JP2014177441A - Aromatic amine derivative, material for organic electroluminescent element, organic electroluminescent element, and electronic equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element emitting with high efficiency, and an aromatic amine derivative capable of being used for the element.SOLUTION: There is provided an aromatic amine derivative represented by the general formula (1), where any two of Rto Rare each independently represented by the general formula (2). In the general formula (2), at least one of Arand Aris a substituent represented by the general formula (3) and Lto Lare single bonds or connecting groups. In the general formula (3), where Ar is a substituted or unsubstituted bivalent aromatic hydrocarbon group having 6 to 18 ring forming carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 15 ring forming atoms.

Description

  The present invention relates to an aromatic amine derivative, a material for an organic electroluminescence element, an organic electroluminescence element, and an electronic apparatus.

  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. 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, higher light emission efficiency is required.

Patent Documents 1 and 2 disclose diaminopyrene dopants having two amino groups substituted with aryl groups.
Patent Document 3 discloses a diaminopyrene dopant having an alkylsilyl group.
Patent Documents 4 and 5 disclose a diaminopyrene dopant having dibenzofuran, and a combination of the dopant material and an anthracene host material.
Patent Document 6 discloses a diaminopyrene dopant having a structure in which a nitrogen atom is directly connected to the 2-position or 4-position of dibenzofuran and dibenzothiophene.

International Publication No. 2004/083162 International Publication No. 2005/108348 JP 2004-204238 A International Publication No. 2009/084512 International Publication No. 2010/122810 JP 2011-231108 A

  However, in order to put the organic EL element into practical use, higher efficiency is required.

  Accordingly, an object of the present invention is to provide an organic electroluminescent device that emits light with high efficiency, an aromatic amine derivative that can be used for the organic electroluminescent device, an organic electroluminescent device material containing the aromatic amine derivative, and the organic electroluminescent device. An object of the present invention is to provide an electronic device including a luminescence element.

  An aromatic amine derivative according to one embodiment of the present invention is represented by the following general formula (1).

(In the general formula (1), R ^{1 to} R ¹⁰ are each independently
Hydrogen atom,
Halogen atoms,
Hydroxyl group,
A cyano group,
A substituted or unsubstituted alkyl group having 1 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 60 ring carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms,
A substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted alkylamino group having 2 to 30 carbon atoms,
A substituted or unsubstituted arylamino group having 6 to 60 ring carbon atoms,
A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms,
A substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms A substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic ring having 5 to 30 ring atoms Selected from any of the groups.
However, any two of R ^{1 to} R ¹⁰ are each independently represented by the following general formula (2). )

(In the general formula (2),
L ¹ , L ² and L ³ are each independently a single bond or a linking group,
A substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 18 ring carbon atoms, or
A substituted or unsubstituted divalent heterocyclic group having 5 to 15 ring atoms.
If at least one of Ar ^1, Ar ² is a substituent represented by the following general formula (3) is a substituent Ar ¹ and Ar ² are both represented by the following formula (3), to each other Identical or different.
Among Ar ¹ and Ar ² , those not represented by the following general formula (3) are:
A substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 15 ring atoms.
Ar ¹ and L ¹ may or may not form a ring by bonding to each other.
Further, Ar ² and L ² may or may not form a ring by bonding to each other. )

(In the general formula (3),
Ar is
A substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 18 ring carbon atoms or a substituted or unsubstituted divalent heterocyclic group having 5 to 15 ring atoms.
n is an integer of 3 to 20, and the plurality of Ars are the same or different from each other. Adjacent Ars may or may not form a ring by bonding to each other.
R is
Hydrogen atom,
Halogen atoms,
Hydroxyl group,
A cyano group,
A substituted or unsubstituted alkyl group having 1 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 60 ring carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms,
A substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted alkylamino group having 2 to 30 carbon atoms,
A substituted or unsubstituted arylamino group having 6 to 60 ring carbon atoms,
It is selected from either a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms or a substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms.
R may or may not be bonded to adjacent Ar to form a ring. )

  On the other hand, the material for an organic electroluminescence device of the present invention includes the aromatic amine derivative of the present invention.

Moreover, the organic electroluminescence device of the present invention has a cathode, an anode, and at least one organic layer disposed between the cathode and the anode, and at least one of the organic layers. The organic layer is characterized by containing the aromatic amine derivative of the present invention.
In addition, an electronic apparatus according to the present invention includes the organic electroluminescence element according to the present invention.

  According to the present invention, an organic electroluminescent device that emits light with high efficiency, an aromatic amine derivative that can be used in the organic electroluminescent device, an organic electroluminescent device material containing the aromatic amine derivative, and the organic electroluminescent device 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 according to one embodiment of the present invention is represented by the following general formula (1).

(In the general formula (1), R ^{1 to} R ¹⁰ are each independently
Hydrogen atom,
Halogen atoms,
Hydroxyl group,
A cyano group,
A substituted or unsubstituted alkyl group having 1 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 60 ring carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms,
A substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted alkylamino group having 2 to 30 carbon atoms,
A substituted or unsubstituted arylamino group having 6 to 60 ring carbon atoms,
A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms,
A substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms A substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic ring having 5 to 30 ring atoms Selected from any of the groups.
However, any two of R ^{1 to} R ¹⁰ are each independently represented by the following general formula (2). )

(In the general formula (2),
L ¹ , L ² and L ³ are each independently a single bond or a linking group,
A substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 18 ring carbon atoms, or
A substituted or unsubstituted divalent heterocyclic group having 5 to 15 ring atoms.
If at least one of Ar ^1, Ar ² is a substituent represented by the following general formula (3) is a substituent Ar ¹ and Ar ² are both represented by the following formula (3), to each other Identical or different.
Among Ar ¹ and Ar ² , those not represented by the following general formula (3) are:
A substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 15 ring atoms.
Ar ¹ and L ¹ may or may not form a ring by bonding to each other.
Further, Ar ² and L ² may or may not form a ring by bonding to each other. )

(In the general formula (3),
Ar is
A substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 18 ring carbon atoms or a substituted or unsubstituted divalent heterocyclic group having 5 to 15 ring atoms.
n is an integer of 3 to 20, and the plurality of Ars are the same or different from each other. Adjacent Ars may or may not form a ring by bonding to each other.
R is
Hydrogen atom,
Halogen atoms,
Hydroxyl group,
A cyano group,
A substituted or unsubstituted alkyl group having 1 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 60 ring carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms,
A substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted alkylamino group having 2 to 30 carbon atoms,
A substituted or unsubstituted arylamino group having 6 to 60 ring carbon atoms,
It is selected from either a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms or a substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms.
R may or may not be bonded to adjacent Ar to form a ring. )

In the aromatic amine derivative, the structure represented by-(Ar) _n -L _1- or-(Ar) _n -L _2- has a monocyclic ring and a condensed ring of an aromatic hydrocarbon group and a heterocyclic group. A structure in which 3 or more and 20 or less are connected is more preferable. However, in the case where the structure is a structure in which three aromatic hydrocarbon and heterocyclic monocycles and condensed rings are connected, L ₁ or L ₂ is preferably a single bond. Here, the term “linkage” does not include condensation, and the condensed ring is counted as one regardless of the number of condensed rings. For example, a naphthylene group is counted as one. However, for example, the groups represented by the following formulas (A) and (B) are counted as two, and for example, the ladder type group represented by the following formula (C) is counted as three. For example, a biphenyl group is a group having two phenylene groups, which are monocyclic aromatic hydrocarbon groups, and is counted as two.

