carbon atoms, An aromatic amine derivative, which is a substituted or unsubstituted arylsilyl group having 6 to 30 ring carbon atoms.

[6] The aromatic amine derivative according to [2], wherein at least one of R ₁₁ to R ₁₈ in the general formula (4) is a substituted or unsubstituted C 1-20 trifluoroalkyl group. An aromatic amine derivative characterized in that

[7] An organic compound layer is provided between the cathode and the anode,
The organic compound layer is an organic electroluminescence device including the aromatic amine derivative according to any one of [1] to [6].

[8] In the organic electroluminescence device according to [7],
The organic compound layer includes a plurality of organic thin film layers including a light emitting layer,
At least one layer among the plurality of organic thin film layers includes the aromatic amine derivative according to any one of [1] to [6]. An organic electroluminescence element.

[9] In the organic electroluminescence device according to [8],
At least one of the plurality of organic thin film layers is composed of the aromatic amine derivative according to any one of [1] to [6], and an anthracene derivative represented by the following general formula (20): An organic electroluminescence device comprising:

(In the general formula (20), Ar ¹¹ and Ar ¹² are each independently
A substituted or unsubstituted monocyclic group having 5 to 30 ring atoms;
A substituted or unsubstituted condensed ring group having 10 to 30 ring atoms, or a group composed of a combination of the monocyclic group and the condensed ring group.
In the general formula (20), R ¹⁰¹ to R ¹⁰⁸ are each independently
Hydrogen atom,
Halogen atoms,
A cyano group, a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms,
A substituted or unsubstituted condensed ring group having 10 to 30 ring atoms,
A group composed of a combination of the monocyclic group and the condensed ring group,
A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms,
A substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms,
A substituted or unsubstituted aryloxy having 6 to 30 ring carbon atoms, or a substituted or unsubstituted silyl group. )

[10] In the organic electroluminescence device according to [9],
Ar ¹¹ and Ar ¹² in the general formula (20) are each independently a substituted or unsubstituted condensed ring group having 10 to 30 ring atoms. An organic electroluminescence device, wherein:

[11] In the organic electroluminescence device according to [9],
One of Ar ¹¹ and Ar ¹² in the general formula (20) is a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms, and the other is a substituted or unsubstituted ring atom having 10 to 30 atoms. An organic electroluminescence device characterized by being a condensed ring group of

[12] In the organic electroluminescence device according to [11],
Ar ¹² in the general formula (20) is selected from a naphthyl group, a phenanthryl group, a benzoanthryl group, and a dibenzofuranyl group, and Ar ¹¹ is an unsubstituted phenyl group, the monocyclic group, or the condensed ring group. An organic electroluminescence device, wherein the organic electroluminescence device is a substituted phenyl group.

[13] In the organic electroluminescence device according to [11],
Ar ¹² in the general formula (20) is a substituted or unsubstituted condensed ring group having 10 to 30 ring atoms, and Ar ¹¹ is an unsubstituted phenyl group. .

[14] In the organic electroluminescence device according to [9],
Ar ¹¹ and Ar ¹² in the general formula (20) are each independently a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms. The organic electroluminescence device.

[15] In the organic electroluminescence device according to [14],
Ar ¹¹ and Ar ¹² in the general formula (20) are each independently a substituted or unsubstituted phenyl group. An organic electroluminescence device, wherein:

[16] In the organic electroluminescence device according to [15],
Ar ¹¹ in the general formula (20) is an unsubstituted phenyl group, and Ar ¹² is a phenyl group having at least one of the monocyclic group and the condensed ring group as a substituent. Electroluminescence element.

[17] In the organic electroluminescence device according to [15],
Ar ¹¹ and Ar ¹² in the general formula (20) are each independently a phenyl group having at least one of the monocyclic group and the condensed ring group as a substituent. An organic electroluminescence device, wherein:

  ADVANTAGE OF THE INVENTION According to this invention, the useful aromatic amine derivative which can be used for the organic thin film layer of the organic EL element which can obtain blue light emission, and the said organic EL element can be provided.

It is a figure which shows schematic structure of an example of the organic electroluminescent element which concerns on embodiment of this invention.

[Aromatic amine derivatives]
The aromatic amine derivative of the present invention is represented by the general formula (1).
Next, R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ , R ₉ and R ₁₀ in the general formula (1) will be described.

Examples of the aryl group having 6 to 30 ring carbon atoms in the general formula (1) include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, Benzanthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, naphthacenyl group, pyrenyl group, 1-chrysenyl group, 2-chrysenyl group, 3-chrysenyl group 4-chrysenyl group, 5-chrycenyl group, 6-chrycenyl group, benzo [c] phenanthryl group, benzo [g] chrysenyl group, 1-triphenylenyl group, 2-triphenylenyl group, 3-triphenylenyl group, 4-triphenylenyl group, 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl 9-fluorenyl group, benzofluorenyl group, dibenzofluorenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, o-terphenyl group, m-terphenyl-4-yl Group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group Group, m-quaterphenyl group, 3-fluoranthenyl group, 4-fluoranthenyl group, 8-fluoranthenyl group, 9-fluoranthenyl group, benzofluoranthenyl group, o-tolyl group, m-tolyl group Group, p-tolyl group, 2,3-xylyl group, 3,4-xylyl group, 2,5-xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, pt- Butyl Fe Le group, p-(2-phenylpropyl) phenyl group, 4'-methylbiphenyl-yl group, 4 "include -t- butyl -p- terphenyl-4-yl group.
As an aryl group in the said General formula (1), it is preferable that ring forming carbon number is 6-20, More preferably, it is preferable that it is 6-12. Among the aryl groups, a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a terphenyl group, and a fluorenyl group are particularly preferable. For the 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group and 4-fluorenyl group, the substituted or unsubstituted alkyl group having 1 to 30 carbon atoms in the general formula (1) is present at the 9-position carbon atom. It is preferably substituted.

