TWI476177B - Organic electroluminescent element and aromatic amine derivative using the same - Google Patents

Description

Aromatic amine derivative and organic electroluminescent element using the same

The present invention relates to an aromatic amine derivative and an organic electroluminescence (EL) device using the same. More specifically, the present invention relates to an aromatic amine derivative which can improve the luminous efficiency of an organic EL element after storage at a high temperature and extend the life of the organic EL element.

The organic EL element is a self-luminous element that utilizes the principle that the fluorescent substance emits light by the recombination energy of a hole injected from the anode and electrons injected from the cathode by applying an electric field. Since CWTang et al. of Eastman‧Kodak Company have proposed a report on the construction of low-voltage-driven organic EL elements by laminated elements (CWTang, SA Vanslyke, Applied Physics Letters, Vol. 51, p. 913, 1987) Etc., research on organic EL elements using organic materials as constituent materials has begun. Regarding the element structure of the organic EL element, a two-layer type including a hole transport (injection) layer and an electron transport light-emitting layer, or a hole transport (injection) layer, a light-emitting layer, and an electron transport (injection) layer are known. The three-layer type and so on. With regard to such a laminated structural element, in order to improve the recombination efficiency of the injected hole and electrons, those skilled in the art have studied the element structure or the formation method.

In general, when an organic EL element is driven or stored in a high-temperature environment, adverse effects such as a change in luminescent color, a decrease in luminous efficiency, an increase in driving voltage, and a shortened luminescent lifetime are caused. In order to prevent such adverse effects, it is necessary to increase the glass transition temperature (Tg) of the hole transport material. Therefore, the hole transporting material must have a large number of aromatic groups in the molecule (for example, the aromatic diamine derivative in the specification of U.S. Patent No. 4,720,432, and the aromatic fused biamine derivative in the specification of U.S. Patent No. 5,061,569. The structure having 8 to 12 benzene rings is usually preferably used.

However, when a thin film is formed by using a hole transporting material having a large number of aromatic groups in the molecule to form an organic EL device, there is a problem in that the outlet of the crucible used for vapor deposition is clogged due to the formation of crystal, or the formation of crystals is caused. On the other hand, the film is defective, resulting in a decrease in the yield of the organic EL element. In addition, although the glass transition temperature (Tg) of a compound having a large number of aromatic groups in the molecule is generally high, considering that the sublimation temperature is high, decomposition or formation of a vapor deposition film during vapor deposition may occur, and thus There is a problem of short life.

On the other hand, a hole-transporting material is known as a monoamine derivative having a carbazole (U.S. Patent No. 6,242,115, Japanese Patent Laid-Open No. Hei. No. 2007-284431, No. 2004-103467, Japanese Patent Laid-Open No. Hei. No. 2008-120769, Japanese Patent Application Laid-Open No. Hei No. Hei 11-273860. However, such compounds cannot sufficiently improve the life or efficiency of the organic EL element, and in particular, there is a problem in improving the life or efficiency of the organic EL element after storage at a high temperature. In addition, an amine derivative in which a carbazole is bonded to an amine by fluorene is known, as disclosed in Japanese Patent Laid-Open No. Hei 11-144873, and Japanese Patent Laid-Open No. 2000-302756. Such amine derivatives are also expected to increase life or efficiency.

As described above, although a report of a hole transport material useful for improving the efficiency or the growth life of an organic EL element has been proposed, the industry is still strongly expected to develop an element material which can impart more excellent performance to an organic EL element.

The present invention has been made to solve the above problems, and an object of the invention is to provide an organic EL device which has high luminous efficiency and a long lifetime even after storage at a high temperature, and an aromatic amine derivative for realizing the organic EL device. Things.

The inventors of the present invention conducted intensive studies to achieve the above object, and found that a novel aromatic amine derivative having a specific structure represented by the general formula (1) is used as a material for an organic EL device, particularly as a hole. When the material is transported, the above problems can be solved, and the present invention has been completed.

First, the inventors of the present invention thought that since the oxazole is stabilized by oxidation or reduction by an amine derivative in which an anthracene is bonded to an amine group, an effect of increasing the life can be obtained. The present inventors have further conducted various studies on the structure of an amine group having excellent reduction stability, and as a result, it has been found that an intermolecular group can be formed by forming an amine group into a group having a moderate steric hindrance. Reduced interaction to inhibit crystallization and effectively increase Tg

In addition, the inventors of the present invention have found that the compound of the present invention having an asymmetric structure can reduce the vapor deposition temperature, thereby suppressing decomposition during vapor deposition, and is excellent in encapsulation properties of the compound and interaction with the light-emitting layer. Therefore, the effect of prolonging the life of the obtained organic EL element and the effect of improving the efficiency can be obtained, and in particular, by combining with the blue light-emitting element, a long-life effect and a high-efficiency effect can be obtained, and the present invention has been completed.

That is, the present invention provides an aromatic amine derivative represented by the formula (1).

Further, the present invention provides an organic EL device in which one or more organic thin film layers containing at least a light-emitting layer are sandwiched between a cathode and an anode of the organic EL device, and at least one layer of the organic thin film layer contains the above-described aromatic The amine derivative is used as a component of the mixture alone or in a mixture.

[Effects of the Invention]

The organic EL device using the aromatic amine derivative of the present invention has high efficiency and long life even after storage at a high temperature.

The above and other objects, features, and advantages of the present invention will become more apparent and understood.

The aromatic amine derivative of the present invention is represented by the formula (1).

[Chemical 2]

[in the formula (1),

R ₁ to R _{4 each} represent a linear or branched alkyl group composed of a hydrocarbon having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or carbon. a trialkylsulfanyl group having 3 to 10, a triarylsulfanyl group having 18 to 30 carbon atoms, an alkylarylsulfanyl group having 8 to 15 carbon atoms, and an aryl group having 6 to 14 carbon atoms;

a and b are independent of 0 to 4, respectively.

c and d are independent of 0 to 3, respectively.

Adjacent plurality of R ₁ to R ₄ may be bonded to form a saturated or unsaturated ring (wherein R ₃ and R _{4 are} not bonded to form an aromatic ring),

R' and R" represent a linear or branched alkyl group composed of a hydrocarbon having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms.

Ar _{1 is} represented by the following formula (2).

Ar _{2 is} represented by the following general formula (3)]

[in equations (2) and (3),

Ar ₃ to Ar ₆ are each independently an arylene group having a core carbon number of 6 to 14,

R ₅ to R ₈ represent a hydrogen atom, a linear, branched or cyclic alkyl group composed of a hydrocarbon having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon number of 3 to 10 a trialkylsulfanyl group, a triarylsulfanyl group having a carbon number of 18 to 30, an alkylarylsulfanyl group having a carbon number of 8 to 15, an aryl group having a core number of 6 to 14 or a biphenyl group;

e and f are independent of 1 to 4, respectively.

g and h are independent of 1 to 5, respectively.

When e to f is greater than or equal to 2, the plurality of R ₅ to R _{8 present} may be the same or different.

a plurality of R ₅ to R ₈ may be bonded to form a saturated ring (wherein R _{8 is} not an aryl group having a carbon number of 6),

In the general formula (2), (Ar ₅ ) may or may not exist, and when (Ar ₅ ) is absent, (Ar ₄ ) is not an arylene group having a nuclear carbon number of 6]

In the aromatic amine derivative represented by the formula (1) of the present invention, R ₁ to R _{4 each} represent a linear or branched alkyl group composed of a hydrocarbon having 1 to 10 carbon atoms and a carbon number of 3 a cycloalkyl group of ～10, an alkoxy group having 1 to 10 carbon atoms, a trialkylalkylene group having 3 to 10 carbon atoms, a triarylsulfanyl group having a carbon number of 18 to 30, and a carbon number of 8 to 15. An alkylarylalkylene group or an aryl group having a core number of 6 to 14.

R ₁ to R _{4 are} preferably a linear or branched alkyl group composed of a hydrocarbon having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. An oxy group, a trialkylsulfanyl group having 3 to 6 carbon atoms, a triarylsulfanyl group having 18 to 21 carbon atoms, an alkylarylalkylene group having 8 to 12 carbon atoms, and a core carbon number of 6 to 10. The aryl group is more preferably a linear or branched alkyl group composed of a hydrocarbon having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms. .

Specific examples of the linear or branched alkyl group composed of a hydrocarbon having 1 to 10 carbon atoms of R ₁ to R ₄ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-butyl group. Dibutyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 1- Methylpentyl, 4-methyl-2-pentyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, 1-methylheptyl, 2-ethylhexyl, 2 -propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, positive癸基等. Preferred are methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, and t-butyl groups.

Specific examples of the cycloalkyl group having 3 to 10 carbon atoms of R ₁ to R ₄ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 4-methylcyclohexyl group, and 1 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, bicyclo[2.2.2]octyl, and the like. Preferred are cyclopentyl, cyclohexyl and cycloheptyl.

Specific examples of the alkoxy group having 1 to 10 carbon atoms of R ₁ to R ₄ include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, and a second butoxy group. , a third butoxy group, a n-pentyloxy group, a n-hexyloxy group, a n-octyloxy group, and the like. Preferred are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second butoxy and tert-butoxy.

Specific examples of the trialkylsulfanyl group having 3 to 10 carbon atoms of R ₁ to R ₄ include a trimethylsulfanyl group, a triethylsulfanyl group, a tripropyldecylalkyl group, and a tert-butyl-dimethyl group.矽 alkyl and the like. Preferred are trimethyldecylalkyl or triethyldecylalkyl.

Specific examples of the triarylsulfanyl group having 18 to 30 carbon atoms of R ₁ to R ₄ include a triphenylsulfonyl group, a tris(4-methylphenyl)decyl group, and a tris(3-methylphenyl group). A decyl group, a tris(2-methylphenyl)decyl group, a trinaphthyl fluorenyl group, and the like. Preferred are triphenyldecylalkyl and tris(4-methylphenyl)decylalkyl.

Specific examples of the alkylarylsulfanyl group having 8 to 15 carbon atoms of R ₁ to R ₄ include dimethylphenyldecylalkyl group, diphenylmethyl group, and dimethyl (4-methylphenyl group).矽 alkyl and the like.

Specific examples of the aryl group having 6 to 14 carbon atoms in R ₁ to R ₄ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthyl group, and a 2-anthyl group. 9-fluorenyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 4-methylphenyl, 3-methylphenyl, 2 -methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4-n-propylphenyl, 4-isopropylphenyl, 2-isopropylphenyl , 4-n-butylphenyl, 4-isobutylphenyl, 4-second butylphenyl, 2-second butylphenyl, 4-tert-butylphenyl, 3-tert-butyl Phenyl, 2-tert-butylphenyl, 4-n-pentylphenyl, 4-isopentylphenyl, 4-tripentylphenyl, 4-n-hexylphenyl, 4-n-heptylbenzene , 4-n-octylphenyl, 4-(2'-ethylhexyl)phenyl, 4-th-octylphenyl, 4-cyclopentylphenyl, 4-cyclohexylphenyl, 4-(4 '-Methylcyclohexyl)phenyl, 3-cyclohexylphenyl, 2-cyclohexylphenyl;

4-ethyl-1-naphthyl, 6-n-butyl-2-naphthyl;

2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,6-Dimethylphenyl, 2,3,5-trimethylphenyl, 3,4,5-trimethylphenyl, 2,4-diethylphenyl, 2,3,6- Trimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2,6-diisobutylphenyl, 2,4-di(t-butyl)phenyl, 2,5-di(t-butyl)phenyl, 3,5-di(t-butyl)phenyl, 2,4-di-neopentyl Phenyl, 2,3,5,6-tetramethylphenyl;

4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl, 2-ethoxyphenyl, 3-n-propoxyphenyl, 4 -isopropoxyphenyl, 2-isopropoxyphenyl, 4-n-butoxyphenyl, 4-isobutoxyphenyl, 2-isobutoxyphenyl, 2-second butoxy Phenylphenyl, 4-n-pentyloxyphenyl, 4-isopentyloxyphenyl, 2-isopentyloxyphenyl, 2-pivalyloxyphenyl, 4-n-hexyloxyphenyl, 2- (2'-ethylbutyl)oxyphenyl, 4-n-octyloxyphenyl, 4-cyclohexyloxyphenyl, 2-cyclohexyloxyphenyl;

2-methoxy-1-naphthyl, 4-methoxy-1-naphthyl, 4-n-butoxy-1-naphthyl, 5-ethoxy-1-naphthyl, 6-ethoxy -2-naphthyl, 6-n-butoxy-2-naphthyl, 7-methoxy-2-naphthyl, 7-n-butoxy-2-naphthyl;