(In the formula (A), R _D and R _E are each independently an unsubstituted methyl group or a phenyl group.
In the formulas (B) and (C), X is an oxygen atom or a sulfur atom.
In the formula (C), Y is an oxygen atom or a sulfur atom. )

In the aromatic amine derivative, R ¹ and R ⁶ are preferably represented by the general formula (2).
In the aromatic amine derivative, R ² and R ⁷ are preferably represented by the general formula (2).

  The general formula (2) is preferably represented by the following general formula (21).

In (Formula ^{(21), L 1 ~L 3} , Ar 2 has the same meaning as ^L 1 ^~L 3, Ar ² in the general formula (2).
R ²¹ , R ²² , or R ²¹ and R ²⁴ are represented by the general formula (3). Other than those represented by the general formula of R ²¹ to R ²⁵ (3) has the same meaning as R in the general formula (3). )

  In the said General formula (3), n is an integer of 3-20, Preferably it is an integer of 4-20, More preferably, it is an integer of 5-20.

  The general formula (3) is preferably represented by either the following general formula (31) or (32).

(In the said General formula (31), R is synonymous with R of the said General formula (3).
Ar ¹¹ and Ar ¹² are each independently
A substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 18 ring carbon atoms or a substituted or unsubstituted divalent heterocyclic group having 5 to 15 ring atoms.
p ^{is, -Ar} 11 -Ar ¹² - are repeated 2 to 10 integer representing the.
Adjacent Ar ¹¹ and Ar ¹² may or may not form a ring by bonding to each other.
Further, there are cases where adjacent Ar ¹¹ and R are bonded to each other to form a ring, and may not. )

(In the said General formula (32), R is synonymous with R of the said General formula (3).
Ar ^{13 to} Ar ¹⁵ are each independently
A substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 18 ring carbon atoms or a substituted or unsubstituted divalent heterocyclic group having 5 to 15 ring atoms.
q ^{is, -Ar 13} -Ar 14 -Ar ¹⁵ - are 2 to 6 integer representing the repetition of.
Adjacent Ar ¹³ and Ar ¹⁴ may or may not form a ring by bonding to each other.
In addition, adjacent Ar ¹⁴ and Ar ¹⁵ may or may not form a ring by bonding to each other.
In addition, adjacent Ar ¹³ and R may or may not form a ring by bonding to each other. )

  Here, as R in the general formulas (3), (31) and (32), among the substituents described in the general formula (3), a hydrogen atom, a fluorine atom, a cyano group, substituted or unsubstituted It is preferably a group selected from an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms, or a substituted or unsubstituted arylsilyl group having 6 to 60 ring carbon atoms. .

Ar ² is a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 18 ring carbon atoms, and preferably has no group represented by the general formula (3) as a substituent.

Further, L ¹ and L ² are preferably single bonds.
Moreover, any two of R ^{1 to} R ¹⁰ have the same structure represented by the general formula (2).

  In the general formula (3), Ar is more preferably a substituent selected from the group consisting of substituents represented by the following formulas 1-1 to 1-21.

(R _B and R _C in Formula 1-5 and R _D in Formula 1-15 are an unsubstituted methyl group or a phenyl group.)

Among the above, Ar is preferably a substituent represented by Formula 1-1.
Moreover, the partial structure consisting of —Ar ¹¹ —Ar ¹² — of the substituent represented by the general formula (31) is any one of the structures represented by the following formulas 2-1 to 2-5. Preferably there is.

Moreover, the partial structure which consists of -Ar < ¹³ > -Ar < ¹⁴ > -Ar < ¹⁵ >-of the substituent represented by the said General formula (32) is the structure represented by following formula 3-1 to formula 3-11, Either is preferable.

In the general formula (2), L ³ is preferably a single bond or a phenylene group.
In the general formulas (2) and (21), L ² is a single bond, and Ar ² is more preferably a group selected from a phenyl group, a dibenzofuranyl group, and a dibenzothiophenyl group.

The aromatic amine derivative represented by the general formula (1) preferably contains a divalent group derived from 9,9-dimethylfluorene in L ¹ of the general formula (21).

  The general formula (1) is preferably represented by the following general formula (11).

(In the general formula ^(11), R 2 to R ⁵ and ^R 7 ^{to R 10} are the same meanings as ^R 2 to R ⁵ and ^R 7 ^{to R 10} in the general formula (1).
R ³¹ , R ³² , or R ³¹ and R ³⁴ are represented by the general formula (3). Other than those represented by the general formula of R ³¹ to R ⁴⁰ (3) has the same meaning as R in the general formula (3).
Ar ²¹ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 ring carbon atoms, and does not have the group represented by the general formula (3) as a substituent. )

  The general formula (1) is preferably represented by the following general formula (12).

(In the general formula ^(12), R 2 to R ⁵ and ^R 7 ^{to R 10} are the same meanings as ^R 2 to R ⁵ and ^R 7 ^{to R 10} in the general formula (1).
Ar and n have the same meanings as Ar and n in the general formula (3), respectively.
R, R ³¹ , R ^{33 to} R ³⁵ , and R ³⁶ have the same meaning as R in the general formula (3), respectively.
r is 5. )

  The general formula (1) is preferably represented by the following general formula (13).

(In the general formula ^(13), R 2 to R ⁵ and ^R 7 ^{to R 10} are the same meanings as ^R 2 to R ⁵ and ^R 7 ^{to R 10} in the general formula (1).
Ar and n have the same meanings as Ar and n in the general formula (3), respectively.
R, R ³¹ , R ^{33 to} R ³⁵ , and R ³⁶ have the same meaning as R in the general formula (3), respectively.
r is 5.
Ar ³⁵ is
A substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 15 ring atoms. )

  Next, the general formulas (1) to (3), (11) to (13), (21), (31) to (32) (hereinafter, these general formulas are collectively referred to as general formula (1), etc.) ) Will be described.