Examples of the heterocyclic group having 5 to 30 ring atoms in the general formula (1) include pyrrolyl group, pyrazinyl group, pyridinyl group, indolyl group, isoindolyl group, imidazolyl group, furyl group, benzofuranyl group, and isobenzofuran group. Nyl group, dibenzofuranyl group, dibenzothiophenyl group, quinolyl group, isoquinolyl group, quinoxalinyl group, carbazolyl group, phenanthridinyl group, acridinyl group, phenanthrolinyl group, phenazinyl group, phenothiazinyl group, phenoxazinyl group, Oxazolyl group, oxadiazolyl group, furazanyl group, thienyl group, benzothiophenyl group, and pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, indole ring, quinoline ring, acridine ring, pyrrolidine ring, dioxane ring, piperidine , Morpholine ring, piperazine ring, carbazole ring, furan ring, thiophene ring, oxazole ring, oxadiazole ring, benzoxazole ring, thiazole ring, thiadiazole ring, benzothiazole ring, triazole ring, imidazole ring, benzimidazole ring, pyran And a group formed from a ring and a dibenzofuran ring.
More specifically, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 5-pyrimidinyl group, 6-pyrimidinyl group, 1 , 2,3-triazin-4-yl group, 1,2,4-triazin-3-yl group, 1,3,5-triazin-2-yl group, 1-imidazolyl group, 2-imidazolyl group, 1- Pyrazolyl group, 1-indolidinyl group, 2-indolidinyl group, 3-indolidinyl group, 5-indolidinyl group, 6-indolidinyl group, 7-indolidinyl group, 8-indolidinyl group, 2-imidazopyridinyl group, 3-imidazopyri Zinyl group, 5-Imidazopyridinyl group, 6-Imidazopyridinyl group, 7-Imidazopyridinyl group, 8-Imidazopyridinyl group, 3-Pyridinyl group Group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group, 2-isoindolyl group Group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group Group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6 -Isobenzofuranyl group, 7-isobenzofuranyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, azacarbazolyl-1-yl Group, azacarbazolyl-2-yl group, azacarbazolyl-3-yl group, azacarbazolyl-4-yl group, azacarbazolyl-5-yl group, azacarbazolyl-6-yl group, azacarbazolyl-7-yl group, azacarbazolyl-8-yl group Azacarbazolyl-9-yl group, 1-phenanthridinyl group, 2-phenanthridinyl group, 3-phenanthridinyl group, 4-phenanthridinyl group, 6-phenanthridinyl group, 7-phenanthridinyl group, 8-phenanthridinyl group, 9- Phenanthridinyl group, 10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl group, 1,7-phenanthrolin-2-yl group, 1,7-phenanthroline-3-yl group, 1,7-phenanthroline-4-yl group, 1,7-phenanthroline-5-yl group, 1,7-phenanthroline-6-yl group, 1,7-phenanthroline- 8-yl group, 1,7-phenanthroline-9-yl group, 1,7-phenanthroline-10-yl group, 1,8-phenanthroline-2-yl group, 1,8-phene group Nthroline-3-yl group, 1,8-phenanthroline-4-yl group, 1,8-phenanthroline-5-yl group, 1,8-phenanthroline-6-yl group, 1,8-phenanthroline-7-yl group 1,8-phenanthroline-9-yl group, 1,8-phenanthroline-10-yl group, 1,9-phenanthroline-2-yl group, 1,9-phenanthroline-3-yl group, 1,9-phenanthroline -4-yl group, 1,9-phenanthroline-5-yl group, 1,9-phenanthroline-6-yl group, 1,9-phenanthroline-7-yl group, 1,9-phenanthroline-8-yl group, 1,9-phenanthroline-10-yl group, 1,10-phenanthroline-2-yl group, 1,10-phenanthroline-3-yl group, 1,10-phenanthrotrol -4-yl group, 1,10-phenanthroline-5-yl group, 2,9-phenanthroline-1-yl group, 2,9-phenanthroline-3-yl group, 2,9-phenanthroline-4-yl group, 2,9-phenanthroline-5-yl group, 2,9-phenanthroline-6-yl group, 2,9-phenanthroline-7-yl group, 2,9-phenanthroline-8-yl group, 2,9-phenanthroline- 10-yl group, 2,8-phenanthroline-1-yl group, 2,8-phenanthroline-3-yl group, 2,8-phenanthroline-4-yl group, 2,8-phenanthroline-5-yl group, 2 , 8-phenanthroline-6-yl group, 2,8-phenanthroline-7-yl group, 2,8-phenanthroline-9-yl group, 2,8-phenanthroline-10-yl group, 2,7-phenanthroline-1-yl group, 2,7-phenanthroline-3-yl group, 2,7-phenanthroline-4-yl group, 2,7-phenanthroline-5-yl group, 2,7-phenanthroline- 6-yl group, 2,7-phenanthroline-8-yl group, 2,7-phenanthroline-9-yl group, 2,7-phenanthroline-10-yl group, 1-phenazinyl group, 2-phenazinyl group, 1- Phenothiazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group, 10-phenothiazinyl group, 1-phenoxazinyl group, 2-phenoxazinyl group, 3-phenoxazinyl group, 4-phenoxazinyl group, 10- Phenoxazinyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazo group Group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrol-1-yl group, 2-methylpyrrol-3-yl group, 2-methylpyrrole-4- Yl group, 2-methylpyrrol-5-yl group, 3-methylpyrrol-1-yl group, 3-methylpyrrol-2-yl group, 3-methylpyrrol-4-yl group, 3-methylpyrrol-5- Yl group, 2-t-butylpyrrol-4-yl group, 3- (2-phenylpropyl) pyrrol-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1-indolyl group, 2- Methyl-3-indolyl group, 4-methyl-3-indolyl group, 2-t-butyl-1-indolyl group, 4-t-butyl-1-indolyl group, 2-t-butyl-3-indolyl group, 4 -T-butyl-3- Ndryl group, 1-dibenzofuranyl group, 2-dibenzofuranyl group, 3-dibenzofuranyl group, 4-dibenzofuranyl group, 1-dibenzothiophenyl group, 2-dibenzothiophenyl group, 3-dibenzothiophenyl group Group, 4-dibenzothiophenyl group, 1-silafluorenyl group, 2-silafluorenyl group, 3-silafluorenyl group, 4-silafluorenyl group, 1-germafluorenyl group, 2-germafluorenyl group, 3-germafluorenyl group Nyl group and 4-germafluorenyl group are mentioned.
The number of ring-forming atoms of the heterocyclic group in the general formula (1) is preferably 5 to 20, and more preferably 5 to 14. Among the above heterocyclic groups, 1-dibenzofuranyl group, 2-dibenzofuranyl group, 3-dibenzofuranyl group, 4-dibenzofuranyl group, 1-dibenzothiophenyl group, 2-dibenzothiophenyl group, 3- A dibenzothiophenyl group, 4-dibenzothiophenyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, and 9-carbazolyl group are preferable. For the 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group and 4-carbazolyl group, the substituted or unsubstituted aryl having 6 to 30 ring carbon atoms in the general formula (1) is attached to the 9th-position nitrogen atom. The group or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms is preferably substituted.

The alkyl group having 1 to 30 carbon atoms in the general formula (1) may be linear, branched or cyclic. Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n- Hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n- Hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl Group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutyl group, 1,2-dihydroxyethyl Group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 2-chloroisobutyl Group, 1,2-dichloroethyl group, 1,3-dichloroisopropyl group, 2,3-dichloro-t-butyl group, 1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl Group, 2-bromoisobutyl group, 1,2-dibromoethyl group, 1,3-dibromoisopropyl group, 2,3-dibromo-t-butyl group, 1,2,3-tribromopropyl group, iodomethyl group, 1 -Iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3-diiodoisopropyl group, 2, -Diiodo-t-butyl group, 1,2,3-triiodopropyl group, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group, 1 , 3-diaminoisopropyl group, 2,3-diamino-t-butyl group, 1,2,3-triaminopropyl group, cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group, 2-cyanoisobutyl group, 1, 2-dicyanoethyl group, 1,3-dicyanoisopropyl group, 2,3-dicyano-t-butyl group, 1,2,3-tricyanopropyl group, nitromethyl group, 1-nitroethyl group, 2-nitroethyl group, 1 , 2-dinitroethyl group, 2,3-dinitro-t-butyl group, 1,2,3-trinitropropyl group.
Examples of the cyclic alkyl group (cycloalkyl group) include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 1-adamantyl group, 2-adamantyl group, 1-norbornyl group, 2- And norbornyl group.
The linear or branched alkyl group in the general formula (1) preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Among the linear or branched alkyl groups, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group Is preferred.
The number of ring-forming carbon atoms of the cycloalkyl group in the general formula (1) is preferably 3 to 10, and more preferably 5 to 8. Among the cycloalkyl groups, a cyclopentyl group and a cyclohexyl group are preferable.
Examples of the halogenated alkyl group in which the alkyl group is substituted with a halogen atom include those in which the alkyl group having 1 to 30 carbon atoms is substituted with one or more halogen groups. Specific examples include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, and a trifluoromethylmethyl group.

  The alkenyl group having 2 to 30 carbon atoms in the general formula (1) may be linear, branched or cyclic, such as vinyl, propenyl, butenyl, oleyl, eicosapentaenyl, docosahexa. Examples include enyl, styryl, 2,2-diphenylvinyl, 1,2,2-triphenylvinyl, 2-phenyl-2-propenyl and the like. Among the alkenyl groups described above, a vinyl group is preferable.

  The alkynyl group having 2 to 30 carbon atoms in the general formula (1) may be linear, branched or cyclic, and examples thereof include ethynyl, propynyl, 2-phenylethynyl and the like. Of the alkynyl groups described above, an ethynyl group is preferred.

  Examples of the alkylsilyl group having 3 to 30 carbon atoms in the general formula (1) include a trialkylsilyl group having an alkyl group exemplified as the alkyl group having 1 to 30 carbon atoms, specifically, a trimethylsilyl group, Triethylsilyl group, tri-n-butylsilyl group, tri-n-octylsilyl group, triisobutylsilyl group, dimethylethylsilyl group, dimethylisopropylsilyl group, dimethyl-n-propylsilyl group, dimethyl-n-butylsilyl group, dimethyl group -T-butylsilyl group, diethylisopropylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triisopropylsilyl group and the like. The three alkyl groups may be the same or different from each other.

Examples of the arylsilyl group having 6 to 30 ring carbon atoms in the general formula (1) include a dialkylarylsilyl group, an alkyldiarylsilyl group, and a triarylsilyl group.
The dialkylarylsilyl group includes, for example, a dialkylarylsilyl group having two alkyl groups exemplified for the alkyl group having 1 to 30 carbon atoms and one aryl group having 6 to 30 ring carbon atoms. . The carbon number of the dialkylarylsilyl group is preferably 8-30. The two alkyl groups may be the same or different.
Examples of the alkyldiarylsilyl group include an alkyldiarylsilyl group having one alkyl group exemplified for the alkyl group having 1 to 30 carbon atoms and two aryl groups having 6 to 30 ring carbon atoms. . The alkyldiarylsilyl group preferably has 13 to 30 carbon atoms. The two aryl groups may be the same or different.
Examples of the triarylsilyl group include a triarylsilyl group having three aryl groups having 6 to 30 ring carbon atoms. The carbon number of the triarylsilyl group is preferably 18-30. The three aryl groups may be the same or different from each other.

Examples of the trifluoroalkyl group having 1 to 20 carbon atoms in the general formula (1) include a trifluoromethyl group and a trifluoroethyl group.
The C1-C30 alkoxy group in the said General formula (1) is represented as -OY. As an example of this Y, the said C1-C30 alkyl group is mentioned. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.
Examples of the halogenated alkoxy group in which the alkoxy group is substituted with a halogen atom include those in which the C 1-30 alkoxy group is substituted with one or more halogen groups.