2,3-Dimethoxyphenyl, 2,4-dimethoxyphenyl, 2,5-dimethoxyphenyl, 2,6-dimethoxyphenyl, 3,4-dimethyl Oxyphenyl, 3,5-dimethoxyphenyl, 3,5-diethoxyphenyl, 3,5-di-n-butoxyphenyl, 2-methoxy-4-methyl Phenyl, 2-methoxy-5-methylphenyl, 2-methyl-4-methoxyphenyl, 3-methyl-4-methoxyphenyl, 3-methyl-5- Oxyphenyl, 3-ethyl-5-methoxyphenyl, 2-methoxy-4-ethoxyphenyl, 2-methoxy-6-ethoxyphenyl, 3,4, 5-trimethoxyphenyl;

4-fluorophenyl, 3-fluorophenyl, 2-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-di Fluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 3,4,5-trifluorophenyl;

2-fluoro-4-methylphenyl, 2-fluoro-5-methylphenyl, 3-fluoro-2-methylphenyl, 3-fluoro-4-methylphenyl, 4-fluoro-2- Methylphenyl, 5-fluoro-2-methylphenyl, 2-chloro-4-methylphenyl, 2-chloro-5-methylphenyl, 2-chloro-6-methylphenyl, 3 -Chloro-2-methylphenyl, 4-chloro-2-methylphenyl, 4-chloro-3-methylphenyl, 2-chloro-4,6-dimethylphenyl, 2-fluoro- 4-methoxyphenyl, 2-fluoro-6-methoxyphenyl, 3-fluoro-4-ethoxyphenyl;

4-trifluoromethylphenyl, 3-trifluoromethylphenyl, 2-trifluoromethylphenyl, 3,5-bis(trifluoromethyl)phenyl;

4-trifluoromethoxyphenyl;

(2-Phenylpropyl)phenyl, 3-methyl-2-naphthyl, 4-methyl-1-naphthyl and the like.

Among these, a substituted or unsubstituted phenyl group or a naphthyl group is preferred.

a and b are independently 0 to 4, preferably 0.

c and d are independently 0 to 3, preferably 0.

In the aromatic amine derivative represented by the formula (1), a plurality of R ₁ to R ₄ may be bonded to form a saturated or unsaturated ring (wherein R ₃ and R _{4 are} not bonded to form an aromatic ring). Specifically, the saturated or unsaturated ring formed by the bonding of R ₁ to R ₄ has the structure described below.

[Specific Example of Saturated, Unsaturated Ring of Carbazole Site]

[Chemical 4]

[Specific example of saturated, unsaturated ring of the 茀 site]

R' and R" represent a linear or branched alkyl group composed of a hydrocarbon having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms.

R' and R" are preferably a linear or branched alkyl group composed of a hydrocarbon having 1 to 6 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms.

Specific examples of the linear or branched alkyl group composed of a hydrocarbon having 1 to 12 carbon atoms of R' and R" include a straight chain or a branched chain as a specific example of R ₁ to R ₄ . alkyl.

Specific examples of the cycloalkyl group having 3 to 10 carbon atoms of R' and R" include a cycloalkyl group exemplified as a specific example of R ₁ to R ₄ .

In the aromatic amine derivative of the present invention, Ar _{1 is} represented by the following formula (2), and Ar ₂ is represented by the following formula (3).

In the formula, Ar ₃ to Ar ₆ are each independently and are an arylene group having a nucleus carbon number of 6 to 14.

R ₅ to R ₈ represent a hydrogen atom, a linear, branched or cyclic alkyl group composed of a hydrocarbon having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon number of 3 to 10 A trialkylsulfanyl group, a triarylsulfanyl group having a carbon number of 18 to 30, an alkylarylsulfanyl group having a carbon number of 8 to 15, an aryl group having a core number of 6 to 14 or a biphenyl group.

e and f are 1 to 4, and g and h are 1 to 5. When e to f is greater than or equal to 2, the plurality of R ₅ to R _{8 present} may be the same or different, and a plurality of R ₅ to R ₈ may be bonded to form a saturated ring. Wherein R _{8 is} not an aryl group having a nucleus number of 6; in the formula (2), (Ar ₅ ) may or may not exist, and when (Ar ₅ ) is absent, (Ar ₄ ) is not a nucleus An arylene group having a carbon number of 6.

In the general formula (2) and the general formula (3), Ar ₃ to Ar ₆ are each independently and are an arylene group having a nucleus carbon number of 6 to 14. Ar ₃ to Ar _{6 are} preferably an arylene group having a core carbon number of 6 to 10.

Specific examples of Ar ₃ to Ar ₆ include benzene, naphthalene, anthracene, phenanthrene, toluene, p-tert-butylbenzene, and p-phenylene. a divalent residue of benzene, 3-methylnaphthalene or 4-methylnaphthalene.

Ar ₃ to Ar _{6 are} preferably a divalent residue of benzene or naphthalene.

In the general formula (2), (Ar ₅ ) may or may not be present, and when (Ar ₅ ) is absent, (Ar ₄ ) is not an arylene group having a nucleus number of 6.

In the general formulae (2) and (3), R ₅ to R ₈ represent a hydrogen atom, a linear, branched or cyclic alkyl group composed of a hydrocarbon having 1 to 10 carbon atoms, and the carbon number is Alkoxy group of 1 to 10, trialkylsulfanyl group having 3 to 10 carbon atoms, triarylsulfanyl group having 18 to 30 carbon atoms, alkylarylalkylene group having 8 to 15 carbon atoms, or nuclear carbon The number is 6 to 14 aryl or biphenyl.

Specific examples of the linear, branched or cyclic alkyl group composed of a hydrocarbon having 1 to 10 carbon atoms of R ₅ to R ₈ include R ₁ to R ₄ in the formula (1). A straight-chain or branched alkyl group composed of a hydrocarbon having 1 to 10 carbon atoms and a linear or branched alkyl group and a cycloalkyl group exemplified as a specific example of a cycloalkyl group having 3 to 10 carbon atoms .

Specific examples of the alkoxy group having 1 to 10 carbon atoms in the range of R ₅ to R ₈ include a specific example of the alkoxy group having 1 to 10 carbon atoms of R ₁ to R ₄ in the formula (1). The alkoxy groups listed.

Specific examples of the trialkylsulfanyl group having 3 to 10 carbon atoms in R ₅ to R ₈ include a trialkylsulfanyl group having 3 to 10 carbon atoms as R ₁ to R ₄ in the formula (1). The trialkylsulfanyl group exemplified in the specific examples.

Specific examples of the triarylsulfanyl group having a carbon number of from 18 to 30 in the case of R ₅ to R ₈ include specific examples of the triarylsulfanyl group having 18 to 30 carbon atoms of R ₁ to R ₄ in the formula (1). The triarylsulfonylalkyl group exemplified in the examples.

Specific examples of the alkylarylalkylene group having 8 to 15 carbon atoms in R ₅ to R ₈ include an alkylaryl group having 8 to 15 carbon atoms as R ₁ to R ₄ in the formula (1). The alkylarylalkylene group exemplified in the specific examples of the decyl group.

Specific examples of the aryl group having 6 to 14 nucleus groups of R ₅ to R ₈ include a specific example of an aryl group having 6 to 14 nucleus groups of R ₁ to R ₄ in the formula (1). The aryl groups listed.

In the formula (2), R ₅ to R _{7 are} preferably a linear, branched or cyclic alkyl group having a hydrogen atom and a hydrocarbon having 1 to 6 carbon atoms, and the carbon number is 1 to 1. 6 alkoxy group, trialkylsulfonyl group having 3 to 6 carbon atoms, aryl group having 6 to 14 carbon atoms, and R ₅ to R ₇ more preferably a hydrogen atom and having a carbon number of 1 to 4 a linear, branched or cyclic alkyl group composed of a hydrocarbon, an aryl group having a core number of 6 to 10, more preferably, R ₅ to R ₆ represent a hydrogen atom, and R ₇ represents a hydrogen atom or An aryl group having a core carbon number of 6 to 10.

In the formula (3), R _{8 is} preferably a linear, branched or cyclic alkyl group having a hydrogen atom and a hydrocarbon having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. An oxy group, a trialkylsulfanyl group having 3 to 6 carbon atoms, an aryl group having a core number of 10 to 14 or a biphenyl group, and R _{8 is} more preferably an aryl group having a hydrogen atom or a nucleus number of 10 or Biphenyl. Further, R _{8 is} not an aryl group having a nucleus number of 6.

In the general formula (2) and the general formula (3), e or f are independently from 1 to 4, and g or h are independently from 1 to 5.

When e to f is greater than or equal to 2, the plurality of R ₅ to R _{8 present} may be the same or different, and a plurality of R ₅ to R ₈ may be bonded to form a saturated ring.

A plurality of R ₅ to R ₈ may be bonded to form a saturated ring. Specifically, a saturated ring formed by bonding a plurality of R ₅ to R ₈ may have a structure as described below.

[Specific example of saturated ring]

Specific examples of the general formula (2) include a group containing the following group.

Ethnic group (2)-1:

[化8]

Ethnic group (2)-2:

Ethnic group (2)-3:

Ethnic group (2)-4:

[11]

Ethnic group (2)-5:

Ethnic group (2)-6:

Specific examples of the general formula (3) include a group containing the following group.

Ethnic group (3)-1:

Ethnic group (3)-2:

Ethnic group (3)-3:

Ethnic group (3)-4:

[化17]

In the aromatic amine derivative represented by the formula (1) of the present invention, the combination of the formula (2) and the formula (3) with respect to Ar ₁ and Ar _{2 is} preferably a group (2)- 1 and ethnic group (3)-1, ethnic group (2)-1 and ethnic group (3)-2, ethnic group (2)-1 and ethnic group (3)-3, ethnic group (2)-1 and ethnic group (3)-4 , ethnic group (2)-2 and ethnic group (3)-1, ethnic group (2)-2 and ethnic group (3)-2, ethnic group (2)-3 and ethnic group (3)-1, ethnic group (2)-3 Ethnic group (3)-2, ethnic group (2)-3 and ethnic group (3)-3, ethnic group (2)-3 and ethnic group (3)-4, ethnic group (2)-4 and ethnic group (3)-1, ethnic group (2)-4 and ethnic group (3)-2, ethnic group (2)-5 and ethnic group (3)-1, ethnic group (2)-5 and ethnic group (3)-2, ethnic group (2)-5 and ethnic group ( 3)-3, ethnic group (2)-5 and ethnic group (3)-4, ethnic group (2)-6 and ethnic group (3)-1, and ethnic group (2)-6 and ethnic group (3)-2. More preferably, the group (2)-1 and the group (3)-1, the group (2)-1 and the group (3)-2, the group (2)-1 and the group (3)-4, the group ( 2)-2 and ethnic group (3)-1, ethnic group (2)-4 and ethnic group (3)-1, ethnic group (2)-5 and ethnic group (3)-1, ethnic group (2)-5 and ethnic group (3 )-2, and ethnic groups (2)-5 and ethnic groups (3)-3. More preferably, the group (2)-1 and the group (3)-1, the group (2)-1 and the group (3)-4.

In the aromatic amine derivative represented by the formula (1) of the present invention, Ar ₁ and Ar _{2 are} preferably a group different from Ar ₁ and Ar ₂ .

Further, the total carbon number of Ar ₁ and Ar ₂ is preferably from 22 to 36, more preferably from 22 to 34, still more preferably from 22 to 30.

In the aromatic amine compound represented by the formula (1) of the present invention, when Ar ₁ and Ar ₂ are the same group, R' and R" preferably represent a hydrocarbon having 2 to 12 carbon atoms. The linear or branched alkyl group or the cycloalkyl group having 3 to 10 carbon atoms is more preferably a linear or branched alkyl group composed of a hydrocarbon having 3 to 12 carbon atoms. Or a cycloalkyl group having a carbon number of 5 to 10.

In the aromatic amine derivative represented by the formula (1) of the present invention, one of the preferred forms of the formula (2) is a group represented by the formula (4), more preferably a formula (6) and a group represented by the formula (7).

In the aromatic amine derivative represented by the formula (1) of the present invention, one of the preferred forms of the formula (3) is a group represented by the formula (5).

In the general formula (4) and the formula _{(5), R 5 ~ R} 8, e, f, g and h are as defined in the general formula (2) and the formula (3) R ₅ ~ R _8, e , f, g and h are the same.