Examples of the aromatic hydrocarbon group having 6 to 30 ring carbon atoms in R ^{1 to} R ¹⁰ of the general formula (1) include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, Fluorenyl group, pyrenyl group, chrysenyl group, fluoranthenyl group, benzo [a] anthryl group, benzo [c] phenanthryl group, triphenylenyl group, benzo [k] fluoranthenyl group, benzo [g] chrysenyl group, benzo [b ] A triphenylenyl group, a picenyl group, a perylenyl group, etc. are mentioned.
As an aromatic hydrocarbon group in this embodiment, it is preferable that ring forming carbon number is 6-20, More preferably, it is still more 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 9-position carbon atom is substituted with a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms in the present embodiment described later. It is preferable that an unsubstituted methyl group is substituted.

L ^{1 to} L ³ , Ar ¹ , Ar ^{2 of} the general formula ( ¹ ), Ar ^{11 to} Ar ^{12 of} the general formula (31), Ar ^{13 to} Ar ¹⁵ of the general formula (32), the general formula (13) As the aromatic hydrocarbon group having 6 to 18 ring carbon atoms in Ar ³⁵ ), among the aromatic hydrocarbon groups having 6 to 30 ring carbon atoms in the above R ^{1 to} R ¹⁰ , the ring forming carbon number is 6 -18 can be mentioned. That is, for example, phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, pyrenyl group, chrysenyl group, fluoranthenyl group, benzo [a] anthryl group, benzo [c] phenanthryl group And a triphenylenyl group.
When a fluorenyl group is selected as the aromatic hydrocarbon group, it is preferably a 9,9-dimethylfluorenyl group having two methyl groups as substituents at the 9-position.

Examples of the heterocyclic group having 5 to 30 ring atoms in R ^{1 to} R ¹⁰ of the general formula (1) include a pyridyl group, pyrimidinyl group, pyrazinyl group, pyridazinyl group, triazinyl group, quinolyl group, isoquinolinyl group, Naphthyridinyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, phenanthridinyl group, acridinyl group, phenanthrolinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, indolyl group, benzimidazolyl group, indazolyl Group, imidazopyridinyl group, benztriazolyl group, carbazolyl group, furyl group, thienyl group, oxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, oxadiazolyl group, thiadiazolyl group, benzofuranyl group, benzothiopheny group Group, benzoxazolyl group, benzothiazolyl group, benzoisoxazolyl group, benzisothiazolyl group, benzoxiadiazolyl group, benzothiadiazolyl group, dibenzofuranyl group, dibenzothiophenyl group, piperidinyl group, pyrrolidinyl Group, piperazinyl group, morpholyl group, phenazinyl group, phenothiazinyl group, phenoxazinyl group and the like.
The number of ring-forming atoms of the heterocyclic group in this embodiment is preferably 5-20, and more preferably 5-14. 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 particularly preferable. As for the 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group and 4-carbazolyl group, the substituted or unsubstituted aromatic hydrocarbon having 6 to 30 ring carbon atoms in the present embodiment 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.

L ^{1 to} L ³ , Ar ¹ , Ar ^{2 of} the general formula ( ¹ ), Ar ^{11 to} Ar ^{12 of} the general formula (31), Ar ^{13 to} Ar ¹⁵ of the general formula (32), the general formula (13) As the heterocyclic group having 5 to 15 ring atoms in Ar ³⁵ of the above formula, among the heterocyclic groups having 5 to 30 ring atoms in R ^{1 to} R ¹⁰ of the general formula (1), the number of ring forming atoms 5 to 15 can be mentioned. That is, for example, pyridyl group, pyrimidinyl group, pyrazinyl group, pyridazinyl group, triazinyl group, quinolyl group, isoquinolinyl group, naphthyridinyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, phenanthridinyl group, acridinyl group, phenanthrolinyl Group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, indolyl group, benzimidazolyl group, indazolyl group, imidazolpyridinyl group, benztriazolyl group, carbazolyl group, furyl group, thienyl group, oxazolyl group , Thiazolyl group, isoxazolyl group, isothiazolyl group, oxadiazolyl group, thiadiazolyl group, benzofuranyl group, benzothiophenyl group, benzoxazolyl group, benzothiazolyl group, benzoisoxazolyl group Benzoisothiazolyl group, benzooxadiazolyl group, benzothiadiazolyl group, dibenzofuranyl group, dibenzothiophenyl group, piperidinyl group, pyrrolidinyl group, piperazinyl group, morpholyl group, phenazinyl group, phenothiazinyl group, phenoxazinyl group Can be mentioned.

The alkyl group having 1 to 30 carbon atoms in the general formula (1) or the like may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, neopentyl group, amyl group, isoamyl group, 1-methylpentyl group, 2-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1- A heptyloctyl group and a 3-methylpentyl group.
The linear or branched alkyl group in the general formula (1) or the like 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 , An amyl group, an isoamyl group, and a neopentyl group are particularly preferable.
Examples of the cycloalkyl group in this embodiment include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, an adamantyl group, and a norbornyl group. The ring-forming carbon number of the cycloalkyl group is preferably 3 to 10, and more preferably 5 to 8. Among the cycloalkyl groups, a cyclopentyl group and a cyclohexyl group are particularly 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, a trifluoromethylmethyl group, a trifluoroethyl group, and a pentafluoroethyl group.

  Examples of the alkylsilyl group having 3 to 30 carbon atoms in the general formula (1) and the like 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, Examples thereof include a dimethyl-t-butylsilyl group, a diethylisopropylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, and a triisopropylsilyl group. The three alkyl groups in the trialkylsilyl group may be the same or different.

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 has, for example, two alkyl groups exemplified as the alkyl group having 1 to 30 carbon atoms, and one dialkylarylsilyl group having one aromatic hydrocarbon group having 6 to 30 ring carbon atoms. Is mentioned. The carbon number of the dialkylarylsilyl group is preferably 8-30.
The alkyldiarylsilyl group has, for example, one alkyl group exemplified for the alkyl group having 1 to 30 carbon atoms, and two alkyldiarylsilyl groups having the two aromatic hydrocarbon groups having 6 to 30 ring carbon atoms. Is mentioned. The alkyldiarylsilyl group preferably has 13 to 30 carbon atoms.
Examples of the triarylsilyl group include a triarylsilyl group having three aromatic hydrocarbon groups having 6 to 30 ring carbon atoms. The carbon number of the triarylsilyl group is preferably 18-30.

Alkoxy group having 1 to 30 carbon atoms in the general formula (1) or the like is represented as -OZ _1. Examples of _{Z 1,} include alkyl groups of 1 to 30 carbon atoms. 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.

Formula (1) aryloxy ring forming C6-30 in such is expressed as -OZ _2. Examples of this Z ₂ include the aromatic hydrocarbon groups having 6 to 30 ring carbon atoms. Examples of the aryloxy group include a phenoxy group.

The alkylamino group having 2 to 30 carbon atoms in the general formula (1) or the like is represented as —NHR _V or —N (R _V ) ₂ . Examples of _{R V,} include alkyl groups of 1 to 30 carbon atoms.