  The aralkyl group having 6 to 30 ring carbon atoms in the general formula (1) is represented as -YZ. As an example of this Y, the alkylene group corresponding to the said C1-C30 alkyl group is mentioned. Examples of this Z include the examples of the aryl group having 6 to 30 ring carbon atoms. The aralkyl group has 7 to 30 carbon atoms (the aryl moiety has 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms), and the alkyl moiety has 1 to 30 carbon atoms (preferably 1 to 20 carbon atoms). More preferably, it is 1-10, and more preferably 1-6). Examples of the aralkyl group include benzyl group, 2-phenylpropan-2-yl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, and phenyl-t-butyl. Group, α-naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β- Naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group, 2-β-naphthylisopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p-methylbenzyl group, m -Methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromine Benzyl group, m-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group P-aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o -Cyanobenzyl group, 1-hydroxy-2-phenylisopropyl group, 1-chloro-2-phenylisopropyl group.

  The aryloxy group having 6 to 30 ring carbon atoms in the general formula (1) is represented as -OZ. Examples of Z include the aryl group having 6 to 30 ring carbon atoms or a monocyclic group and a condensed ring group described later. Examples of the aryloxy group include a phenoxy group.

  Examples of the halogen atom in the general formula (1) include fluorine, chlorine, bromine, iodine, and the like, preferably a fluorine atom.

  In the present invention, “ring-forming carbon” means a carbon atom constituting a saturated ring, an unsaturated ring, or an aromatic ring. “Ring-forming atom” means a carbon atom and a hetero atom constituting a hetero ring (including a saturated ring, an unsaturated ring, and an aromatic ring).

In the case of “substituted or unsubstituted”, examples of the substituent include an aryl group, a heterocyclic group, an alkyl group (a linear or branched alkyl group, a cycloalkyl group, a halogenated alkyl group) as described above, In addition to alkenyl, alkynyl, alkylsilyl, arylsilyl, alkoxy, halogenated alkoxy, aralkyl, aryloxy, halogen, deuterium, cyano, hydroxyl, nitro, carboxy, etc. Is mentioned. Among the substituents mentioned here, an aryl group, a heterocyclic group, an alkyl group, a halogen atom, an alkylsilyl group, an arylsilyl group, a cyano group, and a deuterium atom are preferable, and more preferable in the description of each substituent. The specific substituents are preferred.
“Unsubstituted” in the case of “substituted or unsubstituted” means that a hydrogen atom is substituted.
In the compound described below or a partial structure thereof, the case of “substituted or unsubstituted” is the same as described above.

In the general formula (1), R ₁ and R ₆ are represented by the general formula (2).
In the general formula (2), L ₁ , L ₂ and L ₃ are each independently a single bond, a substituted or unsubstituted divalent residue of an aryl group having 6 to 30 ring carbon atoms, or substituted or This is a divalent residue of an unsubstituted heterocyclic group having 5 to 30 ring atoms.
The divalent residue of the aryl group having 6 to 30 ring carbon atoms is the ring in R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ , R ₉ and R ₁₀ in the general formula (1). Examples thereof include a divalent group derived from an aryl group having 6 to 30 carbon atoms.
The divalent residue of the heterocyclic group having 5 to 30 ring atoms is represented by R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ , R ₉ and R ₁₀ in the general formula (1). And a divalent group derived from a heterocyclic group having 5 to 30 ring atoms.

In the general formula (2), Ar ₁ is a substituent having the general formula (3) as a partial structure.
In the general formula (3), X is an oxygen atom or a sulfur atom. In the said General formula (3), A and B represent a 6-membered ring. Another ring may be further condensed to the 6-membered ring represented by A and B.
The substituent having the general formula (3) as a partial structure is
Fluorine atom,
A cyano group,
A substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms,
It has at least one substituent selected from a substituted or unsubstituted arylsilyl group having 6 to 30 ring carbon atoms and a substituted or unsubstituted trifluoroalkyl group having 1 to 20 carbon atoms.

The alkylsilyl group having 3 to 30 carbon atoms and the arylsilyl group having 6 to 30 ring carbon atoms of the substituent having the general formula (3) as a partial structure are represented by R ₂ , R ₃ of the general formula (1), The same as described for R ₄ , R ₅ , R ₇ , R ₈ , R ₉ and R ₁₀ .
Moreover, trifluoromethyl etc. are mentioned as a C1-C20 trifluoroalkyl group, A trifluoromethyl group is preferable among trifluoroalkyl groups.

In the general formula (2), Ar ₂ is
Fluorine atom,
A cyano group,
A substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms,
6 or more ring-forming carbon atoms having at least one substituent selected from a substituted or unsubstituted arylsilyl group having 6 to 30 ring carbon atoms and a substituted or unsubstituted trifluoroalkyl group having 1 to 20 carbon atoms Or a monovalent substituent having a partial structure of the general formula (3). The aryl group and heterocyclic group of Ar ₂ are the same as those described for R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ , R ₉ and R ₁₀ in the general formula (1). . In addition, the alkylsilyl group and arylsilyl group which are substituents of these aryl groups and heterocyclic groups are R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ , R in the general formula (1). ₉ and R ₁₀ are the same as those described above, and the trifluoroalkyl group is the same as that described in the general formula (3).

In the aromatic amine derivative of the present invention, the monovalent substituent having the general formula (3) as a partial structure is preferably a monovalent residue of the general formula (4).
In the general formula (4), X is an oxygen atom or a sulfur atom.
In the general formula (4), R ₁₁ to R ₁₈ are each independently R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ , R ₉ and R _{10 in the} general formula (1). And those described in the general formula (3).
In the general formula (4), at least one of R ₁₁ to R ₁₈ is a fluorine atom, a cyano group, a substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms, a substituted or unsubstituted ring-forming carbon. It is an arylsilyl group having 6 to 30 carbon atoms, or a substituted or unsubstituted trifluoroalkyl group having 1 to 20 carbon atoms.
However, in the general formula (2), when Ar ₁ is a monovalent residue of the general formula (4), one of R ₁₁ to R ₁₈ is bonded to L ₁ . And when Ar ₂ is a monovalent residue of the general formula (4), one of R ₁₁ to R ₁₈ is a single bond that binds to L ₂ . is there. Thus, when one of R ₁₁ to R ₁₈ is a single bond, the structure of the general formula (4) is, for example, as shown in the following general formula (4A) to general formula (4D). is there. Here, the general formula (4A) indicates that the portion of R ₁₁ in the general formula (4) is a single bond, and does not indicate that it is a methyl group. This also applies to the other general formulas (4B) to (4D). Among these, general formula (4A) when R ₁₁ becomes a single bond and general formula (4C) where R ₁₃ becomes a single bond are preferable.

In the general formula _(4), among the combinations of _{R 11} and _{R 12, R 12} and _{R 13, R 13} and _{R 14, R 15} and _{R 16, R 16} and _{R 17} and _{R 17} and _{R 18,} at least one One or a combination may form a saturated or unsaturated ring. Examples of the case where such a ring may be formed in the general formula (4) include the following general formulas (4E), (4F), and (4G). In the following general formulas (4E), (4F) and (4G), R ₁₁ to R ₂₀ are independently from R ₂ to R ₅ and R ₇ to R ₁₀ in the general formula (1). The same as described.

  Specific examples of the structure of the aromatic amine derivative of the present invention include the following. However, the present invention is not limited to aromatic amine derivatives having these structures.

In the aromatic amine derivative of the present invention, R ₁ and R ₆ in the general formula (1) are preferably represented by the general formula (2). In this case, the aromatic amine derivative has the following general formula: The structure is represented by (1A).

As specific examples of the aromatic amine derivative of the present invention, in the general formula (1), R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ , R ₉ and R ₁₀ , L _{1 to} L ₃ , And aromatic amine derivatives when Ar _{1 to} Ar ₂ are shown in Tables 1 to 74. Incidentally, in the _L 1 ~L ₃ in the table, "-" represents a single bond. Further, in Ar ₁ to Ar ₂ in the table, the chemical formula in its end a line extending from a ring structure outwardly (CH 3, _Ph, CN, benzene ring, etc.) which have not been described is a single bond It does not represent a methyl group. For example, in the following compound 1, Ar ₁ represents a single bond at the 1-position of the dibenzofuran ring, that is, represents an 8-fluoro-1-dibenzofuranyl group. Similarly, Ar ₂ represents a p-fluorophenyl group.

In the specific example of the aromatic amine derivative, for R ₁ and R ₆ , the compounds represented by the general formula (2) have the same structure as each other. However, the present invention is not limited to this. It may be a compound having a different structure.