_{In, R 5 ~ R 7, e} , g and f is defined for the general formula R ₅ ~ R (2) is _7, e, f g, and the same general formula (6) and Formula (7).

Specific examples of the aromatic amine derivative represented by the formula (1) of the present invention include the following compounds.

[Chemistry 20]

[Chem. 21]

[化22]

The aromatic amine derivative represented by the formula (1) of the present invention can be produced by a known method of the aromatic amine derivative itself. For example, a 2,7-dihalogenated indole derivative (for example, 2,7-diiodo-9,9-dialkyl-9H-indole, 2-bromo-7-iodo-9,9-dioxane) The reaction of a group of formula (1-A) with a substituted or unsubstituted oxazole is carried out by reacting a group of 9H-indole, 2-chloro-7-iodo-9,9-dialkyl-9H-indole. The compound represented by the formula (1-A) is then reacted with a compound represented by the formula (2-A) to produce an aromatic amine derivative represented by the formula (1).

In the formula (1-A), Y ₁ represents a halogen atom, R ₁ to R4, R', R", and a to d and R ₁ to R ₄ , R', R" in the formula (1). And a to d indicate the same meaning.

In the general formula (2-A), Ar ₁ and Ar ₂ in the general formula Ar ₁ and Ar (1) ₂ represent the same meanings.

Alternatively, a 2,7-dihalogenated anthracene derivative (for example, 2,7-diiodo-9,9-dialkyl-9H-indole, 2-bromo-7-iodine-9,9-di) Alkyl-9H-indole, 2-chloro-7-iodo-9,9-dialkyl-9H-indole) is reacted with a compound represented by the formula (2-A) to produce a formula (1-B) The compound represented by the formula (1-B) is then reacted with a substituted or unsubstituted carbazole to produce a compound represented by the formula (1).

In the formula (1-B), Y ₁ represents a halogen atom, R ₃ , R ₄ , R', R", Ar ₁ and Ar ₂ and R ₃ , R ₄ , R' in the formula (1), R", Ar ₁ and Ar ₂ represent the same meaning.

Further, the reaction of a 2,7-dihalogenated anthracene derivative, a substituted or unsubstituted carbazole or a compound represented by the formula (2-A) can be carried out, for example, by the following method: palladium ( Palladium) catalyst [eg palladium acetate / tri-tert-butylphosphine, tris(dibenzylideneacetone) dipalladium / dicyclohexylphenylphosphine, tris(dibenzylideneacetone) dipalladium / di (third In the presence of butyl)-2-biphenylphosphine] and a base (for example, potassium carbonate, sodium carbonate, cesium carbonate, sodium butoxide, potassium butoxide), A method of reacting a 7-dihalogenated anthracene derivative with a substituted or unsubstituted carbazole or a compound represented by the formula (2-A): or a copper catalyst (for example, copper powder) 2,7-dihalogenated anthracene derivative, substituted or unsubstituted oxazole or formula (in the presence of copper chloride, copper bromide) and a base (for example, sodium carbonate, potassium carbonate) 2-A) A method in which a compound represented by a reaction is carried out.

The aromatic amine derivative represented by the formula (1) of the present invention can be preferably used as a material for an organic EL device. The organic electroluminescence device of the present invention has one or more organic thin film layers containing a light-emitting layer between the cathode and the anode, and at least one layer of the organic thin film layer contains any one of the above formula (1). Aromatic amine derivatives. In the organic EL device of the present invention, it is preferred that the hole injection layer or the hole transport layer contains the aromatic amine derivative represented by the above formula (1).

Hereinafter, the configuration of the organic EL device of the present invention will be described.

A typical configuration of the organic EL device of the present invention is as follows.

(1) anode / luminescent layer / cathode

(2) Anode/hole injection layer/light-emitting layer/cathode

(3) anode/light emitting layer/electron injection layer/cathode (4) anode/hole injection layer/light emitting layer/electron injection layer/cathode

(5) Anode/organic semiconductor layer/light emitting layer/cathode

(6) Anode/organic semiconductor layer/electron barrier layer/light-emitting layer/cathode

(7) Anode/organic semiconductor layer/light emitting layer/adhesion improving layer/cathode

(8) Anode/hole injection layer/hole transmission layer/light-emitting layer/electron injection layer/cathode

(9) anode / insulating layer / luminescent layer / insulating layer / cathode

(10) Anode/Inorganic Semiconductor Layer/Insulation Layer/Light Emitting Layer/Insulation Layer/Cathode

(11) Anode/organic semiconductor layer/insulation layer/light-emitting layer/insulation layer/cathode

(12) anode/insulation layer/hole injection layer/hole transmission layer/light-emitting layer/insulation layer/cathode

(13) anode/insulation layer/hole injection layer/hole transmission layer/light-emitting layer/electron injection layer/cathode

In these, it is generally preferred to adopt the configuration of (8), but the present invention is not limited to such a configuration.

Further, in the organic EL device of the present invention, the aromatic amine derivative represented by the formula (1) of the present invention can be used in any of the above-mentioned organic thin film layers, and it is preferred that these constituent elements The aromatic amine derivative is contained in the light-emitting belt, and it is particularly preferable that the aromatic amine derivative is contained in the hole injection layer or the hole transport layer. The content of the aromatic amine derivative represented by the formula (1) can be selected from 30 mol% to 100 mol%.

The aromatic amine derivative of the present invention can be preferably used as a material for a hole injection layer or a hole transport layer.

The hole injection layer and the hole transport layer are layers that assist in injecting holes into the light-emitting layer and transport them to the light-emitting region, and the hole injection layer and the hole transport layer have large hole mobility and ionization. The energy is small, usually less than or equal to 5.5 eV.

The material of the hole injection layer and the hole transport layer is preferably a material capable of transporting holes to the light-emitting layer with a lower electric field strength. In addition, as for the hole mobility, for example, when an electric field of 10 ⁴ V/cm to 10 ⁶ V/cm is applied, the hole mobility is preferably at least 10 ^-4 cm ² /V. s.

The aromatic amine derivative of the present invention can be preferably used as a hole transporting material because of its small ionization energy and large hole mobility. Further, since the aromatic amine derivative of the present invention contains a polar group in the molecule, it has good adhesion to the anode and is not easily affected by the cleaning conditions of the substrate, etc., so that it can be preferably used as a hole injecting material. The inventors of the present invention have considered that the organic EL device using the aromatic amine derivative of the present invention has a long life.

The hole injection layer or the hole transport layer can be used by, for example, a vacuum evaporation method, a spin coat method, a cast method, and a Langmuir method. A known method such as a -Blodgett method or an LB method is obtained by forming a film of the aromatic amine derivative of the present invention. The film thickness at the time of forming the hole injection layer or the hole transport layer is not particularly limited, but is usually 5 nm to 5 μm.

If the hole transport belt contains the aromatic amine derivative of the present invention, the hole injection layer or the hole transport layer may be composed of one layer of one or two or more of the above materials, and hole injection. The layer and the hole transport layer may be a hole injection layer and a hole transport layer formed by laminating a hole injection layer and a hole transport layer containing different kinds of compounds.

Further, the organic semiconductor layer is a layer for assisting in injecting holes or electrons into the light-emitting layer, and suitably has a conductivity of 10 ^{- 10} S/cm or more. As the material of such an organic semiconductor layer, conductive dendrimers such as a thiophene-containing oligomer or an arylamine-containing oligomer, and an arylamine-containing dendrimer can be used. Things and so on.

The organic EL element is usually produced on a light-transmissive substrate (translucent substrate). The light-transmitting substrate is a substrate supporting an organic EL element, and the light-transmitting property of the substrate is preferably such that the transmittance of light in a visible light region having a wavelength of 400 nm to 700 nm is 50% or more, and more preferably a smooth substrate is used. .

Preferable examples of such a light-transmitting substrate include a glass plate, a synthetic resin plate, and the like. Examples of the glass plate include, in particular, soda-lime glass, bismuth-containing glass, lead glass, aluminosilicate glass, borosilicate glass. ), a plate formed of bismuth boron silicate glass, quartz, or the like. Further, examples of the synthetic resin sheet include: polycarbonate resin, acryl resin, polyethylene terephthalate resin, polyether sulfide resin. , a plate of polysulphone resin or the like.

The anode has a function of injecting a hole into the hole transport layer or 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 used in the present invention include: indium tin oxide (ITO), an indium zinc oxide (IZO), a mixture of indium tin oxide and cerium oxide (indium tin) Cerium oxide, ITCO), a mixture of IZO and cerium oxide (IZCO), an indium cerium oxide (ICO), a mixture of zinc oxide and aluminum oxide (AZO), tin oxide (NESA) ), gold, silver, platinum, copper, etc.

The anode can be obtained by forming the electrode material into a film by a vapor deposition method or a sputtering method.

Thus, when light from the luminescent layer is emitted from the anode, it is preferred that the light transmittance of the anode is greater than 10%. Further, the sheet resistance of the anode is preferably equal to or less than several hundred Ω/cm ² . Although the film thickness of the anode depends on the material, it is usually selected from the range of 10 nm to 1 μm, and preferably from 10 nm to 200 nm.

As the electrode material, a metal having a small work function (less than or equal to 4 eV), an alloy, a conductive compound, and the like can be used. Specific examples of such an electrode material include: sodium, sodium-potassium alloy, magnesium, lithium, lanthanum, magnesium-silver alloy, aluminum/alumina, Al/Li ₂ O, Al/LiO, Al/LiF, aluminum-lithium alloy , indium, rare earth metals, etc.

The cathode can be obtained by forming the electrode material into a film by vapor deposition or sputtering.

Here, when light from the light-emitting layer is emitted from the cathode, the light transmittance of the cathode is preferably more than 10%. Further, the film resistance of the cathode is preferably equal to or less than several hundred Ω/cm ² . The film thickness of the cathode is usually 10 nm to 1 μm, preferably 50 nm to 200 nm.

In general, since an organic EL element applies an electric field to an ultrathin membrane, it is easy to cause pixel defects due to leakage or short. In order to prevent this, an insulating layer containing an insulating thin film layer may be interposed between the pair of electrodes. Examples of materials for the insulating layer include: aluminum oxide, lithium fluoride, lithium oxide, cesium fluoride, cerium oxide, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, aluminum nitride, titanium oxide, cerium oxide. ,

Cerium oxide, tantalum nitride, boron nitride, molybdenum oxide, niobium oxide, vanadium oxide, and the like. A mixture of two or more of these compounds may be used as an insulating layer, or a laminate of two or more of the two or more compounds may be used as an insulating layer.

In the organic EL device of the present invention, the light-emitting layer has:

(i) Injection function: when an electric field is applied, a hole is injected from the anode or the hole injection layer, and a function of injecting electrons from the cathode or the electron injection layer into the light-emitting layer:

(ii) Transmission function: a function of moving an injected electric charge (electrons and holes) by an electric field force;

(iii) Luminescence function: Provides a recombination site for electrons and holes, and thereby illuminates the function.

Examples of the method of forming the light-emitting layer include a known method such as a vapor deposition method, a spin coating method, or an LB method. A particularly preferred luminescent layer is a molecularly deposited film. The molecular deposition film refers to a film formed by deposition of a material compound in a gas phase state, or a film formed by curing a material compound in a solution state or a liquid phase state. In general, the molecular deposition film and the thin film (molecular accumulation film) formed by the LB method can be distinguished by a difference in agglomerated structure, high-order structure, or a function difference resulting therefrom.

Further, the light-emitting layer can be formed by dissolving a binding agent such as a resin and a compound as a material in a solvent to form a solution, and then forming the solution into a film by a spin coating method or the like.

In the present invention, the light-emitting layer may further contain a light-emitting material containing a pyrene-based derivative and an amine compound or other known metal complex.

The metal complex is preferably a metal complex containing at least one metal selected from the group consisting of Ir, Ru, Pd, Pt, Os, and Re. The ligand preferably has at least one skeleton selected from the group consisting of a pyridine pyridine skeleton, a bipyridyl skeleton, and a phenanthroline skeleton.

Specific examples of such a metal complex include: tris(2-phenylpyridine)fluorene, tris(2-phenylpyridine)fluorene, tris(2-phenylpyridine)palladium, bis(2-phenylpyridine)platinum. , tris(2-phenylpyridine) fluorene, tris(2-phenylpyridine) fluorene, octaethyl platinum porphyrin, octaphenyl platinum porphyrin, octaethyl palladium porphyrin, octaphenyl palladium porphyrin, etc. However, it is not limited to such a complex. An appropriate metal complex can be selected depending on the desired luminescent color, element properties, and host compound.