The arylamino group having 6 to 60 ring carbon atoms in the general formula (1) or the like is represented as —NHR _W or —N (R _W ) ₂ . Examples of R _W, and an aromatic hydrocarbon group of the ring-forming C6-30.

Alkylthio group having 1 to 30 carbon atoms in the general formula (1) or the like is represented as -SR _V. Examples of _{R V,} include alkyl groups of 1 to 30 carbon atoms.
Ring formation arylthio group having 6 to 30 carbon atoms is expressed as -SR _W. Examples of R _W, and an aromatic hydrocarbon group of the ring-forming C6-30.

  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 present invention, the hydrogen atom includes isotopes having different numbers of neutrons, that is, light hydrogen (Protium), deuterium (Deuterium), and tritium (Tritium).

In the present invention, the substituent in the case of “substituted or unsubstituted” includes the aromatic hydrocarbon group, heterocyclic group, alkyl group (straight chain or branched chain alkyl group, cycloalkyl group) as described above. Haloalkyl group), alkoxy group, aryloxy group, aralkyl group, haloalkoxy group, alkylsilyl group, dialkylarylsilyl group, alkyldiarylsilyl group, triarylsilyl group, halogen atom, cyano group, hydroxyl group, nitro group, And a carboxy group. In addition, an alkenyl group and an alkynyl group are also included.
Among the substituents mentioned here, an aromatic hydrocarbon group, a heterocyclic group, an alkyl group, a halogen atom, an alkylsilyl group, an arylsilyl group, and a cyano group are more preferable, and further preferable in the description of each substituent. The specific substituents are preferred.
The term “unsubstituted” in the case of “substituted or unsubstituted” means that a hydrogen atom is bonded without being substituted with the substituent.
In the present specification, “carbon number ab” in the expression “XX group having a substituted or unsubstituted carbon number ab” represents the number of carbon atoms when the XX group is unsubstituted. The number of carbon atoms of the substituent when the XX group is substituted is not included.
In the compound described below or a partial structure thereof, the case of “substituted or unsubstituted” is the same as described above.

  Specific examples of the aromatic amine derivatives represented by the general formulas (1) and (11) to (13) are shown below, but the present invention is not limited to these exemplified compounds.

[Materials for organic EL elements]
The aromatic amine derivative according to one embodiment of the present invention can be used as a material for an organic EL element.

[Organic EL device]
(Element structure of organic EL element)
Hereinafter, an element structure of the organic EL element according to one embodiment of the present invention will be described.
The organic EL element according to one embodiment of the present invention includes an organic layer between a pair of electrodes. This organic layer has at least one layer composed of an organic compound. The organic layer may contain an inorganic compound.
In the organic EL element, at least one of the organic layers has a light emitting layer. Therefore, the organic layer may be composed of, for example, a single light emitting layer, or an organic layer such as a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole barrier layer, or an electron barrier layer. You may have the layer employ | adopted with an EL element.

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 Examples of the structure include layer / light emitting layer / electron injection / transport layer / cathode (e) 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. In the case of a phosphorescent element, the host material mainly has a function of confining excitons generated by the dopant in the light emitting layer.
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.

  In the case of an electron transport layer, the organic layer having the highest electron mobility among the organic layers in the electron transport region existing between the light emitting layer and the cathode. When the electron transport region is composed of one layer, the layer is an electron transport layer. In addition, in the phosphorescent organic EL device, as shown in the configuration (e), a barrier layer that does not necessarily have high electron mobility is used to prevent diffusion of excitation energy generated in the light emitting layer. The organic layer adjacent to the light emitting layer does not necessarily correspond to the electron transport layer.

In FIG. 1, schematic structure of an example of the organic EL element in one Embodiment of this invention is shown.
The organic EL element 1 includes a translucent substrate 2, an anode 3, a cathode 4, and an organic layer 10 disposed between the anode 3 and the cathode 4.
The organic layer 10 has a light emitting layer 5 containing a host material and a dopant material. The organic layer 10 has a hole transport layer 6 between the light emitting layer 5 and the anode 3. Further, the organic layer 10 has an electron transport layer 7 between the light emitting layer 5 and the cathode 4.

(Light emitting layer)
The light emitting layer of the organic EL element provides a field for recombination of electrons and holes, and has a function of connecting this to light emission. The light emitting layer is preferably a molecular deposited film. Here, the molecular deposited film is a thin film formed by deposition from a material compound in a gas phase state or a film formed by solidifying from a material compound in a solution state or a liquid phase state. Can be distinguished from the thin film (molecular accumulation film) formed by the LB method (Langmuir Blodgett method) by the difference in aggregated structure and higher order structure and the functional difference resulting therefrom.

-Dopant material In this embodiment, it is preferable to use the aromatic amine derivative represented by the general formula (1) described above as a dopant material.
The aromatic amine derivative represented by the general formula (1) has a structure represented by the general formula (3). In the general formula (3), Ar represents a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 18 ring carbon atoms, or a substituted or unsubstituted divalent heterocyclic ring having 5 to 15 ring atoms. It is a group and has a structure in which a conjugated system extends long by connecting n of them. Here, n is an integer of 3 to 20, and when L ¹ or L ² to which Ar is bonded is a linking group, a longer conjugated system is formed. Conventionally, a compound in which a conjugated system of a compound is extended is known, but the conjugated system having a structure represented by the general formula (3) is longer than the conventional compound and has such a long conjugated system. The use of compounds as dopant materials has not been studied. The aromatic amine derivative represented by the general formula (1) has high orientation by having a conjugated system in which the general formula (3) extends for a long time. When this aromatic amine derivative is used as a dopant material, it is considered that high orientation contributes and the luminous efficiency of the organic EL element is improved.

  When the light emitting layer contains the aromatic amine derivative as a dopant material, the content of the aromatic amine derivative in the light emitting layer is preferably 0.1% by mass or more and 20% by mass or less, and preferably 1% by mass or more. More preferably, it is 10 mass% or less.

-Host material In this embodiment, it is preferable to use the anthracene derivative represented by the following general formula (100) as a host material.