[Materials for organic EL elements]
The aromatic amine derivative of the present invention can be used as a material for an organic EL device. The material for an organic EL device may contain the aromatic amine derivative of the present invention alone or may contain other compounds. The material for organic EL elements containing the aromatic amine derivative of the present invention can be used as a dopant material, for example.
As a case where the aromatic amine derivative of the present invention and another compound are included, for example, a material for an organic EL device including an anthracene derivative represented by the general formula (20) can be given.
Moreover, the organic EL element material which contains the pyrene derivative represented by following General formula (30) with the aromatic amine derivative of this invention instead of this anthracene derivative is mentioned.
Furthermore, the organic EL element material containing the aromatic amine derivative of this invention, the anthracene derivative represented by the said General formula (20), and the pyrene derivative represented by the following general formula (30) is mentioned.

[Organic EL device]
The organic EL device of the present invention includes an organic compound layer between a cathode and an anode.
The aromatic amine derivative of the present invention is contained in this organic compound layer. Moreover, an organic compound layer is formed using the material for organic EL elements containing the aromatic amine derivative of this invention.
The organic compound layer has at least one organic thin film layer composed of an organic compound. At least one of the organic thin film layers contains the aromatic amine derivative of the present invention alone or as a component of a mixture. In addition, the organic thin film layer may contain the inorganic compound.
At least one of the organic thin film layers is a light emitting layer. Therefore, the organic compound layer may be composed of, for example, a single light emitting layer, such as a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole barrier layer, an electron barrier layer, etc. You may have the layer employ | adopted by a well-known organic EL element. If there are a plurality of organic thin film layers, the aromatic amine derivative of the present invention is contained alone or as a component of the mixture in at least one of the layers.
Preferably, the light emitting layer contains the aromatic amine derivative of the present invention. In this case, the light emitting layer can be composed of only an aromatic amine derivative, or can be composed of an aromatic amine derivative as a host material or a dopant material.

As a typical element configuration of the organic EL element,
(A) Anode / light emitting layer / cathode (b) Anode / hole injection / transport layer / light emitting layer / cathode (c) Anode / light emitting layer / electron injection / transport layer / cathode (d) Anode / hole injection / transport Layer / light emitting layer / electron injection / transport layer / cathode (e) Structure of anode / hole injection / transport layer / light emitting layer / barrier layer / electron injection / transport layer / cathode.
Among the above, the configuration (d) is preferably used, but it is of course not limited thereto.
The “light emitting layer” is an organic layer having a light emitting function, and includes a host material and a dopant material when a doping system is employed. At this time, the host material mainly has a function of encouraging recombination of electrons and holes and confining excitons in the light emitting layer, and the dopant material efficiently emits excitons obtained by recombination. It has a function.

  The above “hole injection / transport layer” means “at least one of a hole injection layer and a hole transport layer”, and “electron injection / transport layer” means “an electron injection layer and an electron transport layer”. "At least one of them". Here, when it has a positive hole injection layer and a positive hole transport layer, it is preferable that the positive hole injection layer is provided in the anode side. Moreover, when it has an electron injection layer and an electron carrying layer, it is preferable that the electron injection layer is provided in the cathode side. Further, the hole injection layer, the light emitting layer, and the electron injection layer may each be formed of two or more layers. In that case, in the case of a hole injection layer, the layer that injects holes from the electrode is a hole injection layer, and the layer that receives holes from the hole injection layer and transports holes to the light emitting layer is a hole transport layer. Call. Similarly, in the case of an electron injection layer, a layer for injecting electrons from an electrode is called an electron injection layer, and a layer for receiving electrons from the electron injection layer and transporting electrons to a light emitting layer is called an electron transport layer.

The organic EL element can prevent the brightness | luminance and lifetime fall by quenching by making the said organic thin film layer into a multilayer structure. If necessary, a light emitting material, a doping material, a hole injection material, and an electron injection material can be used in combination. In addition, depending on the doping material, light emission luminance and light emission efficiency may be improved.
Each of these layers is selected and used depending on factors such as the energy level of the material, heat resistance, and adhesion to the organic layer or metal electrode.

In FIG. 1, schematic structure of an example of the organic EL element in embodiment of this invention is shown.
The organic EL element 1 includes a transparent substrate 2, an anode 3, a cathode 4, and an organic compound layer 10 disposed between the anode 3 and the cathode 4.
The organic compound layer 10 includes a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and an electron injection layer 9 in order from the anode 3 side.

<Light emitting layer>
The light emitting layer of the organic EL element has a function of providing a field for recombination of electrons and holes and connecting this to light emission.
In the organic EL device of the present invention, the aromatic amine derivative of the present invention is contained in at least one layer of the organic thin film layer, and is further represented by the anthracene derivative represented by the general formula (20) and the following general formula (30). It is preferable that at least one of pyrene derivatives is contained. In particular, it is preferable that the light emitting layer contains the aromatic amine derivative of the present invention as a dopant material and an anthracene derivative represented by the above formula (20) as a host material.

(Anthracene derivative)
The anthracene derivative that can be included as a host material in the light emitting layer is represented by the general formula (20).
In the general formula (20), Ar ¹¹ and Ar ¹² are each independently a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms, or a condensed having 10 to 30 ring atoms that are substituted or unsubstituted. It is a group composed of a ring group or a combination of the monocyclic group and the condensed ring group.

In the general formula (20), the monocyclic group is a group composed of only a ring structure having no condensed structure.
The number of ring-forming atoms of the monocyclic group is 5-30, preferably 5-20. Examples of the monocyclic group include aromatic groups such as phenyl group, biphenyl group, terphenyl group, and quarterphenyl group, and heterocyclic groups such as pyridyl group, pyrazyl group, pyrimidyl group, triazinyl group, furyl group, and thienyl group. Is mentioned. Among these, a phenyl group, a biphenyl group, and a terphenyl group are preferable.

In the general formula (20), the condensed ring group is a group in which two or more ring structures are condensed.
The number of ring-forming atoms of the fused ring group is 10-30, preferably 10-20. Examples of the condensed ring group include naphthyl group, phenanthryl group, anthryl group, chrysenyl group, benzoanthryl group, benzophenanthryl group, triphenylenyl group, benzochrysenyl group, indenyl group, fluorenyl group, 9,9-dimethylfluorene. Nyl group, benzofluorenyl group, dibenzofluorenyl group, fluoranthenyl group, benzofluoranthenyl group and other condensed aromatic ring groups, benzofuranyl group, benzothiophenyl group, indolyl group, dibenzofuranyl group, Examples thereof include condensed heterocyclic groups such as a dibenzothiophenyl group, a carbazolyl group, a quinolyl group, and a phenanthrolinyl group. Among these, naphthyl group, phenanthryl group, anthryl group, 9,9-dimethylfluorenyl group, fluoranthenyl group, benzoanthryl group, dibenzothiophenyl group, dibenzofuranyl group, and carbazolyl group are preferable.

  In the general formula (20), as a group composed of a combination of the monocyclic group and the condensed ring group, for example, a phenyl group, a naphthyl group, and a phenyl group are combined in order from the anthracene ring side. Group (see the following compound EM50 etc.).

Specific examples of the alkyl group, silyl group, alkoxy group, aryloxy group, aralkyl group, and halogen atom from R ¹⁰¹ to R ¹⁰⁸ in the general formula (20) include R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same as those described above, and the cycloalkyl group is the same as that exemplified above. Further, the case of “substituted or unsubstituted” in these substituents is the same as described above.
The preferable specific example in General formula (20) is given below.

Ar ¹¹ and Ar ¹² in the general formula (20) and preferable substituents of “substituted or unsubstituted” from R ¹⁰¹ to R ¹⁰⁸ are monocyclic groups, condensed ring groups, alkyl groups, cycloalkyl groups, silyl groups. , An alkoxy group, a cyano group, and a halogen atom (particularly fluorine). Particularly preferred are a monocyclic group and a condensed ring group, and preferred specific substituents are the same as those in the general formula (20) and the general formula (1).

  The anthracene derivative represented by the general formula (20) is preferably any of the following anthracene derivatives (A), (B), and (C), and is selected according to the configuration of the organic EL element to be applied and the required characteristics. .

・ Anthracene derivatives (A)
In the anthracene derivative (A), Ar ¹¹ and Ar ¹² in the general formula (20) are substituted or unsubstituted condensed ring groups having 10 to 30 ring atoms. The anthracene derivative (A) is divided into a case where Ar ¹¹ and Ar ¹² are the same substituted or unsubstituted condensed ring group and a case where Ar ¹¹ and Ar ¹² are different substituted or unsubstituted condensed ring groups. be able to. When Ar ¹¹ and Ar ¹² are different, the case where the substitution positions are different is also included.

As the anthracene derivative (A), an anthracene derivative in which Ar ¹¹ and Ar ¹² in the general formula (20) are different substituted or unsubstituted condensed ring groups is particularly preferable.
In the case of the anthracene derivative (A), preferred specific examples of the condensed ring group in Ar ¹¹ and Ar ¹² in the general formula (20) are as described above. Of these, a naphthyl group, a phenanthryl group, a benzoanthryl group, a 9,9-dimethylfluorenyl group, and a dibenzofuranyl group are preferable.