Further, a phosphorescent dopant or a fluorescent dopant can be used for the light-emitting layer of the organic EL device of the present invention.

The phosphorescent dopant material is a compound that can emit light by a triplet exciton. The phosphorescent dopant material is not particularly limited as long as it can emit light by a triplet exciton, and preferably contains at least one metal selected from the group consisting of Ir, Ru, Pd, Pt, Os, and Re. The metal complex is more preferably a porphyrin metal complex or an orthometalated metal complex. The porphyrin metal complex is preferably a porphyrin platinum complex. The phosphorescent dopant materials may be used singly or in combination of two or more.

There are various ligands which can form ortho-metallated metal complexes. Preferred ligands include 2-phenylpyridine derivatives and 7,8-benzoquinone (7,8). -benzoquinoline) derivative, 2-(2-thienyl)pyridine derivative, 2-(1-naphthyl)pyridine derivative, 2-phenylquinoline derivative or the like. These derivatives may have a substituent as needed. In particular, a fluoride or a derivative having a trifluoromethyl group is a preferred blue-based dopant material. Further, the ortho-metallated metal complex may have a ligand other than the above ligand such as acetylacetonate or picric acid as an ancillary ligand.

The content of the phosphorescent dopant material in the light-emitting layer is not particularly limited and may be appropriately selected as needed, and the content is, for example, 0.1% by weight to 70% by weight, preferably 1% by weight to 30% by weight. If the content of the phosphorescent dopant material is less than 0.1% by weight, the light emission is weak, and the inclusion effect of the dopant material cannot be sufficiently exerted; if the content of the phosphorescent dopant material exceeds 70% by weight, it is called concentration quenching. The phenomenon of concentration quenching becomes apparent, resulting in a decrease in component performance. In addition, the light-emitting layer may also contain a hole transport material, an electron transport material, and a polymer binder as needed.

Further, the film thickness of the light-emitting layer is preferably from 5 nm to 50 nm, more preferably from 7 nm to 50 nm, most preferably from 10 nm to 50 nm. When the film thickness of the light-emitting layer is less than 5 nm, it is difficult to form a light-emitting layer, and it is difficult to adjust the chromaticity. When the film thickness of the light-emitting layer exceeds 50 nm, the driving voltage rises.

The fluorescent dopant material is preferably a compound selected from the following compounds depending on the desired luminescent color: an amine compound, an aromatic compound, a tris(8-hydroxyquinoline) aluminum complex, and the like. a compound, a coumarin derivative, a tetraphenylbutadiene derivative, a bisstyrylarylene derivative, an oxadiazole derivative or the like. Particularly preferred are arylamine compounds and aryldiamine compounds, of which more preferred are styrylamine compounds, styryldiamine compounds, aromatic amine compounds, aromatic diamine compounds, and more preferably more condensation. Cyclic amine derivatives. These fluorescent doping materials may be used alone or in combination of a plurality of fluorescent doping materials.

In the organic EL device of the present invention, it is preferred to contain a styrylamine and/or an arylamine as a fluorescent dopant. The styrylamine compound and/or the arylamine is preferably a compound represented by the following formula (10).

In the formula (10), Ar ₇ to Ar ₉ are a substituted or unsubstituted ring to form an aromatic group having 6 to 40 carbon atoms. u is an integer of 1 to 4, and u is preferably an integer of 1 to 2. Any one of Ar ₇ to Ar ₉ may be a group containing a styryl group. When any of Ar ₇ to Ar ₈ has a styryl group, it is preferred that at least one of Ar ₈ or Ar ₉ is substituted with a styryl group.

Examples of the aromatic group having a ring having 6 to 40 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a coronenyl group, a biphenyl group, and a triphenyl group. (terphenyl), pyrazolyl, furanyl, thienyl, benzoquinthiol, oxadiazolyl, diphenylfluorenyl, indolyl, carbazolyl ( Carbazolyl), pyridyl, benzoquinolyl, fluoranthenyl, indenyl, stilbene, perylenyl, [church] + chrysenyl , picenyl, triphenylenyl, rubicenyl, benzindenyl, phenylmercapto, bisindenyl or sub-formula represented by the following formula (C) and formula (D) Aryl and the like. Among them, a naphthyl group, an anthracenyl group, a [grass (above) + fast) group, a fluorenyl group or an arylene group represented by the formula (D) is preferred.

In the formula (C), r is an integer of from 1 to 3.

Further, examples of preferred substituents for substituting the above aryl group and arylene group include an alkyl group having 1 to 6 carbon atoms (ethyl group, methyl group, isopropyl group, n-propyl group, second butyl group, a third butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, etc., an alkoxy group having 1 to 6 carbon atoms (ethoxy group, methoxy group, isopropoxy group, n-propoxy group, second group) Butyloxy, tert-butoxy, pentyloxy, hexyloxy, cyclopentyloxy, cyclohexyloxy, etc.), aryl group having 5 to 40 carbon atoms, aryl group having 5 to 40 carbon atoms A substituted amino group, an ester group having an aryl group having 5 to 40 carbon atoms, an ester group having an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a halogen atom or the like.

The luminescent material contained in the light-emitting layer is not particularly limited, and examples of the host material include a ruthenium compound, a phenanthrene compound, a fluoranthene compound, a tetracene compound, a triphenyl compound, and a grass (above) + fast (chrysene) compound, hydrazine compound, coronene compound, hydrazine compound, phthaloperylene compound, naphthaloperylene compound, naphthacene compound, pentacene compound, etc. Acyclic aromatic compounds, oxadiazole, bisbenzoquinoxaline, bisstyryl, cyclopentadiene, quinoline metal complex, tris(8-hydroxyquinoline)aluminum complex, tris(4- Methyl-8-quinoline) aluminum complex, tris(5-phenyl-8-quinoline)aluminum complex, aminoquinoline metal complex, benzoquinone metal complex, tri- (P-triphenyl-4-yl)amine, 1-aryl-2,5-bis(2-thienyl)pyrrole derivative, pyran, quinacridone, red fluorene ( Rubrene), distyrylbenzene derivative, distyryl arylene derivative, porphyrin derivative, anthracene derivative, pyrazoline derivative, coumarin color , pyranyl pigment, phthalocyanine pigment, naphthalocyanine dye, croconium pigment, squaliliu m dye, oxobenzoquinone pigment, fluorescent Prime pigment, rhodamine dye, pyrylium pigment, anthraquinone dye, anthraquinone dye, polythiophene pigment, or rare earth complex phosphor, rare earth phosphorescent fault Polymer (such as Ir complex) and a polymer material such as polyvinyl carbazole, polydecane, or polyethylenedioxythiophene (PEDOT), etc., which may be used alone or in combination. Use of two or more mixtures.

The host material which can be used in combination with the compound of the present invention is preferably a compound represented by the following formula (11) to formula (17).

An anthracene derivative represented by the following formula (11).

In the formula (11), A ₂₁ and A ₂₂ are each independently a substituted or unsubstituted aromatic ring group having 6 to 60 carbon atoms. R ₂₁ to R ₂₈ are each independently a hydrogen atom, a substituted or unsubstituted aromatic ring group having 6 to 50 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 atoms, A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted or not a substituted arylalkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 atoms, a substituted or unsubstituted arylthio group having 5 to 50 atoms, A substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkylene group, a carboxyl group, a halogen atom, a cyano group, a nitro group or a hydroxyl group.

An anthracene derivative represented by the following formula (12).

[化30]

In the formula (12), R ₃₀ to R ₃₉ are each independently a hydrogen atom, a substituted or unsubstituted aromatic ring group having 6 to 50 carbon atoms, and a substituted or unsubstituted atomic number of 5 to 5 An aromatic heterocyclic group of 50, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted carbon number of 1 to 50 The alkoxy group, the substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, the substituted or unsubstituted aryloxy group having 5 to 50 atoms, and the substituted or unsubstituted atomic number are 5 to 50 arylthio groups, substituted or unsubstituted alkoxycarbonyl groups having 1 to 50 carbon atoms, substituted or unsubstituted alkylene groups, carboxyl groups, halogen atoms, cyano groups, nitro groups or hydroxyl groups.

An anthracene derivative represented by the following formula (13).

In the formula (13), R ₄₀ to R ₄₉ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group which may be substituted, an alkoxy group, an aryloxy group, an alkylamino group or an alkenyl group ( Alkenyl), an arylamino group or a heterocyclic group which may be substituted.

i and j each represent an integer of 1 to 5, and when i and j are 2 or more, R ₄₀ or R ₄₁ may be the same or different. Further, R ₄₀ or R 4 ₁ may be bonded to each other to form a ring, and R ₄₂ and R ₄₃ , R ₄₄ and R ₄₅ , R ₄₆ and R ₄₇ , and R ₄₈ and R ₄₉ may be bonded to each other to form a ring.

L ₁ represents a single bond, -O-, -S-, -N(R)- (R is an alkyl group or an aryl group which may be substituted), an alkylene group or an arylene group.

An anthracene derivative represented by the following formula (14).

In the formula (14), R ₅₀ to R ₅₉ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamine group or may be substituted. Heterocyclic group.

k, l, m, and n each represent an integer of 1 to 5, and when k, l, m, and n are 2 or more, R ₅₀ and R ₅₁ and R ₅₅ or R ₅₆ may be the same or different. Further, R ₅₂ and R ₅₃ and R _{54 to} each other or R ₅₅ may be bonded to each other to form a ring, and R ₅₂ and R ₅₃ , R ₅₇ and R ₅₈ may be bonded to each other to form a ring.

L ₂ represents a single bond, -O-, -S-, -N(R)- (R is an alkyl group or an aryl group which may be substituted), an alkylene group or an arylene group.

A spirofluorene derivative represented by the following formula (15).

In the formula (15), Ar ₃₁ to Ar ₃₄ are each independently a substituted or unsubstituted biphenyl group or a substituted or unsubstituted naphthyl group.

A compound represented by the following formula (16).

In the formula (16), Ar ₄₁ to Ar ₄₃ each independently represent a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, and Ar ₄₄ to Ar ₄₆ each independently represent a hydrogen atom, substituted or not. The substituted aryl group has a carbon number of 6 to 60.

R ₆₁ to R ₆₃ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon number of 5 to 18; An aryloxy group, an aralkyloxy group having 7 to 18 carbon atoms, an arylamino group having 5 to 16 carbon atoms, a nitro group, a cyano group, an ester group having 1 to 6 carbon atoms or a halogen atom.

An anthracene compound represented by the following formula (17).

In the formula (17), R ₇₁ and R ₇₂ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted group. Or an unsubstituted heterocyclic group, a substituted amino group, a cyano group or a halogen atom. R ₇₁ and R _{72 which} are bonded to different fluorenyl groups may be the same or different from each other, and R ₇₁ and R ₇₂ bonded to the same fluorenyl group may be the same or different.

R ₇₃ and R ₇₄ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. . R ₇₃ and R _{74 which} are bonded to different fluorenyl groups may be the same or different from each other, and R ₇₃ and R ₇₄ bonded to the same fluorenyl group may be the same or different.

Ar ₇₁ and Ar ₇₂ represent a benzene ring in total of three or more substituted or unsubstituted condensed polycyclic aromatic groups, or a benzene ring and a heterocyclic ring in total of three or more substituted or unsubstituted Substituted condensed polycyclic heterocyclic group bonded with carbon and a thiol group. Ar ₇₁ and Ar ₇₂ may be the same or different. v represents an integer of 1 to 10.

Of the above host materials, preferred are anthracene derivatives, more preferably monoterpene derivatives, and particularly preferred are asymmetric anthracenes.

The host compound suitable for phosphorescence luminescence composed of a compound containing a carbazole ring is a compound having a function of transferring energy from an excited state to a phosphorescent compound, and as a result, the phosphorescent compound emits light. The host compound is not particularly limited as long as it can transfer exciton energy to the phosphorescent compound, and can be appropriately selected depending on the purpose. The host compound may have any heterocyclic ring or the like in addition to the carbazole ring.