(In the general formula (100), Ar ¹⁰¹ and Ar ¹⁰² 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
It is a chain group formed by combining two or three groups selected from the monocyclic group and the condensed ring group.
In the chain group, the monocyclic group and the condensed ring group constituting the chain group may be the same or different from each other, and the groups constituting the chain group may be bonded to each other to form a ring. .
In the general formula (100), R ¹⁰¹ to R ¹⁰⁸ are each independently
Hydrogen atom,
Halogen atoms,
Hydroxyl group,
A cyano group,
A substituted or unsubstituted alkyl group having 1 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 60 ring carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms,
A substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted alkylamino group having 2 to 30 carbon atoms,
A substituted or unsubstituted arylamino group having 6 to 60 ring carbon atoms,
A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms,
A substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms; a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms;
Either a substituted or unsubstituted condensed ring group having 10 to 30 ring-forming atoms, or a chain group formed by combining two or three groups selected from the monocyclic group and the condensed ring group To be elected.
Adjacent R ^{101 to} R ¹⁰⁸ may or may not be bonded to each other to form a ring. In addition, R ^{101 to} R ¹⁰⁸ and the carbon atoms constituting the anthracene ring may or may not be bonded to each other to form a ring.
R ¹⁰¹ , R ¹⁰⁴ , R ¹⁰⁵ or R ¹⁰⁸ adjacent to Ar ¹⁰¹ or Ar ¹⁰² may or may not be bonded to form a ring. Further, Ar ¹⁰¹ or Ar ¹⁰² and the carbon atoms constituting the anthracene ring may or may not be bonded to each other to form a ring. )

In the general formula (100), the condensed ring group is a group in which two or more ring structures are condensed. For example, the aromatic hydrocarbon described in R ^{1 to} R ¹⁰ in the general formula (1) Among groups and heterocyclic groups, a group in which two or more ring structures are condensed can be used.
In the general formula (100), the monocyclic group is a monocyclic group that does not include a condensed ring structure of two or more rings. For example, in the general formula (1), R ¹ to Of the aromatic hydrocarbon group and heterocyclic group described in R ¹⁰ , a monocyclic group can be used.

  The number of ring-forming atoms of the monocyclic group is 5-30, preferably 5-20. Examples of the monocyclic group include aromatic hydrocarbon groups such as a phenyl group, a biphenyl group, a terphenyl group, and a quarterphenyl group, and a complex such as a pyridyl group, a pyrazyl group, a pyrimidyl group, a triazinyl group, a furyl group, and a thienyl group. A cyclic group is mentioned. Among these, a phenyl group, a biphenyl group, and a terphenyl group are preferable.

  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 (100), as the chain group composed of the 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. (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 (100) are the same as R ^{1 to} R ¹⁰ in the general formula (1). The cycloalkyl group is the same as that described above.
Ar ¹⁰¹ and Ar ¹⁰² in the general formula (100), and preferred 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 above-mentioned general formula (100) and the above-mentioned general formula (1).
In the general formula (100), the hydrogen atom includes isotopes having different numbers of neutrons, that is, light hydrogen (Protium), deuterium (Deuterium), and tritium (Tritium).

  The anthracene derivative represented by the general formula (100) is preferably any of the following anthracene derivatives (A), (B), and (C), and is selected depending on the configuration of the organic EL element to be applied and the required characteristics. .

・ Anthracene derivatives (A)
In the anthracene derivative (A), Ar ¹⁰¹ and Ar ¹⁰² in the general formula (100) are substituted or unsubstituted condensed ring groups having 10 to 30 ring atoms. The anthracene derivative (A) is divided into a case where Ar ¹⁰¹ and Ar ¹⁰² are the same substituted or unsubstituted condensed ring group and a case where Ar ¹⁰¹ and Ar ¹⁰² are different substituted or unsubstituted condensed ring groups. be able to. When Ar ¹⁰¹ and Ar ¹⁰² are different, the case where the substitution positions are different is also included.

As the anthracene derivative (A), an anthracene derivative in which Ar ¹⁰¹ and Ar ¹⁰² in the general formula (100) 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 ¹⁰¹ and Ar ¹⁰² in the general formula (100) 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 ¹⁰¹ and Ar ¹⁰² in the general formula (100) is a substituted or unsubstituted aromatic hydrocarbon group having 5 to 30 ring atoms, and the other is substituted or unsubstituted. A condensed ring group having 10 to 30 ring atoms.
As a preferred form of the anthracene derivative (B), Ar ¹⁰² is selected from a naphthyl group, a phenanthryl group, a benzoanthryl group, a 9,9-dimethylfluorenyl group, and a dibenzofuranyl group, and Ar ¹⁰¹ is an unsubstituted group. Or a case in which at least one of the monocyclic group and the condensed ring group is a substituted phenyl group.
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 ¹⁰² is a substituted or unsubstituted condensed ring group having 10 to 30 ring atoms and Ar ¹⁰¹ 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 ¹⁰¹ and Ar ¹⁰² in the general formula (100) 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 ¹⁰¹ and Ar ¹⁰² are each independently a substituted or unsubstituted phenyl group.
As a more preferable form of the anthracene derivative (C), when Ar ¹⁰¹ is an unsubstituted phenyl group and Ar ¹⁰² is the monocyclic group, Ar ¹⁰¹ and Ar ¹⁰² are each independently the monocyclic And a phenyl group having at least one of the group and the condensed ring group as a substituent.

Specific examples of the preferable monocyclic group and condensed ring group as the substituent which Ar ¹⁰¹ and Ar ¹⁰² in the general formula (100) have are as described above. The aromatic hydrocarbon 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 benzoanthryl group is more preferred.

  Examples of the structure of the anthracene derivative represented by the general formula (100) include the following. However, the present invention is not limited to the anthracene derivatives having these structures.

In the general formula (100A), R ¹⁰¹ and R ¹⁰⁵ each independently represent 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 chain group formed by bonding 2 to 3 groups selected from the monocyclic group and the condensed ring group, a substituted or unsubstituted carbon number of 1 to 30 Alkyl groups, substituted or unsubstituted cycloalkyl groups having 3 to 30 ring carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted Alternatively, it is an unsubstituted aryloxy having 6 to 30 ring carbon atoms, or a substituted or unsubstituted silyl group.

In General Formula (100A), Ar ¹²¹ and Ar ¹¹¹ each independently represent 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 General Formula (100A), Ar ¹²² and Ar ¹¹² 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 formation. It is a condensed ring divalent residue having 10 to 30 atoms.
In General Formula (100A), Ar ¹²³ and Ar ¹¹³ 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.

In the general formula (100B), Ar ¹²¹ 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 General Formula (100B) above, Ar ¹²² and Ar ¹¹² 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 (100B), Ar ¹²³ and Ar ¹¹³ 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.

In General Formula (100C), Ar ¹²² represents a substituted or unsubstituted monovalent 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 (100C), Ar ¹¹² 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 General Formula (100C), Ar ¹²³ and Ar ¹¹³ 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.

In General Formula (100D), Ar ¹²² 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 General Formula (100D) above, Ar ¹¹² 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 General Formula (100D), Ar ¹²³ and Ar ¹¹³ 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.

In General Formula (100E), Ar ¹²² and Ar ¹¹² 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 formation. It is a condensed ring divalent residue having 10 to 30 atoms.
In General Formula (100E), Ar ¹²³ and Ar ¹¹³ 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.

In the general formulas (100A) to (100E), as preferred substituents of “substituted or unsubstituted” from Ar ¹¹¹ to Ar ¹¹³ and Ar ¹²¹ to Ar ¹²³ , a monocyclic group, a condensed ring group, an alkyl group, a cyclo Examples thereof include an alkyl group, a silyl group, 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 the groups in the general formula (100) and the groups in the general formula (1).
In the general formulas (100A) to (100E), hydrogen atoms include isotopes having different numbers of neutrons, that is, light hydrogen (Protium), deuterium (Deuterium), and tritium (Tritium).