・ Anthracene derivatives (B)
In the anthracene derivative (B), one of Ar ¹¹ and Ar ¹² in the general formula (20) is a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms, and the other is a substituted or unsubstituted ring. It is a condensed ring group having 10 to 30 atoms.
As a preferable form of the anthracene derivative (B), Ar ¹² is selected from a naphthyl group, a phenanthryl group, a benzoanthryl group, a 9,9-dimethylfluorenyl group, and a dibenzofuranyl group, and Ar ¹¹ is unsubstituted. Or a phenyl group in which at least one of the monocyclic group and the condensed ring group is substituted.
In the case of the anthracene derivative (B), specific groups of preferred monocyclic groups and condensed ring groups are as described above.

Another preferred form of the anthracene derivative (B) includes a case where Ar ¹² is a substituted or unsubstituted condensed ring group having 10 to 30 ring atoms and Ar ¹¹ is an unsubstituted phenyl group. . In this case, as the condensed ring group, a phenanthryl group, a 9,9-dimethylfluorenyl group, a dibenzofuranyl group, and a benzoanthryl group are particularly preferable.

・ Anthracene derivatives (C)
In the anthracene derivative (C), Ar ¹¹ and Ar ¹² in the general formula (20) are each independently a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms.
A preferred form of the anthracene derivative (C) includes a case where Ar ¹¹ and Ar ¹² are each independently a substituted or unsubstituted phenyl group.
As a more preferable form of the anthracene derivative (C), Ar ¹¹ is an unsubstituted phenyl group, and Ar ¹² is a phenyl group having at least one of the monocyclic group and the condensed ring group as a substituent. And Ar ¹¹ and Ar ¹² are each independently a phenyl group having at least one of the monocyclic group and the condensed ring group as a substituent.

Specific examples of the preferable monocyclic group and condensed ring group as the substituent that Ar ¹¹ and Ar ¹² in the general formula (20) have are as described above. The monocyclic group as a substituent is more preferably a phenyl group or a biphenyl group, and the condensed ring group as a substituent is a naphthyl group, a phenanthryl group, a 9,9-dimethylfluorenyl group, a dibenzofuranyl group, a benzoan group. A tolyl group is more preferred.

  Specific examples of the structure of the anthracene derivative represented by the general formula (20) include the following. However, the present invention is not limited to the anthracene derivatives having these structures.

In the general formula (20A), R ¹⁰¹ and R ¹⁰⁵ are each independently a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms, a substituted or unsubstituted group. A condensed ring group having 10 to 30 ring atoms, a group composed of a combination of a monocyclic group and a condensed ring group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted ring forming carbon A cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted ring structure having 6 to 30 carbon atoms Aryloxy or a substituted or unsubstituted silyl group.

In the general formula (20A), Ar ⁵¹ and Ar ⁵⁴ each independently represents a substituted or unsubstituted monocyclic divalent residue having 5 to 30 ring atoms, or a substituted or unsubstituted ring atom having 10 atoms. -30 condensed ring divalent residues.
In the general formula (20A), Ar ⁵² and Ar ⁵⁵ are each independently a single bond, a substituted or unsubstituted monocyclic divalent residue having 5 to 30 ring atoms, or a substituted or unsubstituted ring. It is a condensed ring divalent residue having 10 to 30 atoms.
In the general formula (20A), Ar ⁵³ and Ar ⁵⁶ each independently represent a hydrogen atom, a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted ring atom having 10 atoms. -30 condensed ring groups.
All or some of the hydrogen atoms in the general formula (20A) may be deuterium atoms.

In the general formula (20B), Ar ⁵¹ is a substituted or unsubstituted monocyclic divalent residue having 5 to 30 ring atoms, or a substituted or unsubstituted condensed ring divalent having 10 to 30 ring atoms. Residue.
In the general formula (20B), Ar ⁵² and Ar ⁵⁵ each independently represent a single bond, a substituted or unsubstituted monocyclic divalent residue having 5 to 30 ring atoms, or a substituted or unsubstituted ring. It is a condensed ring divalent residue having 10 to 30 atoms.
In General Formula (20B), Ar ⁵³ and Ar ⁵⁶ each independently represent a hydrogen atom, a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted ring atom having 10 atoms. -30 condensed ring groups.
All or some of the hydrogen atoms in the general formula (20B) may be deuterium atoms.

In the general formula (20C), Ar ⁵² represents a substituted or unsubstituted monocyclic divalent residue having 5 to 30 ring atoms, or a substituted or unsubstituted condensed ring divalent having 10 to 30 ring atoms. Residue.
In the above general formula (20C), Ar ⁵⁵ is a single bond, a substituted or unsubstituted monovalent divalent residue having 5 to 30 ring atoms, or a substituted or unsubstituted condensed ring having 10 to 30 ring atoms. It is a ring divalent residue.
In the general formula (20C), Ar ⁵³ and Ar ⁵⁶ each independently represent a hydrogen atom, a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted ring atom having 10 atoms. -30 condensed ring groups.
All or some of the hydrogen atoms in the general formula (20C) may be deuterium atoms.

In the general formula (20D), Ar ⁵² represents a substituted or unsubstituted monocyclic divalent residue having 5 to 30 ring atoms, or a substituted or unsubstituted condensed ring divalent having 10 to 30 ring atoms. Residue.
In the above general formula (20D), Ar ⁵⁵ is a single bond, a substituted or unsubstituted monocyclic divalent residue having 5 to 30 ring atoms, or a substituted or unsubstituted condensed ring having 10 to 30 ring atoms. It is a ring divalent residue.
In the general formula (20D), Ar ⁵³ and Ar ⁵⁶ are each independently a hydrogen atom, a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted ring atom having 10 atoms. -30 condensed ring groups.
All or some of the hydrogen atoms in the general formula (20D) may be deuterium atoms.

In the general formula (20E), Ar ⁵² and Ar ⁵⁵ are each independently a single bond, a substituted or unsubstituted monocyclic divalent residue having 5 to 30 ring atoms, or a substituted or unsubstituted ring. It is a condensed ring divalent residue having 10 to 30 atoms.
In the general formula (20E), Ar ⁵³ and Ar ⁵⁶ each independently represent a hydrogen atom, a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted ring atom having 10 atoms. -30 condensed ring groups.
All or some of the hydrogen atoms in the general formula (20E) may be deuterium atoms.

More specifically, the following can be mentioned. However, the present invention is not limited to the anthracene derivatives having these structures.
Of the specific structures of the following anthracene derivatives, in the compounds EM36, EM44, EM77, EM85, EM86, etc., the line extending from the 9th position of the fluorene ring represents a methyl group, that is, the fluorene ring is 9 , 9-dimethylfluorene ring.
Further, among the specific structures of the following anthracene derivatives, in the compounds EM151, EM154, EM157, EM161, EM163, EM166, EM169, EM173, etc., a line extending in a cross shape outward from the ring structure is a tertiary butyl group. Represents.
Further, among the specific structures of the following anthracene derivatives, in the compounds EM152, EM155, EM158, EM164, EM167, EM170, EM171, EM180, EM181, EM182, EM183, EM184, EM185, etc., a line extending from the silicon atom (Si) Represents a methyl group, that is, the substituent having the silicon atom represents a trimethylsilyl group.

(Pyrene derivative)
As another form of the organic EL device of the present invention, at least one of the organic thin film layers comprises an aromatic amine derivative represented by the general formula (1) and a pyrene derivative represented by the following general formula (30). The form to contain is mentioned. The light emitting layer preferably contains an aromatic amine derivative as a dopant material and a pyrene derivative as a host material.

In the general formula (30), Ar ¹¹¹ and Ar ²²² are each independently a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms.
In the general formula (30), L ¹ and L ² each independently represent a substituted or unsubstituted divalent aryl group or heterocyclic group having 6 to 30 ring carbon atoms.
In the general formula (30), m is an integer of 0 to 1, n is an integer of 1 to 4, s is an integer of 0 to 1, and t is an integer of 0 to 3.
In the general formula (30), L ¹ or Ar ¹¹¹ is bonded to any one of the 1-5 positions of pyrene, and L ² or Ar ²²² is bonded to any of the 6-10 positions of pyrene.
Further, Ar ¹¹¹ and Ar ²²² in the general formula (30), and the case of “substituted or unsubstituted” in the substituents of L ¹ and L ² are the same as described above.

L ¹ and L ² in the general formula (30) are preferably
A substituted or unsubstituted phenylene group,
A substituted or unsubstituted biphenylene group,
A substituted or unsubstituted naphthylene group,
It is selected from a substituted or unsubstituted terphenylene group, a substituted or unsubstituted fluorenylene group, and a divalent aryl group composed of a combination of these groups.