Specific examples of such a host compound include: a carbazole derivative, a triazole derivative, an oxazole derivative, an oxadiazole derivative, an imidazole derivative, a polyarylalkane derivative, a pyrazoline derivative, and a pyrazoline. Pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amine-substituted chalcone derivatives, styrylpurine derivatives, fluorenone derivatives, hydrazine Hydrazone) derivative, anthracene derivative, silazane derivative, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylene compound, porphyrin compound, quinodimethane derivative , anthrone derivative, diphenylquinone derivative, thiopyrandioxide derivative, carbodiimide derivative, fluorenylene methane derivative, stilbene a pyrazine derivative, a heterocyclic tetracarboxylic anhydride such as naphthoquinone, a phthalocyanine derivative, a metal complex of an 8-quinolinol derivative or a metal phthalocyanine, or a benzoxazole or a variety of gold represented by a metal complex of benzothiazole as a ligand It is a polyvalent decane compound, a poly(N-vinylcarbazole) derivative, an aniline copolymer, a thiophene oligomer, a conductive polymer oligomer such as polythiophene, a polythiophene derivative, or a polyphenylene derivative. A polymer compound such as a polyphenylenevinylene derivative or a polyfluorene derivative. The host compound may be used singly or in combination of two or more kinds.

Specific examples include the following compounds.

Next, the electron injecting layer and the electron transporting layer are layers which assist in injecting electrons into the light emitting layer and transporting them to the light emitting region, and are layers having a large electron mobility. Further, the adhesion improving layer is a layer formed of a material having a particularly good adhesion to the cathode in the electron injecting layer.

Further, it is known that in an organic EL device, light emitted from an electrode (in this case, a cathode) is reflected, so that interference occurs between light directly emitted from the anode and light emitted through the electrode. In order to effectively utilize the interference effect, the film thickness of the electron transport layer can be appropriately selected in the range of several nm to several μm. When the film thickness of the electron transport layer is particularly thick, in order to avoid voltage rise, it is preferred that the electron mobility is at least 10 ^-5 cm ² /Vs when an electric field of 10 ⁴ V/cm to 10 ⁶ V/cm is applied. .

The material for the electron injecting layer is preferably a metal complex of 8-hydroxyquinoline or a derivative thereof, or an oxadiazole derivative. As a specific example of the metal complex of the above 8-hydroxyquinoline or 8-hydroxyquinoline derivative, chelating with oxine (usually 8-hydroxyquinoline or 8-hydroxyquinoline) can be used. A metal chelate octane compound such as tris(8-hydroxyquinoline)aluminum is used as an electron injecting material.

On the other hand, the oxadiazole derivative may, for example, be an electron transfer compound represented by the following formula.

In the formula, Ar ₈₁ , Ar ₈₂ , Ar ₈₃ , Ar ₈₅ , Ar ₈₆ and Ar ₈₉ each represent a substituted or unsubstituted aryl group, and may be the same or different. Further, Ar ₈₄ , Ar ₈₇ and Ar ₈₈ represent a substituted or unsubstituted arylene group, which may be the same or different.

Examples of the aryl group include a phenyl group, a biphenyl group, an anthracenyl group, an anthracenyl group and an anthracenyl group Further, examples of the arylene group include a phenylene group, a naphthylene group, a biphenylylene group, an anthranylene group, an anthranylene group, and an anthranylene group. Further, examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cyano group. The electron transfer compound preferably has a property of forming a film.

The hole injection layer and the hole transport layer are layers that assist in injecting holes into the light-emitting layer and are transmitted to the light-emitting region. The hole injection layer and the hole transport layer have large hole mobility and small ionization energy. Usually less than or equal to 5.5eV.

The material of the hole injection layer and the hole transport layer is preferably such that the hole can be transported to the material of the light-emitting layer with a lower electric field strength. Further, as for the hole mobility, for example, when an electric field of 10 ⁴ V/cm to 10 ⁶ V/cm is applied, the hole mobility is preferably at least 10 ^-4 cm ² /V‧s.

When the aromatic amine derivative of the present invention is used in a hole transport belt, the aromatic amine derivative of the present invention can be used alone to form a hole injection layer or a hole transport layer, and the aromatic of the present invention can also be used. Amine derivatives are used in combination with other materials.

The material which forms the hole injection layer and the hole transport layer by mixing with the aromatic amine derivative of the present invention is not particularly limited as long as it has the above-mentioned preferable properties, and can be used as a power source from the conventional photoconductive material. Any material is selected from the material of the charge transport material of the hole or the material for the hole injection layer and the hole transport layer of the organic EL element. In the present invention, a material having a hole transporting ability and which can be used for a hole transporting belt is referred to as a hole transporting material.

The aromatic amine derivative used for the hole injection layer and the hole transport layer may be a compound represented by the following formula.

Ar ₂₁₁ to Ar ₂₁₃ , Ar ₂₂₁ to Ar ₂₂₃ and Ar ₂₀₃ to Ar ₂₀₈ are each a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 carbon atoms, or a substituted or unsubstituted atomic number of 5 to 5 50 aromatic heterocyclic groups. p, q, s, t, w, and y are each an integer of 0 to 3.

Specific examples of the substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group. , 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-fused tetraphenyl, 2-fused tetraphenyl, 9-fused tetraphenyl, 1-oxime Base, 2-indenyl, 4-indenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, p-triphenyl-4-yl, p-triphenyl-3-yl, p-terphenyl 2-based, m-triphenyl-4-yl, m-triphenyl-3-yl, m-triphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-tert-butylphenyl , p-(2-phenylpropyl)phenyl, 3-methyl-2-naphthyl, 4-methyl-1-naphthyl, 4-methyl-1-indenyl, 4'-methylbiphenyl Base, 4"-t-butyl-p-tert-triphenyl-4-yl.

Specific examples of the substituted or unsubstituted aromatic heterocyclic group having 5 to 50 atoms include 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, pyrazinyl, 2-pyridyl, and 3 -pyridyl, 4-pyridyl, 1-indenyl, 2-indenyl, 3-indenyl, 4-indenyl, 5-indenyl, 6-fluorenyl, 7-fluorenyl , 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isodecyl, 6-isoindenyl, 7-isodecyl, 2-furyl, 3-furyl, 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, 7-benzofuran Base, 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofuranyl, Quinolinyl, 3-quinolyl, 4-quinolyl, 5-quinolinyl, 6-quinolinyl, 7-quinolyl, 8-quinolinyl, 1-isoquinolinyl, 3-iso Quinolinyl, 4-isoquinolyl, 5-isoquinolinyl, 6-isoquinolinyl, 7-isoquinolinyl, 8-isoquinolinyl, 2-quinoxalinyl, 5-quinoxaline Lolinyl, 6-quinoxalinyl, 1-phenanthridinyl, 2-cylindinyl 3-cyridinyl, 4-cyridinyl, 6-cyridinyl, 7-cyridinyl, 8-cyridinyl, 9-cyridinyl, 10-cyridinyl, 1-acridinyl (1- Acridinyl), 2-acridinyl, 3-acridinyl, 4-acridinyl, 9-acridinyl, 1,7-morpholin-2-yl, 1,7-morpholin-3-yl, 1 , 7-morpholin-4-yl, 1,7-morpholin-5-yl, 1,7-morpholin-6-yl, 1,7-morpholin-8-yl, 1,7-morpholine- 9-yl, 1,7-morpholin-10-yl, 1,8-morpholin-2-yl, 1,8-morpholin-3-yl, 1,8-morpholin-4-yl, 1, 8-morpholin-5-yl, 1,8-morpholin-6-yl, 1,8-morpholin-7-yl, 1,8-morpholin-9-yl, 1,8-morpholine-10 -yl, 1,9-morpholin-2-yl, 1,9-morpholin-3-yl, 1,9-morpholin-4-yl, 1,9-morpholin-5-yl, 1,9 -morpholin-6-yl, 1,9-morpholin-7-yl, 1,9-morpholin-8-yl, 1,9-morpholin-10-yl, 1,10-morpholin-2- 1,10-morpholin-3-yl, 1,10-morpholin-4-yl, 1,10-morpholin-5-yl, 2,9-morpholin-1-yl, 2,9- Polinolin-3-yl, 2,9-morpholin-4-yl, 2,9-morpholin-5-yl, 2,9-morpholin-6-yl, 2,9-morpholin-7-yl , 2,9-morpholin-8-yl, 2,9-morpholin-10-yl, 2,8-morpholin-1-yl, 2,8-morpholin-3-yl, 2,8-morph啉-4-yl, 2,8-morpholin-5-yl, 2,8-morpholin-6-yl, 2,8-morpholin-7-yl, 2,8-morpholine -9-yl, 2,8-morpholin-10-yl, 2,7-morpholin-1-yl, 2,7-morpholin-3-yl, 2,7-morpholin-4-yl, 2 , 7-morpholin-5-yl, 2,7-morpholin-6-yl, 2,7-morpholin-8-yl, 2,7-morpholin-9-yl, 2,7-morpholine- 10-yl, 1-phenazinyl, 2-cyanozinyl, 1-phenothiazinyl, 2-morphothazinyl, 3-morphothazinyl, 4-morphine Thiazinyl, 10-morphothrazinyl, 1-phenoxazinyl, 2-phinoxazinyl, 3-morphoxazinyl, 4-morphoxazinyl, 10-morphoxazinyl , 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-oxadiazolyl, 5-oxadiazolyl, 3-furazanyl, 2 -thienyl, 3-thienyl, 2-methylpyrrol-1-yl, 2-methylpyrrol-3-yl, 2-methylpyrrol-4-yl, 2-methylpyrrole-5-yl, 3 -methylpyrrol-1-yl, 3-methylpyrrol-2-yl, 3-methylpyrrol-4-yl, 3-methylpyrrole-5-yl, 2-tert-butylpyrrol-4-yl , 3-(2-phenylpropyl)pyrrol-1-yl, 2-methyl-1-indolyl, 4-methyl-1-indolyl, 2-methyl-3-indolyl, 4-methyl-3-indolyl, 2-tert-butyl-1-indenyl, 4-tert-butyl 1-indenyl, 2-tert-butyl-3-indenyl, 4 - Tributyl-3-indolyl group.

Further, a compound represented by the following formula can be used in the hole injection layer and the hole transport layer.

[39]

Ar ₂₃₁ to Ar ₂₃₄ are each a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 atoms.

L is a linking group and is a single bond, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 atoms. X is an integer from 0 to 5.

Specific examples of the substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 carbon atoms and the substituted or unsubstituted aromatic heterocyclic group having 5 to 50 atoms include the same as described above. Group.

Further, specific examples of the material of the hole injection layer and the hole transport layer include, for example, a triazole derivative, an oxadiazole derivative, an imidazole derivative, a polyarylalkane derivative, a pyrazoline derivative, and pyridyl. An oxazolinone derivative, a phenylenediamine derivative, an arylamine derivative, a chalcone derivative substituted with an amine group, an oxazole derivative, a styrylpurine derivative, an anthrone derivative, an anthracene derivative, An anthracene derivative, a decazane derivative, a polydecane system, an aniline copolymer, a conductive polymer oligomer (particularly a thiophene oligomer), and the like.

The above-mentioned materials can be used as the material of the hole injection layer and the hole transport layer, preferably a porphyrin compound, an aromatic tertiary amine compound, and a styrylamine compound, and particularly preferably an aromatic three. Amine compounds.

Further, a compound having two fused aromatic rings in the molecule, for example, 4,4'-bis(N-(1-naphthyl)-N-phenylamino)biphenyl (hereinafter abbreviated as NPD), and 4,4',4"-tris(N-(3-methylphenyl)-N-phenylamine group formed by linking three triphenylamine units into starburst Triphenylamine (hereinafter abbreviated as MTDATA) and the like.

In addition, a nitrogen-containing heterocyclic derivative represented by the following formula may be used in the hole injection layer and the hole transport layer.

In the above formula, R ₁₂₁ to R ₁₂₆ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted impurity. Any of the groups in the ring group. Wherein, R ₁₂₁ to R ₁₂₆ may be the same or different. Further, R ₁₂₁ and R ₁₂₂ , R ₁₂₃ and R ₁₂₄ , R ₁₂₅ and R ₁₂₆ , R ₁₂₁ and R ₁₂₆ , R ₁₂₂ and R ₁₂₃ , R ₁₂₄ and R ₁₂₅ may form a fused ring.

Further, a compound represented by the following formula may be used in the hole injection layer and the hole transport layer.

In the above formula, R ₁₃₁ to R ₁₃₆ are a substituent, and an electron withdrawing group such as a cyano group, a nitro group, a sulfonyl group, a carbonyl group, a trifluoromethyl group or a halogen is preferable.

As indicated by such materials, a charge accepting material can also be used as a hole injecting material. The specifics of these materials are as shown above.

Further, in addition to the above aromatic dimethylene-based compound described as a material of the light-emitting layer, an inorganic compound such as p-type Si or p-type SiC can be used as a material for the hole injection layer and the hole transport layer.