  Examples of materials other than the general formula (100) that can be used in the light emitting layer together with the aromatic amine derivative of the present embodiment include naphthalene, phenanthrene, rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene, and tetraphenyl. Condensed polycyclic aromatic compounds such as cyclopentadiene, pentaphenylcyclopentadiene, fluorene, spirofluorene and their derivatives, organometallic complexes such as tris (8-quinolinolato) aluminum, triarylamine derivatives, styrylamine 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.

(Hole injection / transport layer)
The hole injection / transport layer is a layer that assists hole injection into the light emitting layer and transports it to the light emitting region, and has a high hole mobility and a low ionization energy.
As a material for forming the hole injection layer and the hole transport layer, a material that transports holes to the light emitting layer with lower electric field strength is preferable. For example, an aromatic amine compound is preferably used. Further, as the material for the hole injection layer, it is preferable to use a porphyrin compound, an aromatic tertiary amine compound or a styrylamine compound. In particular, an aromatic tertiary amine compound such as hexacyanohexaazatriphenylene (HAT) is used. It is preferable to use it.

(Electron injection / transport layer)
The electron injection / transport layer is a layer that assists injection of electrons into the light emitting layer and transports it to the light emitting region, and a compound having a high electron mobility is used.
As the compound used in the electron injecting / transporting layer, for example, an aromatic heterocyclic compound containing one or more hetero atoms in the molecule is preferably used, and a nitrogen-containing ring derivative is particularly preferable. As the nitrogen-containing ring derivative, a heterocyclic compound having a nitrogen-containing 6-membered ring or 5-membered ring skeleton is preferable.

  In the organic EL element, any compound other than the compounds exemplified above can be selected and used for the organic layer other than the light emitting layer from materials used in the conventional organic EL element.

(substrate)
The organic EL element is manufactured on a light-transmitting substrate. This translucent substrate is a substrate that supports an anode, an organic layer, a cathode, and the like constituting the organic EL element, and is preferably a smooth substrate having a light transmittance in the visible region of 400 nm to 700 nm of 50% or more.
Examples of the translucent substrate include a glass plate and a polymer plate.
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.

(Anode and cathode)
The anode of the organic EL element plays a role of injecting holes into the light emitting layer, and it is effective to have a work function of 4.5 eV or more.
Specific examples of the anode material include indium tin oxide alloy (ITO), tin oxide (NESA), indium zinc oxide, gold, silver, platinum, and copper.
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 / □ (Ω / sq. Ohm per square) 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 cathode, a material having a small work function is preferable for the purpose of injecting electrons into the light emitting layer.
The cathode material is not particularly limited, and specifically, indium, aluminum, magnesium, magnesium-indium alloy, magnesium-aluminum alloy, aluminum-lithium alloy, aluminum-scandium-lithium alloy, magnesium-silver alloy and the like can be used.
Similarly to the anode, the cathode can be formed, for example, on the electron transport layer or the electron injection layer by a method such as vapor deposition. Moreover, the aspect which takes out light emission from a light emitting layer from a cathode side is also employable. 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 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.

(Method for forming each layer of organic EL element)
The method for forming each layer of the organic EL element is not particularly limited. Conventionally known methods such as vacuum deposition and spin coating can be used. The organic layer used in the organic EL device is a vacuum deposition method, a molecular beam deposition method (MBE method, MBE; Molecular Beam Epitaxy) or a solution dipping method dissolved in a solvent, a spin coating method, a casting method, a bar coating method, a roll coating. It can form by the well-known method by application | coating methods, such as a method and an inkjet method. In particular, the light emitting layer of this embodiment can be more suitably formed by the various coating methods described above.

(Thickness of each layer of organic EL element)
The thickness of the light emitting layer is preferably 5 nm to 50 nm, more preferably 7 nm to 50 nm, and most preferably 10 nm to 50 nm. By setting the thickness of the light emitting layer to 5 nm or more, it becomes easy to form the light emitting layer and adjust the chromaticity. By setting the film thickness of the light emitting layer to 50 nm or less, an increase in driving voltage can be suppressed.
The film thickness of each of the other organic layers is not particularly limited, but is usually preferably in the range of several nm to 1 μm. By making such a film thickness range, defects such as pinholes caused by the film thickness being too thin are prevented, and an increase in driving voltage caused by the film thickness being too thick is suppressed, resulting in deterioration of efficiency. Can be prevented.

[Electronics]
The organic EL element of the present invention can be suitably used as an electronic device such as a display device such as a television, a mobile phone, or a personal computer, or a light emitting device for lighting or a vehicular lamp.

[Modification of Embodiment]
In addition, this invention is not limited to the above-mentioned embodiment, The change in the range which can achieve the objective of this invention, improvement, etc. are included in this invention.

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 sufficient that at least one light emitting layer contains the aromatic amine derivative represented by the general formula (1), and the other light emitting layers are of a fluorescent light emitting type. It may be a light emitting layer or a phosphorescent light emitting layer.
In addition, when the organic EL element has a plurality of light emitting layers, these light emitting layers may be provided adjacent to each other, or a so-called tandem organic material in which a plurality of light emitting units are stacked via an intermediate layer. It may be an EL element.

In the present invention, it is also preferable that the light emitting layer contains a charge injection auxiliary material.
When a light emitting layer is formed using a host material having a wide energy gap, the difference between the ionization potential (Ip) of the host material and Ip of the hole injection / transport layer, etc. increases, and holes are injected into the light emitting layer. This may make it difficult to increase the driving voltage for obtaining sufficient luminance.
In such a case, by adding a hole injection / transport charge injection auxiliary agent to the light emitting layer, hole injection into the light emitting layer can be facilitated and the driving voltage can be lowered.

As the charge injection auxiliary agent, for example, a general hole injection / transport material or the like can be used.
Specific examples include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, fluorenone derivatives, hydrazone derivatives, stilbenes. Derivatives, silazane derivatives, polysilane-based, aniline-based copolymers, conductive polymer oligomers (particularly thiophene oligomers), and the like can be given.

  Examples of the hole-injecting material include those described above, and porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds, particularly aromatic tertiary amine compounds are preferred.

In addition, for example, 4,4′-bis (N- (1-naphthyl) -N-phenylamino) biphenyl (hereinafter abbreviated as NPD) having two condensed aromatic rings in the molecule, or triphenylamine 4,4 ′, 4 ″ -tris (N- (3-methylphenyl) -N-phenylamino) triphenylamine (hereinafter abbreviated as MTDATA) and the like in which three units are connected in a starburst type. it can.
A hexaazatriphenylene derivative or the like can also be suitably used as the hole injecting material.
In addition, inorganic compounds such as p-type Si and p-type SiC can also be used as the hole injection material.