M in the general formula (30) is preferably an integer of 0 to 1.
N in the general formula (30) is preferably an integer of 1 to 2.
S in the general formula (30) is preferably an integer of 0 to 1.
T in the general formula (30) is preferably an integer of 0 to 2.
The aryl groups of Ar ¹¹¹ and Ar ²²² in the general formula (30) are described in R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ , R ₉ and R ₁₀ in the general formula (1). It is the same as what I did. A substituted or unsubstituted aryl group having 6 to 20 ring carbon atoms is preferable, and a substituted or unsubstituted aryl group having 6 to 16 ring carbon atoms is more preferable. Preferable specific examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, a biphenyl group, an anthryl group, and a pyrenyl group.

(Other uses of compounds)
The aromatic amine derivative of the present invention, the anthracene derivative represented by the above general formula (20) and the pyrene derivative represented by the above general formula (30), in addition to the light emitting layer, a hole injection layer, a hole transport layer, It can also be used for an electron injection layer and an electron transport layer.

(Other materials that can be used for the light emitting layer)
Examples of materials other than the general formula (20) and the general formula (30) that can be used in the light emitting layer together with the aromatic amine derivative of the present invention include naphthalene, phenanthrene, rubrene, anthracene, tetracene, pyrene, perylene, chrysene, Condensed polycyclic aromatic compounds such as decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, fluorene, spirofluorene and their derivatives, organometallic complexes such as tris (8-quinolinolato) aluminum, triarylamine derivatives, styryl Amine derivatives, stilbene derivatives, coumarin derivatives, pyran derivatives, oxazone derivatives, benzothiazole derivatives, benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives, cinnamic acid ester derivatives, Diketopyrrolopyrrole derivatives, acridone derivatives, quinacridone derivatives, but is not limited thereto.

(Content)
When the organic thin film layer contains the aromatic amine derivative of the present invention as a dopant material, the content of the aromatic amine derivative is preferably 0.1% by mass or more and 20% by mass or less, and preferably 1% by mass or more and 10% by mass. The following is more preferable.

<Board>
The organic EL element of the present invention is produced on a light-transmitting substrate. Here, the translucent substrate is a substrate that supports the organic EL element, and is preferably a smooth substrate having a light transmittance in the visible region of 400 nm or more and 700 nm or less of 50% or more. The substrate preferably further has mechanical and thermal strength.
Specifically, a glass plate, a polymer plate, etc. are mentioned.
Examples of the glass plate include those using soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz and the like as raw materials.
Examples of the polymer plate include those using polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone and the like as raw materials. A polymer film can also be used as the substrate.

<Anode and cathode>
As the conductive material used for the anode of the organic EL device of the present invention, a material having a work function larger than 4 eV is suitable, and carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum Further, palladium, etc. and their alloys, metal oxides such as tin oxide and indium oxide used for ITO substrates and NESA substrates, and organic conductive resins such as polythiophene and polypyrrole are used. The anode is produced by forming a thin film of these conductive materials by a method such as vapor deposition or sputtering.
When light emitted from the light-emitting layer is extracted from the anode side, it is preferable that the light transmittance in the visible region of the anode be greater than 10%. The sheet resistance of the anode is preferably several hundred Ω / □ or less. Although the film thickness of the anode depends on the material, it is usually selected in the range of 10 nm to 1 μm, preferably 10 nm to 200 nm.

As the conductive material used for the cathode of the organic EL device of the present invention, those having a work function smaller than 4 eV are suitable, and magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum , Lithium fluoride and the like and alloys thereof are used, but not limited thereto. Examples of alloys include magnesium / silver, magnesium / indium, lithium / aluminum, and the like, but are not limited thereto. The ratio of the alloy is controlled by the temperature of the vapor deposition source, the atmosphere, the degree of vacuum, etc., and is selected to an appropriate ratio. Similarly to the anode, the cathode can be produced by forming a thin film by a method such as vapor deposition or sputtering. Moreover, the aspect which takes out light emission from a cathode side is also employable.
In addition, when light emitted from the light emitting layer is extracted from the cathode side, it is preferable that the light transmittance in the visible region of the cathode be greater than 10%. The sheet resistance of the cathode is preferably several hundred Ω / □ or less. The layer thickness of the cathode depends on the material, but is usually selected in the range of 10 nm to 1 μm, preferably 50 nm to 200 nm.

  If necessary, the anode and the cathode may be formed of two or more layers.

  In the organic EL device of the present invention, in order to emit light efficiently, it is desirable that at least one surface is sufficiently transparent in the light emission wavelength region of the device. The substrate is also preferably transparent. The transparent electrode is set using the above-described conductive material so that predetermined translucency is ensured by a method such as vapor deposition or sputtering.

<Hole injection / transport layer>
For the hole injection / transport layer, the following hole injection materials and hole transport materials are used.
As a hole injection material, a compound having the ability to transport holes, the hole injection effect from the anode, the hole injection effect excellent for the light emitting layer or the light emitting material, and the thin film forming ability Is preferred. Specifically, phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, benzidine-type triphenylamine, diamine-type triphenylamine, hexacyanohexaazatriphenylene, and their derivatives, and polyvinylcarbazole, polysilane, conductive polymers, etc. Examples include, but are not limited to, polymer materials.

  Among the hole injection materials that can be used in the organic EL device of the present invention, a more effective hole injection material is a phthalocyanine derivative.

Examples of the phthalocyanine (Pc) derivatives include H2Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl2SiPc, (HO) AlPc, (HO) GaPc, VOPc, and OPP Although there exist phthalocyanine derivatives and naphthalocyanine derivatives, such as MoOPc and GaPc-O-GaPc, it is not limited to these.
In addition, carriers can be sensitized by adding an electron acceptor such as a TCNQ derivative to the hole injection material.

A preferred hole transport material that can be used in the organic EL device of the present invention is an aromatic tertiary amine derivative.
Examples of aromatic tertiary amine derivatives include N, N′-diphenyl-N, N′-dinaphthyl-1,1′-biphenyl-4,4′-diamine, N, N, N ′, N′-tetra. Biphenyl-1,1′-biphenyl-4,4′-diamine or the like, or an oligomer or polymer having an aromatic tertiary amine skeleton is not limited thereto.

<Electron injection / transport layer>
The following electron injection materials are used for the electron injection / transport layer.
As the electron injecting material, a compound having an ability to transport electrons, an electron injecting effect from the cathode, an excellent electron injecting effect for the light emitting layer or the light emitting material, and an excellent thin film forming ability is preferable.

In the organic EL device of the present invention, more effective electron injection materials are metal complex compounds and nitrogen-containing heterocyclic derivatives.
Examples of the metal complex compound include 8-hydroxyquinolinate lithium, bis (8-hydroxyquinolinato) zinc, tris (8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, and bis. (10-Hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, and the like may be mentioned, but are not limited thereto.

  As the nitrogen-containing heterocyclic derivative, for example, oxazole, thiazole, oxadiazole, thiadiazole, triazole, pyridine, pyrimidine, triazine, phenanthroline, benzimidazole, imidazopyridine and the like are preferable, and among them, benzimidazole derivative, phenanthroline derivative, imidazopyridine Derivatives are preferred.

A preferred form of the organic EL device of the present invention includes a form in which at least one of an electron donating dopant and an organometallic complex is further contained in these electron injection materials. More preferably, in order to facilitate reception of electrons from the cathode, at least one of an electron donating dopant and an organometallic complex is doped in the vicinity of the interface between the organic thin film layer and the cathode.
According to such a configuration, it is possible to improve the light emission luminance and extend the life of the organic EL element.
Examples of the electron donating dopant include at least one selected from alkali metals, alkali metal compounds, alkaline earth metals, alkaline earth metal compounds, rare earth metals, rare earth metal compounds, and the like.
Examples of the organometallic complex include at least one selected from an organometallic complex containing an alkali metal, an organometallic complex containing an alkaline earth metal, an organometallic complex containing a rare earth metal, and the like.

Examples of the alkali metal include lithium (Li) (work function: 2.93 eV), sodium (Na) (work function: 2.36 eV), potassium (K) (work function: 2.28 eV), rubidium (Rb) (work Function: 2.16 eV), cesium (Cs) (work function: 1.95 eV) and the like, and those having a work function of 2.9 eV or less are particularly preferable. Of these, K, Rb and Cs are preferred, Rb or Cs is more preferred, and Cs is most preferred.
Examples of the alkaline earth metal include calcium (Ca) (work function: 2.9 eV), strontium (Sr) (work function: 2.0 eV to 2.5 eV), barium (Ba) (work function: 2.52 eV). A work function of 2.9 eV or less is particularly preferable.
Examples of the rare earth metal include scandium (Sc), yttrium (Y), cerium (Ce), terbium (Tb), ytterbium (Yb) and the like, and those having a work function of 2.9 eV or less are particularly preferable.
Among the above metals, preferred metals are particularly high in reducing ability, and by adding a relatively small amount to the electron injection region, it is possible to improve the light emission luminance and extend the life of the organic EL element.