The aromatic amine derivative of the present invention can be formed into a film by a known method such as a vacuum deposition method, a spin coating method, a casting method or an LB method to obtain a hole injection layer and a hole transport layer.

The film thickness of the hole injection layer and the hole transport layer is not particularly limited, but is usually 5 nm to 5 μm. The hole injection layer and the hole transport layer may be composed of one or two or more of the above materials, as long as the aromatic amine derivative of the present invention is contained in the hole transport belt, or A hole injection layer and a hole transport layer formed of different kinds of compounds are laminated to obtain a hole injection layer and a hole transport layer.

Further, an organic semiconductor layer may be provided as a layer for assisting injection of a hole into the light-emitting layer, and the organic semiconductor layer suitably has a conductivity of 10 ^-10 S/cm or more. As the material of such an organic semiconductor layer, a conductive oligomer such as a thiophene-containing oligomer or an arylamine-containing oligomer, or a conductive dendrimer such as an arylamine-containing dendrimer can be used.

As a method of producing the organic EL device of the present invention, for example, an anode, a light-emitting layer, a hole injection layer, and an electron injection layer can be formed using the above materials and methods, and finally a cathode is formed. Further, an organic EL element may be fabricated from the cathode to the anode in the reverse order of the above.

Hereinafter, a production example of an organic EL element in which an anode/hole injection layer/light-emitting layer/electron injection layer/cathode is sequentially provided on a light-transmitting substrate will be described.

First, a film made of an anode material is formed on a suitable light-transmitting substrate by a vapor deposition method or a sputtering method so as to have a film thickness of 1 μm or less, preferably 10 nm to 200 nm. .

Then, a hole injection layer is provided on the anode. The hole injection layer can be formed by a vacuum vapor deposition method, a spin coating method, a casting method, or an LB method as described above. In terms of easily obtaining a homogeneous film and being less likely to cause pinholes, it is preferred to form a hole injection layer by a vacuum deposition method.

When the hole injection layer is formed by a vacuum deposition method, the vapor deposition conditions vary depending on the compound to be used (the material of the hole injection layer), the crystal structure of the target hole injection layer, or the recombination structure. Preferably, the evaporation source temperature is 50 ° C to 450 ° C, the vacuum degree is 10 ^-7 Torr to 10 ^-3 Torr, the evaporation rate is 0.01 nm / s to 50 nm / s, and the substrate temperature is -50 ° C to 300 ° C. The film thickness is appropriately selected within the range of 5 nm to 5 μm.

Next, a light-emitting layer is provided on the hole injection layer. The light-emitting layer can also be obtained by forming a thin film of a light-emitting material by a method such as a vacuum deposition method, a sputtering method, a spin coating method, or a casting method using the light-emitting material of the present invention. In order to obtain a homogeneous film easily, and it is difficult to generate pinholes, it is preferred to form a light-emitting layer by a vacuum deposition method.

When the light-emitting layer is formed by a vacuum deposition method, the vapor deposition conditions vary depending on the compound to be used, and in general, it is preferably selected from the same conditions as those for forming the hole injection layer. The film thickness of the light-emitting layer is preferably in the range of 10 nm to 40 nm.

Thereafter, an electron injecting layer is provided on the light emitting layer. At this time, similarly to the hole injection layer and the light-emitting layer, since it is necessary to obtain a homogeneous film, it is preferable to form the electron injection layer by a vacuum deposition method. The vapor deposition conditions can be selected from the same conditions as the hole injection layer and the light-emitting layer.

Then, a cathode is laminated, whereby an organic EL element can be obtained. The cathode is formed of a metal and can be formed by a vapor deposition method, a sputtering method, or the like. From the viewpoint of protecting the base organic film layer from damage during film formation, it is preferred to form a cathode by vacuum evaporation.

The above-described organic EL device is preferably produced by continuously performing from the anode to the cathode in a single vacuum process.

The method for forming each layer of the organic EL device of the present invention is not particularly limited. A conventionally known vacuum vapor deposition method, spin coating method, or the like can be employed. The organic thin film layer containing the compound represented by the above formula (1) in the organic EL device of the present invention can be formed by a known method: vacuum evaporation method, molecular beam epitaxy method (MBE (molecular beam) (epitaxy) method, or a dipping method of a solution obtained by dissolving a compound represented by the above formula (1) in a solvent, and a coating method such as a spin coating method, a casting method, a bar coating method, or a roll coating method.

The film thickness of each organic layer of the organic EL device of the present invention is not particularly limited, and in general, in order to prevent occurrence of defects such as pinholes and to improve efficiency, it is preferably in the range of several nm to 1 μm.

Further, when a DC voltage is applied to the organic EL element, when the anode is set to a positive (+) polarity, the cathode is set to a negative (-) polarity, and a voltage of 5 V to 40 V is applied, light emission can be observed. Further, if the polarity is reversed, no current flows even when a voltage is applied, and no light is emitted at all. Further, when an alternating voltage is applied, uniform light emission can be observed only when the anode has a positive (+) polarity and the cathode has a negative (-) polarity. The waveform of the applied alternating current can be an arbitrary waveform.

[Examples]

Hereinafter, the present invention will be described in more detail based on Synthesis Examples and Examples.

The structural formulas of the intermediates 1 to 14 are as follows.

[化42]

Synthesis Example 1 (Synthesis of Intermediate 1)

Under a stream of argon, 47 g of 4-bromobiphenyl, 23 g of iodine, 9.4 g of periodic acid dihydrate, 42 mL of water, 360 mL of acetic acid, and 11 mL of sulfuric acid were placed in a 1000 mL three-necked flask, and stirred at 65 ° C for 30 minutes, and then stirred. The reaction was carried out at 90 ° C for 6 hours. The reaction was poured into ice water and filtered. It was washed with water and then with methanol, whereby 67 g of a white powder was obtained. The white powder was identified as Intermediate 1 by FD-MS (field desorption mass spectrometry).

Synthesis Example 2 (Synthesis of Intermediate 2)

The same reaction as in Synthesis Example 1 was carried out except that 2-bromo-9,9-dimethylindole was used instead of 4-bromobiphenyl to obtain 61 g of a white powder. The white powder was identified as Intermediate 2 by FD-MS analysis.

Synthesis Example 3 (Synthesis of Intermediate 3)

45 g of intermediate 1, carbazole 21 g, cuprous iodide 240 mg, tripotassium phosphate 56 g, 1,4-dioxane 160 mL, and reverse-1 were placed in a 500 mL three-necked flask under a stream of argon. 2.5 ml of 2-cyclohexanediamine was reacted at 130 ° C for 24 hours. After completion of the reaction, extraction was carried out with toluene and dried over magnesium sulfate. The dried product was concentrated under reduced pressure, and the obtained crude product was purified using a column. The crystals were recrystallized using toluene, and the crystals were collected by filtration and dried to obtain 33 g of Intermediate 3 as a white powder.

Synthesis Example 4 (Synthesis of Intermediate 4)

To a three-necked flask, 250 g of m-triphenyl (manufactured by Aldrich Co., Ltd.), 50 g of hydroiodic acid dihydrate, 75 g of iodine, 750 ml of acetic acid, and 25 ml of concentrated sulfuric acid were added, and the mixture was reacted at 70 ° C for 3 hours. After the reaction, 5 L of methanol was injected, followed by stirring for 1 hour. The reaction solution was filtered, and the obtained crystal was purified by column chromatography, and recrystallized from acetonitrile to obtain intermediate 4 as a white powder (3'-phenyl-4-iodine Benzo) 64 g and 3-phenyl-5-iodobiphenyl 17 g. The intermediate 4 was identified by analysis of FD-MS and H-NMR (H-nuclear magnetic resonance).

Synthesis Example 5 (Synthesis of Intermediate 5)

Toluene 300 mL, 2 M carbonic acid were added to 39.9 g of Intermediate 2 (100 mmol), phenylboric acid 12.4 g (105 mmol), and tetrakis(triphenylphosphine)palladium (0) 2.31 g (2.00 mmol) under argon. 150 mL of a sodium aqueous solution was heated under reflux for 10 hours.

Immediately after the completion of the reaction, the mixture was filtered, and then the aqueous layer was removed. The organic layer was dried over sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to give white crystals (yield: 81%). The white powder was identified as Intermediate 5 by FD-MS analysis.

Synthesis Example 6 (Synthesis of Intermediate 6)

The same reaction as in Synthesis Example 5 was carried out except that Intermediate 1 was used instead of Intermediate 2, and 1-naphthylboronic acid was used instead of phenylboronic acid to obtain 30.2 g of a white powder. The white powder was identified as Intermediate 6 by FD-MS analysis.

Synthesis Example 7 (Synthesis of Intermediate 7)

The same reaction as in Synthesis Example 5 was carried out except that Intermediate 1 was used instead of Intermediate 2, and 4-diphenylboronic acid was used instead of phenylboronic acid to obtain 32.1 g of a white powder. The white powder was identified as Intermediate 7 by FD-MS analysis.

Synthesis Example 8 (Synthesis of Intermediate 8)

Under an argon atmosphere, 400 mL of anhydrous THF (anhydrous tetrahydrofuran) was added to 29.6 g (100 mmol) of the by-product 3-phenyl-5-iodobiphenyl obtained in Synthesis Example 4, and stirred at -40 ° C. And 1.6 mL (100 mmol) of 1.6 M n-butyllithium in hexane was added during stirring. The reaction solution was stirred for 1 hour while heating to 0 °C. The reaction solution was again cooled to -78 ° C, and a solution of 26.0 g (250 mmol) of trimethyl borate in 50 mL of dry THF was added dropwise.

The reaction solution was stirred at room temperature for 5 hours. After adding 200 mL of 1N hydrochloric acid, the mixture was stirred for 1 hour, and then the aqueous layer was removed. The organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained solid was washed with toluene to obtain 19.2 g of a boronic acid compound. Identification was performed by FD-MS analysis.

To a solution of 28.3 g (100 mmol) of 4-iodobromobenzene, 28.5 g (105 mmol) of the above boric acid compound, and 2.31 g (2.00 mmol) of tetrakis(triphenylphosphine)palladium(0) under an argon atmosphere, 300 mL of toluene was added. 150 mL of 2M sodium carbonate aqueous solution was heated under reflux for 10 hours.

Immediately after the completion of the reaction, the mixture was filtered, and then the aqueous layer was removed. The organic layer was dried over sodium sulfate and concentrated. The residue was purified by a silica gel column chromatography to give white powder (yield: 26.2 g). The white powder was identified as Intermediate 8 by FD-MS analysis.

Synthesis Example 9 (synthesis of intermediate 9)

The same reaction as in Synthesis Example 5 was carried out except that the intermediate 1 was used instead of the intermediate 2, and 4-tert-butylphenylboronic acid was used instead of the phenylboronic acid to obtain 32.1 g of a white powder. The white powder was identified as Intermediate 9 by FD-MS analysis.

Synthesis Example 10 (Synthesis of Intermediate 10)

The same reaction as in Synthesis Example 5 was carried out except that 4-bromoiodobenzene was used instead of Intermediate 2, and 2-diphenylboronic acid was used instead of phenylboronic acid to obtain 23.6 g of a white powder. The white powder was identified as intermediate 10 by FD-MS analysis.

Synthesis Example 11 (Synthesis of Intermediate 11)

The same reaction as in Synthesis Example 5 was carried out except that 4-bromoiodobenzene was used instead of Intermediate 2, and 9,9-dimethyl-9H茀-2-boronic acid was used instead of phenylboronic acid to obtain 28.9 g of a white powder. The white powder was identified as the intermediate 11 by FD-MS analysis.

Synthesis Example 12 (Synthesis of Intermediate 12)

The same reaction as in Synthesis Example 5 was carried out except that 3-bromoiodobenzene was used instead of Intermediate 2, and 2-diphenylboronic acid was used instead of phenylboronic acid to obtain 21.3 g of a colorless liquid. The white powder was identified as intermediate 12 by FD-MS analysis.

Synthesis Example 13 (Synthesis of Intermediate 13)

The same reaction as in Synthesis Example 5 was carried out except that 3-bromoiodobenzene was used instead of Intermediate 2, and 4-diphenylboronic acid was used instead of phenylboronic acid to obtain 24.1 g of a white powder. The white powder was identified as the intermediate 13 by FD-MS analysis.

Synthesis Example 14 (Synthesis of Intermediate 14)

In addition to using 3-bromoiodobenzene instead of intermediate 2, and using 2-naphthalene boronic acid

The same reaction as in Synthesis Example 5 was carried out, except for phenylboronic acid, to obtain 21.5 g of a white powder. The white powder was identified as intermediate 14 by FD-MS analysis.

The structural formula of the intermediates Am1 to Am16 is as follows.

[化43]

Synthesis Example 15 (Synthesis of Intermediate Aml)

Under the argon gas flow, 30.7 g of 4-bromo-p-triphenyl, 9.1 g of aniline, 13.0 g of sodium t-butoxide (manufactured by Hiroshima Kasei Co., Ltd.), and tris(dibenzylideneacetone) dipalladium (0) 460 mg ( The product was manufactured by Aldrich Co., Ltd., 210 mg of tris(t-butyl)phosphine and 500 mL of dehydrated toluene, and reacted at 80 ° C for 8 hours.

After cooling, 2.5 L of water was added, and the mixture was filtered with celite, and the filtrate was extracted with toluene and dried over anhydrous magnesium sulfate. The dried product was concentrated under reduced pressure, and the obtained crude product was purified by column column, and recrystallized with toluene, and crystals were obtained by filtration and then dried to obtain a pale yellow powder (15.7 g). The pale yellow powder was identified as the intermediate Aml by FD-MS analysis.

Synthesis Example 16 (Synthesis of Intermediate Am2)

The same reaction as in Synthesis Example 15 was carried out except that Intermediate 4 was used instead of 4-bromo-p-triphenylbenzene to obtain 16.3 g of a white powder. The white powder was identified as the intermediate Am2 by FD-MS analysis.

Synthesis Example 17 (Synthesis of Intermediate Am3)

The same reaction as in Synthesis Example 15 was carried out except that Intermediate 5 was used instead of 4-bromo-p-triphenylbenzene to obtain 18.1 g of a white powder. The white powder was identified as the intermediate Am3 by FD-MS analysis.

Synthesis Example 18 (Synthesis of Intermediate Am4)

The same reaction as in Synthesis Example 15 was carried out except that Intermediate 6 was used instead of 4-bromo-p-triphenylbenzene to obtain 15.9 g of a white powder. The white powder was identified as the intermediate Am4 by FD-MS analysis.

Synthesis Example 19 (Synthesis of Intermediate Am5)

The same reaction as in Synthesis Example 15 was carried out except that 1-bromonaphthalene was used instead of 4-bromo-p-triphenyl, and 4-amino-para-triphenyl was used instead of aniline to obtain 22.4 g of a white powder. The white powder was identified as the intermediate Am5 by FD-MS analysis.

Synthesis Example 20 (Synthesis of Intermediate Am6)

The same reaction as in Synthesis Example 15 was carried out except that Intermediate 7 was used instead of 4-bromo-p-triphenylbenzene to obtain 20.8 g of a white powder. The white powder was identified as the intermediate Am6 by FD-MS analysis.

Synthesis Example 21 (Synthesis of Intermediate Am7)

The same reaction as in Synthesis Example 15 was carried out except that Intermediate 4 was used instead of 4-bromo-p-triphenylbenzene to obtain 22.5 g of a white powder. The white powder was identified as the intermediate Am7 by FD-MS analysis.

Synthesis Example 22 (Synthesis of Intermediate Am8)

The same reaction as in Synthesis Example 15 was carried out except that the intermediate 9 was used instead of 4-bromo-p-triphenylbenzene to obtain 17.4 g of a white powder. The white powder was identified as the intermediate Am8 by FD-MS analysis.

Synthesis Example 23 (Synthesis of Intermediate Am9)

32.7g (100mmol) of bis(4-bromophenyl)amine, 41.6g (210mmol) of 2-biphenylboronic acid, 1.15g (1.00mmol) of tetrakis(triphenylphosphine)palladium (0) under argon atmosphere Into the mixture, 750 mL of toluene and 300 mL of a 2 M sodium carbonate aqueous solution were added, and the mixture was heated under reflux for 15 hours.

Immediately after the completion of the reaction, the mixture was filtered, and then the aqueous layer was removed. The organic layer was dried over sodium sulfate and concentrated. The residue was purified by a silica gel column chromatography to give 30.3 g of a glassy solid. The white powder was identified as the intermediate Am9 by FD-MS analysis.

Synthesis Example 24 (Synthesis of Intermediate Am10)

The same reaction as in Synthesis Example 15 was carried out except that the intermediate 10 was used instead of 4-bromo-p-triphenylbenzene to obtain 13.2 g of a white powder. The white powder was identified as the intermediate Am10 by FD-MS analysis.

Synthesis Example 25 (Synthesis of Intermediate Am11)

The same reaction as in Synthesis Example 15 was carried out except that the intermediate 11 was used instead of 4-bromo-p-triphenylbenzene to obtain 14.8 g of a white powder. The white powder was identified as the intermediate Am11 by FD-MS analysis.

Synthesis Example 26 (Synthesis of Intermediate Am12)

The same reaction as in Synthesis Example 15 was carried out except that the intermediate 10 was used instead of 4-bromo-p-triphenyl, and 4-amino-para-triphenyl was used instead of aniline to obtain 22.5 g of a white powder. The white powder was identified as the intermediate Am12 by FD-MS analysis.

Synthesis Example 27 (Synthesis of Intermediate Am13)

The same reaction as in Synthesis Example 15 was carried out except that the intermediate 12 was used instead of 4-bromo-p-triphenylbenzene to obtain 11.6 g of a white powder. The white powder was identified as the intermediate Am13 by FD-MS analysis.

Synthesis Example 28 (Synthesis of Intermediate Am14)

The same reaction as in Synthesis Example 15 was carried out except that the intermediate 12 was used instead of 4-bromo-p-triphenyl, and 4-amino-para-triphenyl was used instead of aniline to obtain 20.9 g of a white powder. The white powder was identified as the intermediate Am14 by FD-MS analysis.

Synthesis Example 29 (Synthesis of Intermediate Am15)

The same reaction as in Synthesis Example 15 was carried out except that the intermediate 13 was used instead of 4-bromo-p-triphenylbenzene to obtain 14.3 g of a white powder. The white powder was identified as the intermediate Am15 by FD-MS analysis.

Synthesis Example 30 (Synthesis of Intermediate Am16)

The same reaction as in Synthesis Example 15 was carried out except that the intermediate 14 was used instead of 4-bromo-p-triphenylbenzene to obtain 10.4 g of a white powder. The white powder was identified as the intermediate Am16 by FD-MS analysis.

The structural formulas of the compounds H1 to H16 which are the aromatic amine derivatives of the present invention produced in Synthesis Examples 1 to 16 are as follows.

Compounds H1 to H8:

[化44]

Compound H9～H16:

Synthesis Example 1 (Synthesis of Compound H1)

Under argon gas flow, 8.0 g of intermediate 3, 6.4 g of intermediate Am1, sodium tributoxide sodium 2.6 g (manufactured by Hiroshima Kasei Co., Ltd.), tris(dibenzylideneacetone) dipalladium (0) 92 mg were added (Aldrich Co., Ltd.) Manufactured, 42 mg of tris(t-butyl)phosphine and 100 mL of dehydrated toluene were reacted at 80 ° C for 8 hours.

After cooling, 500 mL of water was added, and the mixture was filtered with celite, and the filtrate was extracted with toluene and dried over anhydrous magnesium sulfate. The dried product was concentrated under reduced pressure, and the obtained crude product was purified by column column, and then recrystallized with toluene, and crystals were removed by filtration and dried to give 7.1 g of pale yellow powder. The pale yellow powder was identified as compound H1 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa), and as a result, after sublimation purification, no impurity peak was observed in high performance liquid chromatography (HPLC) analysis. Peak) high purity compound H1.

Synthesis Example 2 (Synthesis of Compound H2)

The same reaction as in Synthesis Example 1 was carried out except that the intermediate Am2 was used instead of the intermediate Am1 to obtain 6.6 g of a pale yellow powder. The pale yellow powder was identified as compound H2 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa), and as a result, after sublimation purification, a high-purity compound H2 which was not confirmed to have an impurity peak in the HPLC analysis was obtained.

Synthesis Example 3 (Synthesis of Compound H3)

The same reaction as in Synthesis Example 1 was carried out except that the intermediate Am3 was used instead of the intermediate Am1 to obtain 7.31 g of a pale yellow powder. The pale yellow powder was identified as compound H3 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa), and as a result, after sublimation purification, a high-purity compound H3 in which an impurity peak was not observed in the HPLC analysis was obtained.

Synthesis Example 4 (Synthesis of Compound H4)

The same reaction as in Synthesis Example 1 was carried out except that the intermediate Am4 was used instead of the intermediate Am1 to obtain 7.9 g of a pale yellow powder. The pale yellow powder was identified as compound H4 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa), and as a result, after sublimation purification, a high-purity compound H4 which was not confirmed to have an impurity peak in the HPLC analysis was obtained.

Synthesis Example 5 (Synthesis of Compound H5)

The same reaction as in Synthesis Example 1 was carried out except that the intermediate Am5 was used instead of the intermediate Am1 to obtain 8.3 g of a pale yellow powder. The pale yellow powder was identified as compound H5 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa), and as a result, after sublimation purification, a high-purity compound H5 which was not confirmed to have an impurity peak in the HPLC analysis was obtained.

Synthesis Example 6 (Synthesis of Compound H6)

The same reaction as in Synthesis Example 1 was carried out except that the intermediate Am6 was used instead of the intermediate Am1 to obtain 7.9 g of a pale yellow powder. The pale yellow powder was identified as compound H6 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa), and as a result, after sublimation purification, a high-purity compound H6 which was not confirmed to have an impurity peak in the HPLC analysis was obtained.

Synthesis Example 7 (Synthesis of Compound H7)

The same reaction as in Synthesis Example 1 was carried out except that the intermediate Am7 was used instead of the intermediate Am1 to obtain 6.5 g of a pale yellow powder. The pale yellow powder was identified as compound H7 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa), and as a result, after sublimation purification, a high-purity compound H7 which was not confirmed to have an impurity peak in the HPLC analysis was obtained.

Synthesis Example 8 (Synthesis of Compound H8)

The same reaction as in Synthesis Example 1 was carried out except that the intermediate Am8 was used instead of the intermediate Am1 to obtain 6.2 g of a pale yellow powder. The pale yellow powder was identified as compound H8 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa), and as a result, after sublimation purification, a high-purity compound H8 in which an impurity peak was not observed in the HPLC analysis was obtained.

Synthesis Example 9 (Synthesis of Compound H9)

The same reaction as in Synthesis Example 1 was carried out except that the intermediate Am9 was used instead of the intermediate Am1 to obtain 5.9 g of a pale yellow powder. The pale yellow powder was identified as compound H9 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa), and as a result, after sublimation purification, a high-purity compound H9 which was not confirmed to have an impurity peak in the HPLC analysis was obtained.

Synthesis Example 10 (Synthesis of Compound H10)

The same reaction as in Synthesis Example 1 was carried out except that the intermediate Am10 was used instead of the intermediate Am1 to obtain 4.6 g of a pale yellow powder. The pale yellow powder was identified as compound H10 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa), and as a result, after sublimation purification, a high-purity compound H10 in which an impurity peak was not observed in the HPLC analysis was obtained.

Synthesis Example 11 (Synthesis of Compound H11)

The same reaction as in Synthesis Example 1 was carried out except that the intermediate Am11 was used instead of the intermediate Am1 to obtain 5.4 g of a pale yellow powder. The pale yellow powder was identified as compound H11 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa), and as a result, after sublimation purification, a high-purity compound H11 in which an impurity peak was not observed in the HPLC analysis was obtained.

Synthesis Example 12 (Synthesis of Compound H12)

The same reaction as in Synthesis Example 1 was carried out except that the intermediate Am12 was used instead of the intermediate Am1 to obtain 6.7 g of a pale yellow powder. The pale yellow powder was identified as compound H12 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa). As a result, after sublimation purification, a high-purity compound H12 which was not confirmed to have an impurity peak in the HPLC analysis was obtained.

Synthesis Example 13 (Synthesis of Compound H13)

The same reaction as in Synthesis Example 1 was carried out except that the intermediate Am13 was used instead of the intermediate Am1 to obtain 4.8 g of a pale yellow powder. The pale yellow powder was identified as compound H13 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa), and as a result, after sublimation purification, a high-purity compound H13 in which an impurity peak was not observed in the HPLC analysis was obtained.

Synthesis Example 14 (Synthesis of Compound H14)

The same reaction as in Synthesis Example 1 was carried out except that the intermediate Am14 was used instead of the intermediate Am1 to obtain 6.2 g of a pale yellow powder. The pale yellow powder was identified as compound H14 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa), and as a result, after sublimation purification, a high-purity compound H14 which was not confirmed to have an impurity peak in the HPLC analysis was obtained.

Synthesis Example 15 (Synthesis of Compound H15)

The same reaction as in Synthesis Example 1 was carried out except that the intermediate Am15 was used instead of the intermediate Am1 to obtain 5.8 g of a pale yellow powder. The pale yellow powder was identified as compound H15 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa), and as a result, after sublimation purification, a high-purity compound H15 which was not confirmed to have an impurity peak in the HPLC analysis was obtained.

Synthesis Example 16 (Synthesis of Compound H16)

The same reaction as in Synthesis Example 1 was carried out except that the intermediate Am16 was used instead of the intermediate Am1 to obtain a pale yellow powder (4.2 g). The pale yellow powder was identified as compound H16 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa). As a result, after sublimation purification, a high-purity compound H16 which was not confirmed to have an impurity peak in the HPLC analysis was obtained.

Synthesis Comparative Example 1 (comparison of Comparative Compound 4)

The same reaction as in Synthesis Example 1 was carried out except that N,N-diphenylamine was used instead of the intermediate Am1 to obtain 3.6 g of a pale yellow powder. The pale yellow powder was identified as Comparative Compound 4 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa), and as a result, the high-purity comparative compound 4 in which the impurity peak was completely removed could not be obtained by one sublimation purification.

Synthesis Comparative Example 2 (comparison of Comparative Compound 5)

The same reaction as in Synthesis Example 1 was carried out except that N-(4-methoxyphenyl)-N-phenylamine was used instead of the intermediate Aml to obtain 3.6 g of a pale yellow powder. The pale yellow powder was identified as Comparative Compound 5 by FD-MS analysis. Then, the compound was subjected to sublimation purification under vacuum (2 × 10 ^-4 Pa), and as a result, the high-purity comparative compound 5 in which the impurity peak was completely removed could not be obtained by one sublimation purification.

Example 1 (Manufacturing of Organic EL Element)

A 25 mm × 75 mm × 1.1 mm thick glass substrate (manufactured by Geomatic Co., Ltd.) with an ITO transparent electrode was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then ultraviolet (ultraviolet) cleaning was performed for 30 minutes.

The cleaned glass substrate with the transparent electrode wire was attached to a substrate holder of the vacuum evaporation apparatus. Next, the following compound H232 was vapor-deposited on the surface on the side where the transparent electrode line was formed so as to cover the transparent electrode, and a H232 film having a film thickness of 60 nm was formed as a hole injection layer.

On the H232 film, the above compound H1 (Synthesis Example 1) was vapor-deposited to form a hole transport layer having a film thickness of 20 nm. Then, the following compound EM1 was vapor-deposited to form a light-emitting layer having a film thickness of 40 nm. At the same time, the following styrene-based amine compound D1 as a luminescent molecule was vapor-deposited so that the weight ratio of EM1 to D1 was 40:2.

The following A1q was formed into a film having a film thickness of 10 nm on the film. This layer functions as an electron injecting layer. Thereafter, Li (a source of Li: manufactured by Saes Getter Co., Ltd.) as a reducing dopant material was subjected to binary vapor deposition with Alq to form an Alq:Li film (film thickness: 10 nm) as an electron injection layer (cathode). Metal Al was vapor-deposited on the Alq:Li film to form a metal cathode, whereby an organic EL element was formed.

Then, the obtained organic EL device was stored at 105 ° C for 8 hours, and then the luminous efficiency was measured, and the luminescent color was observed. The luminance was measured using a CS1000 manufactured by Minolta, and the luminous efficiency at 10 mA/cm ² was calculated. Further, the half life of the light emission at the initial luminance of 5000 cd/m ² , room temperature, and direct-current (DC) constant current driving was measured, and the results are shown in Table 1.

Example 2 to Example 4 (manufacture of organic EL device)

An organic EL device was produced in the same manner as in Example 1 except that the compound H2, the compound H3, and the compound H5 described above were used as the hole transporting material instead of the compound H1.

In the same manner as in Example 1, the obtained organic EL device was stored at 105 ° C for 8 hours, and then the luminous efficiency was measured, and the luminescent color was observed, and the initial luminance was measured at 5000 cd/m ² , room temperature, and DC constant current driving. The half life of the product is shown in Table 1.

Example 5 (Manufacturing of Organic EL Element)

An organic EL device was fabricated in the same manner as in Example 2 except that the following arylamine compound D2 was used instead of the amine compound D1 having a styryl group. Me is a methyl group.

Further, in the same manner as in Example 1, the obtained organic EL device was stored at 105 ° C for 8 hours, and then the luminous efficiency was measured, and the luminescent color was observed, and the initial luminance was measured at 5000 cd/m ² , room temperature, and DC constant current driving. The half life of the luminescence is shown in Table 1.

Comparative Example 1 to Comparative Example 5 (manufacture of organic EL device)

An organic EL device was produced in the same manner as in Example 1 except that Comparative Compound 1 to Comparative Compound 5 were used instead of Compound H1 as a hole transporting material.

Further, in the same manner as in Example 1, the obtained organic EL device was stored at 105 ° C for 8 hours, and then the luminous efficiency was measured, and the luminescent color was observed, and the initial luminance was measured at 5000 cd/m ² , room temperature, and DC constant current driving. The half life of the luminescence is shown in Table 1.

[48]

Comparative Example 6 (manufacture of organic EL device)

An organic EL device was fabricated in the same manner as in Example 5 except that the above Comparative Compound 4 was used instead of the compound H1 as a hole transporting material.

Further, in the same manner as in Example 1, the obtained organic EL device was stored at 105 ° C for 8 hours, and then the luminous efficiency was measured, and the luminescent color was observed, and the initial luminance was measured at 5000 cd/m ² , room temperature, and DC constant current driving. The half life of the luminescence is shown in Table 1.

Example 6 (Manufacturing of Organic EL Element)

An organic EL device was fabricated in the same manner as in Example 1 except that the following charge acceptor compound was formed into a film of 10 nm between the anode and H232, and the film thickness of H232 was changed to 50 nm.

Further, in the same manner as in Example 1, the obtained organic EL device was stored at 105 ° C for 8 hours, and then the luminous efficiency was measured to observe the luminescent color. Further, the half life of the light emission at the initial luminance of 5000 cd/m ² , room temperature, and DC constant current driving was measured. As a result, the luminous efficiency was 5.4 cd/A, the luminescent color was blue, and the half life was 410 hours.

Comparative Example 7 (manufacture of organic EL device)

An organic EL device was fabricated in the same manner as in Example 6 except that the above Comparative Compound 4 was used instead of the compound H1 as a hole transporting material.

Further, in the same manner as in Example 1, the obtained organic EL device was stored at 105 ° C for 8 hours, and then the luminous efficiency was measured to observe the luminescent color. Further, the half life of the light emission at the initial luminance of 5000 cd/m ² , room temperature, and DC constant current driving was measured. As a result, the luminous efficiency was 3.5 cd/A, the luminescent color was blue, and the half life was 110 hours.

[Industrial availability]

The aromatic amine derivative of the present invention can realize an organic EL device which has high luminous efficiency and long life even after storage at a high temperature.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

Claims (15)

An aromatic amine derivative represented by the following formula (1): In the formula (1), R ₁ and R _{2 each} represent a linear or branched alkyl group composed of a hydrocarbon having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a carbon number of 1 to 2. Alkoxy group of 10, trialkylsulfanyl group having a carbon number of 3 to 10, triarylsulfanyl group having a carbon number of 18 to 30, alkylarylalkylalkyl group having a carbon number of 8 to 15, or a nuclear carbon number of 6 to 14 aryl groups, a and b are independently 0 to 4, and adjacent R ₁ and R ₂ may be bonded to form a saturated or unsaturated ring, and R ₃ and R _{4 are} represented by a carbon number of 1~ a straight or branched alkyl group composed of 6 hydrocarbons, a cycloalkyl group having 5 to 7 carbon atoms, or an aryl group having a core number of 6 to 10, and c and d are independently 0 to 3, adjacent to each other. A plurality of R ₃ and R ₄ may be bonded to form a saturated or unsaturated ring (wherein R ₃ and R _{4 are} not bonded to each other to form a ring), and R′ and R′′ represent a hydrocarbon having 1 to 12 carbon atoms; a linear or branched alkyl group or a cycloalkyl group having a carbon number of 3 to 10, Ar ₁ represented by the following formula (2), Ar ₂ represented by the following formula (3), and Ar ₁ and Ar ₂ mutually different groups] [In the formulae (2) and (3), Ar ₃ to Ar ₆ are each independently an arylene group having a core carbon number of 6 to 14, and R ₅ to R ₈ represent a hydrogen atom and a hydrocarbon having a carbon number of 1 to 10; a linear, branched or cyclic alkyl group, an alkoxy group having 1 to 10 carbon atoms, a trialkylsulfanyl group having 3 to 10 carbon atoms, a triarylalkylene group having a carbon number of 18 to 30, An alkylaryl decyl group having a carbon number of 8 to 15, an aryl group having a nucleus number of 6 to 14 or a biphenyl group, and e and f are independently 1 to 4, and g and h are independently 1 to 5, respectively. When e~h is greater than or equal to 2, a plurality of R ₅ to R ₈ are respectively the same or different, and a plurality of R ₅ to R ₈ may be bonded to form a saturated ring (wherein R _{8 is} not a nuclear carbon number of 6) Aryl), in the general formula (2), (Ar ₅ ) may be present or absent, and when (Ar ₅ ) is absent, (Ar ₄ ) is not an arylene group having a nucleus number of 6]. The aromatic amine derivative according to claim 1, wherein in the above formula (1), Ar _{1 is} represented by the following formula (4), and Ar ₂ is represented by the following formula (5): [In the formulas (4) and (5), the definitions of R ₅ to R ₈ and e to h are the same as those of the above formula (2) and the above formula (3)]. The aromatic amine derivative according to claim 1, wherein in the above formula (1), Ar _{1 is} represented by the following formula (6) or (7), and Ar ₂ is represented by the formula (5) Indicates: In the formulae (5) to (7), the definitions of R ₅ to R ₈ and e to h are the same as those of the above formula (2) and the above formula (3). The aromatic amine derivative according to claim 1, wherein R ₈ of the above formula (3) is a hydrogen atom. The aromatic amine derivative according to claim 3, wherein R ₈ of the above formula (5) is a hydrogen atom. The aromatic amine derivative according to claim 3, wherein R ₈ of the above formula (5) is a hydrogen atom, and R ₅ to R ₇ of the above formula (6) or the above formula (7) are A hydrogen atom. The aromatic amine derivative according to any one of claims 1 to 6, which is a material for an organic electroluminescence device. The aromatic amine derivative according to any one of claims 1 to 6, which is a hole transport material for an organic electroluminescence device. An organic electroluminescence device having an organic thin film layer containing one or more layers containing at least a light-emitting layer between a cathode and an anode of the organic electroluminescence device; and at least one layer of the organic thin film layer containing The aromatic amine derivative according to any one of the first to sixth aspects of the invention, as a component of a single or a mixture. An organic electroluminescence device having an organic thin film layer containing one or more layers containing at least a light-emitting layer between a cathode and an anode of the organic electroluminescence device; and the organic thin film layer having a hole transport layer The hole transport layer contains the aromatic amine derivative as described in any one of claims 1 to 6 as a component of a single or a mixture. An organic electroluminescence device having between one or more of a cathode and an anode of the organic electroluminescence device and comprising at least a light-emitting layer An organic thin film layer of the layer; and the organic thin film layer has a multi-layered hole transport layer, wherein a hole transport layer of the plurality of hole transport layers directly contacting the light-emitting layer contains the first to sixth items as claimed in the patent scope The aromatic amine derivative according to any one of them is a component of a single or a mixture. An organic electroluminescence device having an organic thin film layer containing one or more layers containing at least a light-emitting layer between a cathode and an anode of the organic electroluminescence device; and the organic thin film layer having a hole injection layer The hole injection layer contains the aromatic amine derivative as described in any one of claims 1 to 6. The organic electroluminescence device according to any one of claims 10 to 12, wherein the light-emitting layer contains a styrylamine compound and/or an arylamine compound. The organic electroluminescent device according to any one of claims 10 to 12, wherein the organic thin film layer has a multilayer hole injection layer or a hole transport layer, and the multilayer hole injection layer or electricity At least one of the hole transport layers contains a charge acceptor material. The organic electroluminescence device according to any one of claims 10 to 12, which emits blue light.