  Further, in the above embodiment, the aromatic amine derivative of the present invention is used as a dopant material in the light emitting layer. However, the aromatic amine derivative of the present invention can be used in addition to the light emitting layer, for example, a hole injection layer, a hole transport It can also be used for other organic layers such as a layer, an electron injection layer, and an electron transport layer.

  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 Compound 1

Under an argon stream, 1,6-dibromopyrene (1.8 g), amine 1 (6 g), Pd ₂ (dba) ₃ (140 mg), tert-Bu ₃ P (2.746 M in toluene solution) (190 μl), tert -BuONa (1.5 g) was put into a dehydrated toluene solution (100 ml) and stirred at 120 ° C for 5 and a half hours. After allowing to cool, the produced precipitate was collected by filtration and washed with toluene, methanol, water, acetone and ethyl acetate to obtain a crude product. The crude product was purified by silica gel chromatography (developing solvent: toluene) and reprecipitation (toluene-methanol) to obtain 1 g of Compound 1. The compound 1 was identified by analysis of FD-MS (field desorption mass spectrum).
FDMS, calcd for C ₇₆ H ₅₂ N ₂ = 992, found m / z = 992 (M ⁺ )

DESCRIPTION OF SYMBOLS 1 ... Organic EL element 2 ... Substrate 3 ... Anode 4 ... Cathode 5 ... Light emitting layer 6 ... Hole transport layer 7 ... Electron transport layer 10 ... Organic layer

Claims (28)

An aromatic amine derivative represented by the following general formula (1):
(In the general formula (1), R ^{1 to} R ¹⁰ are each independently
Hydrogen atom,
Halogen atoms,
Hydroxyl group,
A cyano group,
A substituted or unsubstituted alkyl group having 1 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 60 ring carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms,
A substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted alkylamino group having 2 to 30 carbon atoms,
A substituted or unsubstituted arylamino group having 6 to 60 ring carbon atoms,
A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms,
A substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms A substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic ring having 5 to 30 ring atoms Selected from any of the groups.
However, any two of R ^{1 to} R ¹⁰ are each independently represented by the following general formula (2). )
(In the general formula (2),
L ¹ , L ² and L ³ are each independently a single bond or a linking group,
A substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 18 ring carbon atoms, or
A substituted or unsubstituted divalent heterocyclic group having 5 to 15 ring atoms.

If at least one of Ar ^1, Ar ² is a substituent represented by the following general formula (3) is a substituent Ar ¹ and Ar ² are both represented by the following formula (3), to each other Identical or different.
Among Ar ¹ and Ar ² , those not represented by the following general formula (3) are:
A substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 15 ring atoms.
Ar ¹ and L ¹ may or may not form a ring by bonding to each other.
Further, Ar ² and L ² may or may not form a ring by bonding to each other. )
(In the general formula (3),
Ar is
A substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 18 ring carbon atoms or a substituted or unsubstituted divalent heterocyclic group having 5 to 15 ring atoms.
n is an integer of 3 to 20, and the plurality of Ars are the same or different from each other. Adjacent Ars may or may not form a ring by bonding to each other.
R is
Hydrogen atom,
Halogen atoms,
Hydroxyl group,
A cyano group,
A substituted or unsubstituted alkyl group having 1 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 60 ring carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms,
A substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted alkylamino group having 2 to 30 carbon atoms,
A substituted or unsubstituted arylamino group having 6 to 60 ring carbon atoms,
It is selected from either a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms or a substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms.
R may or may not be bonded to adjacent Ar to form a ring. ) The aromatic amine derivative according to claim 1, wherein R ¹ and R ⁶ are represented by the general formula (2). The aromatic amine derivative according to claim 1, wherein R ² and R ⁷ are represented by the general formula (2). The aromatic amine derivative according to any one of claims 1 to 3, wherein the general formula (2) is represented by the following general formula (21).
In (Formula ^{(21), L 1 ~L 3} , Ar 2 has the same meaning as ^L 1 ^~L 3, Ar ² in the general formula (2).
R ²¹ , R ²² , or R ²¹ and R ²⁴ are represented by the general formula (3). Other than those represented by the general formula of R ²¹ to R ²⁵ (3) has the same meaning as R in the general formula (3). ) The aromatic amine derivative according to any one of claims 1 to 4, wherein the general formula (3) is represented by any one of the following general formulas (31) and (32). Aromatic amine derivatives.
(In the said General formula (31), R is synonymous with R of the said General formula (3).
Ar ¹¹ and Ar ¹² are each independently
A substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 18 ring carbon atoms or a substituted or unsubstituted divalent heterocyclic group having 5 to 15 ring atoms.
p ^{is, -Ar} 11 -Ar ¹² - are repeated 2 to 10 integer representing the.
Adjacent Ar ¹¹ and Ar ¹² may or may not form a ring by bonding to each other.
Further, there are cases where adjacent Ar ¹¹ and R are bonded to each other to form a ring, and may not. )
(In the said General formula (32), R is synonymous with R of the said General formula (3).
Ar ^{13 to} Ar ¹⁵ are each independently
A substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 18 ring carbon atoms or a substituted or unsubstituted divalent heterocyclic group having 5 to 15 ring atoms.
q ^{is, -Ar 13} -Ar 14 -Ar ¹⁵ - are 2 to 6 integer representing the repetition of.
Adjacent Ar ¹³ and Ar ¹⁴ may or may not form a ring by bonding to each other.
In addition, adjacent Ar ¹⁴ and Ar ¹⁵ may or may not form a ring by bonding to each other.
In addition, adjacent Ar ¹³ and R may or may not form a ring by bonding to each other. ) In the aromatic amine derivative according to any one of claims 1 to 5,
Ar ² is a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 18 ring carbon atoms, and has no group represented by the general formula (3) as a substituent. Aromatic amine derivatives. In the aromatic amine derivative according to any one of claims 1 to 6,
An aromatic amine derivative, wherein L ¹ and L ² are a single bond. In the aromatic amine derivative according to any one of claims 1 to 7,
Any two of R ^{1 to} R ¹⁰ have the same structure represented by the general formula (2), an aromatic amine derivative. In the aromatic amine derivative according to any one of claims 1 to 6,
Ar in said general formula (3) is a substituent chosen from the group which consists of a substituent represented by the following formula 1-1 to formula 1-21, The aromatic amine derivative characterized by the above-mentioned.
(R _B and R _C in Formula 1-5 and R _D in Formula 1-15 are an unsubstituted methyl group or a phenyl group.) The aromatic amine derivative according to claim 9,
Ar in the general formula (3) is a substituent represented by the formula 1-1, and an aromatic amine derivative. In the aromatic amine derivative according to claim 5,
The partial structure consisting of —Ar ¹¹ —Ar ¹² — of the substituent represented by the general formula (31) is any one of structures represented by the following formulas 2-1 to 2-5. An aromatic amine derivative characterized by
In the aromatic amine derivative according to claim 5,
The partial structure consisting of —Ar ¹³ —Ar ¹⁴ —Ar ¹⁵ — of the substituent represented by the general formula (32) is any one of the structures represented by the following formulas 3-1 to 3-11. An aromatic amine derivative characterized in that
In the aromatic amine derivative according to any one of claims 1 to 12,
The said general formula (1) is represented by the following general formula (11), The aromatic amine derivative characterized by the above-mentioned.
(In the general formula ^(11), R 2 to R ⁵ and ^R 7 ^{to R 10} are the same meanings as ^R 2 to R ⁵ and ^R 7 ^{to R 10} in the general formula (1).
R ³¹ , R ³² , or R ³¹ and R ³⁴ are represented by the general formula (3). Other than those represented by the general formula of R ³¹ to R ⁴⁰ (3) has the same meaning as R in the general formula (3).
Ar ²¹ is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 ring carbon atoms, and does not have the group represented by the general formula (3) as a substituent. ) In the aromatic amine derivative according to any one of claims 1 to 12,
The said general formula (1) is represented by the following general formula (12), The aromatic amine derivative characterized by the above-mentioned.
(In the general formula ^(12), R 2 to R ⁵ and ^R 7 ^{to R 10} are the same meanings as ^R 2 to R ⁵ and ^R 7 ^{to R 10} in the general formula (1).
Ar and n have the same meanings as Ar and n in the general formula (3), respectively.
R, R ³¹ , R ^{33 to} R ³⁵ , and R ³⁶ have the same meaning as R in the general formula (3), respectively.
r is 5. ) In the aromatic amine derivative according to any one of claims 1 to 12,
The said general formula (1) is represented by the following general formula (13), The aromatic amine derivative characterized by the above-mentioned.
(In the general formula ^(13), R 2 to R ⁵ and ^R 7 ^{to R 10} are the same meanings as ^R 2 to R ⁵ and ^R 7 ^{to R 10} in the general formula (1).
Ar and n have the same meanings as Ar and n in the general formula (3), respectively.
R, R ³¹ , R ^{33 to} R ³⁵ , and R ³⁶ have the same meaning as R in the general formula (3), respectively.
r is 5.
Ar ³⁵ is
A substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 15 ring atoms. )   An organic electroluminescent element material comprising the aromatic amine derivative according to any one of claims 1 to 15. A cathode,
The anode,
Having at least one organic layer disposed between the cathode and the anode,
At least one organic layer among the organic layers contains the aromatic amine derivative according to any one of claims 1 to 15. An organic electroluminescence device, wherein: The organic electroluminescence device according to claim 17,
At least one layer of the organic layers is a light emitting layer containing the aromatic amine derivative. An organic electroluminescence device, wherein: The organic electroluminescence device according to claim 18,
The light emitting layer further contains an anthracene derivative represented by the following general formula (100). An organic electroluminescence device, wherein:
(In the general formula (100), Ar ¹⁰¹ and Ar ¹⁰² 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
It is a chain group formed by combining two or three groups selected from the monocyclic group and the condensed ring group.
In the chain group, the monocyclic group and the condensed ring group constituting the chain group may be the same or different from each other, and the groups constituting the chain group may be bonded to each other to form a ring. .
In the general formula (100), R ¹⁰¹ to R ¹⁰⁸ are each independently
Hydrogen atom,
Halogen atoms,
Hydroxyl group,
A cyano group,
A substituted or unsubstituted alkyl group having 1 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 60 ring carbon atoms,
A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms,
A substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms,
A substituted or unsubstituted alkylamino group having 2 to 30 carbon atoms,
A substituted or unsubstituted arylamino group having 6 to 60 ring carbon atoms,
A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms,
A substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms; a substituted or unsubstituted monocyclic group having 5 to 30 ring atoms;
Either a substituted or unsubstituted condensed ring group having 10 to 30 ring-forming atoms, or a chain group formed by combining two or three groups selected from the monocyclic group and the condensed ring group To be elected.
Adjacent R ^{101 to} R ¹⁰⁸ may or may not be bonded to each other to form a ring. In addition, R ^{101 to} R ¹⁰⁸ and the carbon atoms constituting the anthracene ring may or may not be bonded to each other to form a ring.
R ¹⁰¹ , R ¹⁰⁴ , R ¹⁰⁵ or R ¹⁰⁸ adjacent to Ar ¹⁰¹ or Ar ¹⁰² may or may not be bonded to form a ring. Further, Ar ¹⁰¹ or Ar ¹⁰² and the carbon atoms constituting the anthracene ring may or may not be bonded to each other to form a ring. ) The organic electroluminescence device according to claim 19,
Ar ¹⁰¹ and Ar ¹⁰² in the general formula (100) are each independently a substituted or unsubstituted condensed ring group having 10 to 30 ring carbon atoms. An organic electroluminescence device, wherein: The organic electroluminescence device according to claim 19,
One of Ar ¹⁰¹ and Ar ¹⁰² in the general formula (100) is a substituted or unsubstituted monocyclic group having 5 to 30 ring carbon atoms, and the other is a substituted or unsubstituted ring forming carbon atom having 10 to 30 carbon atoms. An organic electroluminescence device characterized by being a condensed ring group of The organic electroluminescence device according to claim 21, wherein
Ar ¹⁰² in the general formula (100) is selected from a naphthyl group, a phenanthryl group, a benzoanthryl group, and a dibenzofuranyl group;
Ar ¹⁰¹ is an unsubstituted phenyl group or a phenyl group in which at least one of the monocyclic group and the condensed ring group is substituted. An organic electroluminescence device, wherein: The organic electroluminescence device according to claim 21, wherein
Ar ¹⁰² in the general formula (100) is a substituted or unsubstituted condensed ring group having 10 to 30 ring carbon atoms, and Ar ¹⁰¹ is an unsubstituted phenyl group. . The organic electroluminescence device according to claim 19,
Ar ¹⁰¹ and Ar ¹⁰² in the general formula (100) are each independently a substituted or unsubstituted monocyclic group having 5 to 30 ring carbon atoms. An organic electroluminescence device, wherein: The organic electroluminescence device according to claim 24,
Ar ¹⁰¹ and Ar ¹⁰² in the general formula (100) are each independently a substituted or unsubstituted phenyl group. An organic electroluminescence device, wherein: The organic electroluminescence device according to claim 25,
Ar ¹⁰¹ in the general formula (100) is an unsubstituted phenyl group, and Ar ¹⁰² is a phenyl group having at least one of the monocyclic group and the condensed ring group as a substituent. Electroluminescence element. The organic electroluminescence device according to claim 25,
Ar ¹⁰¹ and Ar ¹⁰² in the general formula (100) 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   An electronic apparatus comprising the organic electroluminescence element according to any one of claims 17 to 27.