Examples of the alkali metal compound include lithium oxide (Li ₂ O), cesium oxide (Cs ₂ O), alkali oxides such as potassium oxide (K ₂ O), lithium fluoride (LiF), sodium fluoride (NaF), fluorine. Examples thereof include alkali halides such as cesium fluoride (CsF) and potassium fluoride (KF), and lithium fluoride (LiF), lithium oxide (Li ₂ O), and sodium fluoride (NaF) are preferable.
Examples of the alkaline earth metal compound include barium oxide (BaO), strontium oxide (SrO), calcium oxide (CaO), and barium strontium oxide (Ba _x Sr _1-x O) (0 <x <1), Examples thereof include barium calcium oxide (Ba _x Ca _1-x O) (0 <x <1), and BaO, SrO, and CaO are preferable.
The rare earth metal compound, ytterbium fluoride _(YbF 3), scandium fluoride _(ScF 3), scandium oxide _(ScO 3), yttrium oxide _{(Y 2 O} 3), cerium oxide _{(Ce 2 O} 3), gadolinium fluoride _(GdF 3), such as terbium fluoride (TbF ₃₎ can be _{mentioned, YbF 3, ScF 3, TbF} 3 are preferable.

As described above, the organometallic complex is not particularly limited as long as it contains at least one of alkali metal ions, alkaline earth metal ions, and rare earth metal ions as metal ions. The ligands include quinolinol, benzoquinolinol, acridinol, phenanthridinol, hydroxyphenyl oxazole, hydroxyphenyl thiazole, hydroxydiaryl thiadiazole, hydroxydiaryl thiadiazole, hydroxyphenylpyridine, hydroxyphenylbenzimidazole, hydroxybenzotriazole, Hydroxyfulborane, bipyridyl, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, β-diketones, azomethines, and derivatives thereof are preferable, but not limited thereto.
The electron donating dopant and the organometallic complex may be used singly or in combination of two or more.

(Method for forming each layer of organic EL element)
Each layer of the organic EL device of the present invention can be formed by any of dry deposition methods such as vacuum deposition, sputtering, plasma, and ion plating, and wet deposition methods such as spin coating, dipping, flow coating, and inkjet. can do.

In the case of the wet film forming method, the material for forming each layer is dissolved or dispersed in an appropriate solvent such as ethanol, chloroform, tetrahydrofuran, dioxane or the like to form a thin film, and any solvent may be used.
As a solution suitable for such a wet film-forming method, an organic EL material-containing solution containing the aromatic amine derivative of the present invention and a solvent can be used as a material for an organic EL element.

  In any organic thin film layer, an appropriate resin or additive may be used for improving the film formability and preventing pinholes in the film.

(Thickness of each layer of organic EL element)
The film thickness is not particularly limited, but must be set to an appropriate film thickness. If the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. If the film thickness is too thin, pinholes and the like are generated, and sufficient light emission luminance cannot be obtained even when an electric field is applied. The normal film thickness is suitably in the range of 5 nm to 10 μm, but more preferably in the range of 10 nm to 0.2 μm.

(Use of organic EL elements)
The organic EL device of the present invention can be used for a flat light emitter such as a flat panel display, a light source such as a copying machine, a printer, a backlight of a liquid crystal display or an instrument, a lighting device, a display board, a marker lamp, and the like. Moreover, the compound of this invention can be used not only in an organic EL element but in fields, such as an electrophotographic photoreceptor, a photoelectric conversion element, a solar cell, an image sensor.

[Modification of Embodiment]

  The present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  For example, in the organic EL device of the present invention, in the light emitting layer, in addition to at least one selected from the aromatic amine derivatives represented by the general formula (1), a light emitting material, a doping material, a hole injection material, At least one of the hole transport material and the electron injection material may be contained in the same layer. In addition, in order to improve the stability of the organic EL device obtained by the present invention against temperature, humidity, atmosphere, etc., a protective layer is provided on the surface of the device, or the entire device is protected by silicon oil, resin, etc. It is also possible to do.

  Moreover, the structure of an organic EL element is not limited to the structural example of the organic EL element 1 shown in FIG. For example, an electron barrier layer may be provided on the anode side of the light emitting layer, and a hole barrier layer may be provided on the cathode side of the light emitting layer.

Further, the light emitting layer is not limited to one layer, and a plurality of light emitting layers may be stacked. When the organic EL element has a plurality of light emitting layers, it is preferable that at least one light emitting layer contains the aromatic amine derivative of the present invention. In this case, the other light emitting layer may be a fluorescent light emitting layer that includes a fluorescent light emitting material and emits fluorescence, or may be a phosphorescent light emitting layer that includes a phosphorescent light emitting material and emits phosphorescence.
Further, when the organic EL element has a plurality of light emitting layers, these light emitting layers may be provided adjacent to each other, or may be laminated via other layers (for example, charge generation layers). .

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated in more detail, this invention is not restrict | limited at all to the description content of these Examples.

<Synthesis of compounds>
Synthesis Example 1 (Synthesis of Compound 1)
A synthesis scheme of Compound 1 is shown below.

In a 300 mL eggplant flask under an argon stream,
Amine compound 1 (7.7 g (22 mmol)),
1,6-dibromopyrene (3.6 g (10 mmol)),
Sodium tert-butoxide (2 g),
Tris (dibenzylideneacetone) dipalladium (0) [Pd ₂ (dba) ₃ ] (550 mg),
Tri-tert-butylphosphine (115 mg),
100mL dehydrated toluene
And reacted at 85 ° C. for 7 hours.
After completion of the reaction, the reaction solution was filtered, the resulting crude product was purified by silica gel chromatography (toluene), and the resulting solid was recrystallized from toluene. The obtained solid was dried under reduced pressure to obtain 4.5 g of Compound 1. The obtained compound 1 was analyzed by FD-MS (field desorption mass spectrum). The results are shown below.
_{FDMS, calcd for C 54 H 46} F 2 N 2 O 2 Si 2 = 896, found m / z = 896 (M +)

Synthesis Examples 2-3 (Synthesis of compounds 2 and 3)
The same procedure as in Compound Synthesis Example 1 was performed except that the amine compound 1 of the compound synthesis example 1 was changed to the amine compound 2 or the amine compound 3 shown below to obtain the compound 2 and the compound 3 shown below. The amine compound 2 and the amine compound 3 used in the synthesis were 22 mmol, like the amine compound 1 in the synthesis example 1.

<Production of organic EL element>
Example 1
A transparent electrode made of indium tin oxide having a thickness of 120 nm was provided on a glass substrate having a size of 25 mm × 75 mm × 1.1 mm. This transparent electrode serves as an anode.
Subsequently, the glass substrate was cleaned by irradiating with ultraviolet rays and ozone, and then placed in a vacuum deposition apparatus.
First, N ′, N ″ -bis [4- (diphenylamino) phenyl] -N ′, N ″ -diphenylbiphenyl-4,4′-diamine was deposited to a thickness of 60 nm as a hole injection layer. After that, N, N, N ′, N′-tetrakis (4-biphenyl) -4,4′-benzidine was vapor-deposited to a thickness of 20 nm as a hole transport layer thereon.
Next, an anthracene derivative EM2 as a host material and compound 1 as a dopant material were co-evaporated on the hole transport layer at a mass ratio of 40: 2, thereby forming a light-emitting layer having a thickness of 40 nm.
On the light emitting layer, tris (8-hydroxyquinolinato) aluminum was deposited to a thickness of 20 nm as an electron injection layer.
Next, lithium fluoride was vapor-deposited on the electron injection layer to a thickness of 1 nm.
Next, aluminum was deposited on the lithium fluoride film to a thickness of 150 nm. The aluminum film and lithium fluoride film serve as a cathode.
Thus, the organic EL element of Example 1 was produced.
When the organic EL element of Example 1 was driven at a current density of 10 mA / cm ² , blue light emission was observed. Thus, it was confirmed that Compound 1 is useful as an organic electroluminescence element material.

-Examples 2-3
The organic EL device of Example 2 was produced in the same manner as in Example 1 of the organic EL device, except that Compound 1 as the dopant material of the organic EL device of Example 1 was changed to Compound 2.
The organic EL element of Example 3 was produced in the same manner as Example 1 of the organic EL element except that Compound 1 which was a dopant material of the organic EL element of Example 1 was changed to Compound 3.
The organic EL elements of Examples 2 and 3 were driven at a current density of 10 mA / cm ² in the same manner as the organic EL element of Example 1. As a result, blue light emission was also observed for the organic EL elements of Examples 2 and 3. Thus, it was confirmed that compounds 2 and 3 are useful as organic EL device materials.

Example 4
The organic EL element of Example 4 was produced in the same manner as Example 1 of the organic EL element, except that EM2 which is the host material of the organic EL element of Example 1 was changed to EM367.
The organic EL element of Example 4 was driven at a current density of 10 mA / cm ² in the same manner as the organic EL element of Example 1. As a result, blue light emission was also observed for the organic EL element of Example 4. Thus, Compound 1 was confirmed to be useful as an organic EL device material.

-Examples 5-6
The organic EL element of Example 5 was produced in the same manner as in Example 4 of the organic EL element except that Compound 1 as the dopant material of the organic EL element of Example 4 was changed to Compound 2.
The organic EL element of Example 6 was produced in the same manner as Example 4 of the organic EL element except that Compound 1 which was a dopant material of the organic EL element of Example 4 was changed to Compound 3.
The organic EL elements of Examples 5 and 6 were driven at a current density of 10 mA / cm ² in the same manner as the organic EL element of Example 1. As a result, blue light emission was also observed for the organic EL elements of Examples 5 and 6. Thus, it was confirmed that compounds 2 and 3 are useful as organic EL device materials.

  In addition, about the aromatic amine derivative of this invention, although the example which light-emitted blue in the said Example is shown, it is not limited to this. An aromatic amine derivative having a structure in which an aryl group or the like is directly bonded to a pyrene ring can emit green light. For example, the said compounds 117-124, 245-256, 381-388, 513-520 are mentioned.

  The organic EL device of the present invention can be used for a flat light emitter such as a flat panel display of a wall-mounted television, a light source such as a copying machine, a printer, a backlight of a liquid crystal display or instruments, a display board, a marker lamp, and the like.

  DESCRIPTION OF SYMBOLS 1 ... Organic EL element, 3 ... Anode, 4 ... Cathode, 7 ... Light emitting layer, 10 ... Organic compound layer.

Claims (17)

An aromatic amine derivative represented by the following general formula (1).
(In the general formula (1), R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently
Hydrogen atom,
Deuterium atom,
Halogen atoms,
A cyano group,
A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms;
A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms,
A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms,
A substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms,
A substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms,
A substituted or unsubstituted trifluoroalkyl group having 1 to 20 carbon atoms,
A substituted or unsubstituted arylsilyl group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms,
A substituted or unsubstituted aralkyl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms.
However, in the general formula (1), R ₁ and R ₆ are represented by the following general formula (2). )
(In the general formula (2), L ₁ , L ₂ and L ₃ are each independently
Single bond,
It is a divalent residue of a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a divalent residue of a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms.
In the general formula (2), Ar ₁ is a substituent having the following general formula (3) as a partial structure. )
(In the general formula (3), X represents an oxygen atom or a sulfur atom. In the general formula (3), A and B represent a 6-membered ring. The 6-membered ring represented by A and B. In addition, another ring may be condensed.
The substituent having the general formula (3) as a partial structure is
Fluorine atom,
A cyano group,
A substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms,
It has at least one substituent selected from a substituted or unsubstituted arylsilyl group having 6 to 30 ring carbon atoms and a substituted or unsubstituted trifluoroalkyl group having 1 to 20 carbon atoms.
In the general formula (2), Ar ₂ is
Fluorine atom,
A cyano group,
A substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms,
6 or more ring-forming carbon atoms having at least one substituent selected from a substituted or unsubstituted arylsilyl group having 6 to 30 ring carbon atoms and a substituted or unsubstituted trifluoroalkyl group having 1 to 20 carbon atoms An aryl group of -30, a heterocyclic group having 5-30 ring-forming atoms, or a substituent having the general formula (3) as a partial structure. ) The aromatic amine derivative according to claim 1,
The aromatic amine derivative, wherein the substituent having the general formula (3) as a partial structure is a monovalent residue of the following general formula (4).
(In the general formula (4), X represents an oxygen atom or a sulfur atom.
In the general formula (4), R ₁₁ to R ₁₈ are each independently
Hydrogen atom,
Deuterium atom,
Halogen atoms,
A cyano group,
A substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms;
A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms,
A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms,
A substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms,
A substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms,
A substituted or unsubstituted arylsilyl group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms,
A substituted or unsubstituted aralkyl group having 6 to 30 ring carbon atoms,
It is a substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted trifluoroalkyl group having 1 to 20 carbon atoms.
In the general formula (4), at least one of R ₁₁ to R ₁₈ is
Fluorine atom,
A cyano group,
A substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms,
It is a substituted or unsubstituted arylsilyl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted trifluoroalkyl group having 1 to 20 carbon atoms.
However, in the general formula (2), when Ar ₁ is a monovalent residue of the general formula (4), one of R ₁₁ to R ₁₈ is bonded to L ₁ . And when Ar ₂ is a monovalent residue of the general formula (4), one of R ₁₁ to R ₁₈ is a single bond that binds to L ₂ . is there.
In the general formula _(4), among the combinations of _{R 11} and _{R 12, R 12} and _{R 13, R 13} and _{R 14, R 15} and _{R 16, R 16} and _{R 17} and _{R 17} and _{R 18,} at least one One or a combination may form a saturated or unsaturated ring. ) The aromatic amine derivative according to claim 2,
An aromatic amine derivative, wherein at least one of R ₁₁ to R ₁₈ in the general formula (4) is a fluorine atom. The aromatic amine derivative according to claim 2,
An aromatic amine derivative, wherein at least one of R ₁₁ to R ₁₈ in the general formula (4) is a cyano group. The aromatic amine derivative according to claim 2,
At least one of R ₁₁ to R ₁₈ in the general formula (4) is a substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms, or a substituted or unsubstituted arylsilyl having 6 to 30 ring carbon atoms. An aromatic amine derivative characterized by being a group. The aromatic amine derivative according to claim 2,
An aromatic amine derivative, wherein at least one of R ₁₁ to R ₁₈ in the general formula (4) is a substituted or unsubstituted trifluoroalkyl group having 1 to 20 carbon atoms. An organic compound layer is provided between the cathode and the anode,
The said organic compound layer is an organic electroluminescent element containing the aromatic amine derivative as described in any one of Claim 1-6. The organic electroluminescence device according to claim 7,
The organic compound layer includes a plurality of organic thin film layers including a light emitting layer,
At least one layer among the plurality of organic thin film layers includes the aromatic amine derivative according to any one of claims 1 to 6. An organic electroluminescence device, wherein: The organic electroluminescent device according to claim 8, wherein
At least one layer of the plurality of organic thin film layers comprises the aromatic amine derivative according to any one of claims 1 to 6 and an anthracene derivative represented by the following general formula (20). An organic electroluminescence device comprising:
(In the general formula (20), Ar ¹¹ and Ar ¹² are each independently
A substituted or unsubstituted monocyclic group having 5 to 30 ring atoms;
A substituted or unsubstituted condensed ring group having 10 to 30 ring atoms, or a group composed of a combination of the monocyclic group and the condensed ring group.
In the general formula (20), R ¹⁰¹ to R ¹⁰⁸ are each independently
Hydrogen atom,
Halogen atoms,
A cyano group, a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms,
A substituted or unsubstituted condensed ring group having 10 to 30 ring atoms,
A group composed of a combination of the monocyclic group and the condensed ring group,
A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms,
A substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms,
A substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms,
A substituted or unsubstituted aryloxy having 6 to 30 ring carbon atoms, or a substituted or unsubstituted silyl group. ) The organic electroluminescence device according to claim 9,
Ar ¹¹ and Ar ¹² in the general formula (20) are each independently a substituted or unsubstituted condensed ring group having 10 to 30 ring atoms. An organic electroluminescence device, wherein: The organic electroluminescence device according to claim 9,
One of Ar ¹¹ and Ar ¹² in the general formula (20) is a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms, and the other is a substituted or unsubstituted ring atom having 10 to 30 atoms. An organic electroluminescence device characterized by being a condensed ring group of The organic electroluminescence device according to claim 11,
Ar ¹² in the general formula (20) is selected from a naphthyl group, a phenanthryl group, a benzoanthryl group, and a dibenzofuranyl group, and Ar ¹¹ is an unsubstituted phenyl group or the monocyclic group and the condensed ring group. An organic electroluminescence device, wherein at least one of them is a substituted phenyl group. The organic electroluminescence device according to claim 11,
Ar ¹² in the general formula (20) is a substituted or unsubstituted condensed ring group having 10 to 30 ring atoms, and Ar ¹¹ is an unsubstituted phenyl group. . The organic electroluminescence device according to claim 9,
Ar ¹¹ and Ar ¹² in the general formula (20) are each independently a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms. The organic electroluminescence device. The organic electroluminescence device according to claim 14,
Ar ¹¹ and Ar ¹² in the general formula (20) are each independently a substituted or unsubstituted phenyl group. An organic electroluminescence device, wherein: The organic electroluminescence device according to claim 15,
Ar ¹¹ in the general formula (20) is an unsubstituted phenyl group, and Ar ¹² is a phenyl group having at least one of the monocyclic group and the condensed ring group as a substituent. Organic electroluminescence device. The organic electroluminescence device according to claim 15,
Ar ¹¹ and Ar ¹² in the general formula (20) are each independently a phenyl group having at least one of the monocyclic group and the condensed ring group as a substituent. An organic electroluminescence device, wherein: