JPH0649079A - SILANAMINE DERIVATIVE, PRODUCTION METHOD THEREOF, AND EL DEVICE USING THE SILANAMINE DERIVATIVE - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] To provide a silanamin derivative having a low ionization potential, which is easy to purify, slow in recrystallization during thin film formation, a method for producing the same, and a novel organic EL device capable of being driven at a low voltage. provide. [Structure] Formula (I) obtained by reacting diarylamine with halogenated silane (Ar ¹ is a C 1-6 alkyl group, a C 1-6 alkoxy group, a (alkyl-substituted) phenoxy group or a (vinyl group-substituted) aryl group having 6 to 20 nuclear carbon atoms, and Ar ² is
(i) (C1-6 alkyl group substituted) is an arylene group having 6 to 20 nuclear carbon atoms, and Ar ³ is (i) (aryl group having 6 to 12 carbon atoms substituted) is an aryl group. Silanamine derivative. Also provided is a compound layer having a single-layer structure or a multi-layer structure including an organic light-emitting layer, and a pair of electrodes sandwiching the compound layer, and at least one of the compound layers contains a silanamin derivative of the formula (I). Organic EL device.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silanamin derivative, and more particularly to a silanamin derivative which can be used as a material for an organic EL device, an electrophotographic photoreceptor or the like, and a method for producing the same. The present invention also relates to an organic EL device using the silanamin derivative.

[0002]

2. Description of the Related Art N, N'-di-trimethylsilyluric acid,
Silanamine derivatives represented by N-trimethylsilylimidazole, trimethylsilyldiethylamine and the like are S
It is a compound having an i-N bond and has been conventionally used as a silylation reagent. Also, US Pat.
No. 50 discloses cyclodisilazanes that can be used as a material for a hole transport layer that constitutes an organic EL device.

By the way, as another compound preferable as a material for the hole transport layer, aromatic tertiary amines (including monoamines, diamines and triamines, hereinafter sometimes referred to as amine-based materials) are known (hereinafter, referred to as amine-based materials). See, for example, JP-A-63-295695). The ionization potential of this amine-based material is generally lower than the ionization potential of the above cyclodisilazanes. For example, one of the diamine-based materials, TPD [N, N'-bis- (m-
Trily) -N, N'diphenyl-1,1'-biphenyl] has an ionization potential of about 5.5 eV,
The ionization potential of hexaphenylcyclodisilazane, which is one of the cyclodisilazanes, is about 5.7 eV, and the former is lower than the latter.

Since the driving voltage of the organic EL element can be lowered when the ionization potential of the hole transport layer is small, the material of the hole transport layer of the organic EL element is the above amine-based material rather than the above cyclodisilazanes. Is preferred. The characteristic that the ionization potential is small is a characteristic required also for the charge transport material of the electrophotographic photoreceptor.

[0005]

However, in the case of amine-based materials, for example, in the case of 4,4'-di-t-butyl-triphenylamine, it is difficult to purify after synthesis, and, for example, in TPD. In this case, there is a problem that when the film is thinned, recrystallization is caused with time and the device life is deteriorated.

Therefore, a first object of the present invention is to provide a silanamin derivative which is easy to purify after synthesis, is slow in recrystallization when formed into a thin film, and has a low ionization potential, and a method for producing the same. It is in. The second object of the present invention is to provide a novel organic E that can be driven at a low voltage.
It is to provide an L element.

[0007]

The silanamine derivative of the present invention which achieves the first object is a compound represented by the general formula (I):

[Chemical 3] (In the formula, Ar ¹ is (i) an aryl group having 6 to 20 carbon atoms, or (ii) an alkyl group having 1 to 6 carbon atoms;
6-20 nuclear carbon atoms substituted with an alkoxy group, a phenoxy group, an alkyl-substituted phenoxy group or a vinyl group
Ar ² is an arylene group having (i) an arylene group having 6 to 20 carbon atoms, or (ii) an arylene group having 6 to 20 carbon atoms substituted with an alkyl group having 1 to 6 carbon atoms. And Ar ³ is (i) an aryl group having 6 to 12 carbon atoms, or (ii) an aryl group having 6 to 12 nuclear carbon atoms substituted with an alkyl group having 1 to 3 carbon atoms). It is what is done.

Further, the method for producing this silanamin derivative is represented by the general formula (II)

[Chemical 4] (In the formula, Ar ¹ is (i) an aryl group having 6 to 20 carbon atoms, or (ii) an alkyl group having 1 to 6 carbon atoms;
6-20 nuclear carbon atoms substituted with an alkoxy group, a phenoxy group, an alkyl-substituted phenoxy group or a vinyl group
Ar ² is an arylene group having (i) an arylene group having 6 to 20 carbon atoms, or (ii) an arylene group having 6 to 20 carbon atoms substituted with an alkyl group having 1 to 6 carbon atoms. And a general formula (III) (Ar ³ ) ₃ SiX (III) (wherein Ar ³ is (i) an aryl group having 6 to 12 carbon atoms, or (ii) It is an aryl group having 6 to 12 nuclear carbon atoms substituted with an alkyl group having 1 to 3 carbon atoms, and X is a halogen atom). .

The organic EL device of the present invention that achieves the second object described above includes a compound layer having a single-layer structure or a multi-layer structure including at least an organic light emitting layer, and a pair of electrodes sandwiching the compound layer. And at least one of the compound layers contains the above-mentioned silanamin derivative of the present invention.

The present invention will be described in detail below. First, the silanamin derivative of the present invention will be described. This silanamin derivative has the general formula (I) as described above.

[Chemical 5] It is represented by.

Here, Ar ¹ is (i) an aryl group having 6 to 20 carbon atoms, or (ii) an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenoxy group, an alkyl group. It is an aryl group having 6 to 20 nuclear carbon atoms substituted with a substituted phenoxy group or a vinyl group. Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl group, biphenyl group, naphthyl group, anthranyl group, phenanthryl group,
Examples thereof include a pyrenyl group. In addition, specific examples of the alkyl group having 1 to 6 carbon atoms which may be substituted on the aryl group include:
Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-
A butyl group, an n-pentyl group, an n-hexyl group and the like can be mentioned. Specific examples of the alkoxy group having 1 to 6 carbon atoms which can be substituted with the aryl group having 6 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and a hexanoxy group. Further, specific examples of the alkyl-substituted phenoxy group include the phenoxy group substituted with the above-exemplified alkyl group having 1 to 6 carbon atoms.

Ar ² in the above general formula (I) is
(i) an arylene group having 6 to 20 carbon atoms, or (i
i) Nucleus having 6 to 6 carbon atoms substituted with an alkyl group having 1 to 6 carbon atoms
20 arylene groups. Specific examples of the arylene group having 6 to 20 carbon atoms (arylene group having 6 to 20 carbon atoms) include phenylene group, biphenylene group, naphthylene group,
Examples thereof include anthranylene group, phenanthrylene group, and pyrenylene group. In addition, specific examples of the alkyl group having 1 to 6 carbon atoms which can be substituted on the arylene group include the same alkyl groups as those mentioned in the description of Ar ¹ .

Ar ³ in the above general formula (I)
Is (i) an aryl group having 6 to 12 carbon atoms, or (i
i) 6 to 6 nuclear carbon atoms substituted with an alkyl group having 1 to 3 carbon atoms
12 aryl groups. Specific examples of the aryl group having 6 to 12 carbon atoms include phenyl group, biphenyl group, naphthyl group, anthranyl group, phenanthryl group and pyrenyl group. Further, specific examples of the alkyl group having 1 to 3 carbon atoms which may be substituted on the aryl group include a methyl group,
Examples include an ethyl group, an n-propyl group and an i-propyl group. Specific examples of the silanamin derivative of the present invention represented by the above general formula (I) are shown in FIGS.

The silanamine derivative of the present invention is different from the conventional silazane derivative in that it has an ionization potential of, for example, 5.6 eV or less. Further, the silanamin derivative of the present invention can be easily formed into a thin film by a known vacuum deposition method. Furthermore, it is possible to easily form a thin film by a casting method, a coating method, a spin coating method, or the like using a solution in which the silanamin derivative of the present invention is dispersed in a polymer such as polycarbonate, polyurethane, polystyrene, polyarylate, or polyester. it can.
These thin films have an electron function of transporting holes and are characterized in that recrystallization with time is slower than that of a conventional amine-based material (for example, TPD) thin film.

The silanamin derivative of the present invention having the above characteristics can be applied to a hole transport layer, a hole transport binder, or a light emitting layer of an organic EL device, and can also be used for an electrophotographic photoreceptor. It can also be applied to a hole transport layer and the like.
When applied to an organic EL element, the ionization potential is as low as 5.6 eV or less, for example, and thus the applied voltage is reduced. In addition, when applied to an electrophotographic photoreceptor, it brings about good hole injection from the charge generation layer. In addition, it can be used as an organic nonlinear material, a fluorescent material, a binder for firing ceramics, and the like.

The silanamine derivative of the present invention can be efficiently synthesized, for example, by the following method of the present invention.
Then, the reaction product can be easily purified. As described above, the method for producing the silanamin derivative of the present invention has the general formula (II)

[Chemical 6] And a halogenated silane represented by the general formula (III) (Ar ³ ) ₃ SiX (III) are reacted with each other.

Here, Ar ¹ and A in the general formula (II)
r ² and Ar ³ in the general formula (III) are Ar in the general formula (I), which represents the silanamin derivative of the present invention.
^{The same as 1} , ¹ , Ar ² and Ar ³ . In addition, the general formula (III)
X in is a halogen atom, and specific examples thereof include fluorine, chlorine, bromine, and iodine. General formula (II)
Specific examples of the diarylamine represented by are shown in FIGS. A specific example of the halogenated silane represented by the general formula (III) is shown in FIG.

The reaction between the diarylamine represented by the general formula (II) and the halogenated silane represented by the general formula (III) can be carried out, for example, as follows. First, the diarylamine represented by the general formula (II) is placed in a reaction vessel which has been replaced with an inert gas such as argon gas, and a solvent is added and dissolved. As the solvent at this time, diethyl ether, THF (tetrahydrofuran), dioxane, toluene, dimethoxyethane or the like can be used. Preferred solvents include THF, especially THF distilled from sodium lines under a stream of argon.

Then 2 to 4 equivalents of base are added to this solution. Examples of the base include sodium alkoxide, sodium hydride, potassium t-butoxide, n-butyllithium, DBU (1,8-diazabicyclo [5.4.
0. ] Strong bases such as undec-7-ene) are preferred. A particularly preferred base is n-butyllithium. The preferable addition amount of the base is about 2.5 equivalents. After adding the base, the mixture is heated at about 30 to 120 ° C. for about 0.5 to 3 hours. A desirable heating time is about 0.5 hour, and it is preferable to heat at about 50 ° C.

Next, 2 to 4 equivalents of the halogenated silane represented by the general formula (III) is dissolved in a solvent and added dropwise to the reaction solution. As the solvent at this time, diethyl ether,
Although THF, dioxane, toluene, dimethoxyethane or the like can be used, it is preferable to use the same solvent as that used for dissolving the diarylamine. The amount of halogenated silane dropped is preferably about 2.5 equivalents. The reaction temperature can be appropriately selected within a range of -78 ° C to 120 ° C, but sufficiently good results can be obtained even at room temperature. The reaction time can be appropriately selected within the range of 8 to 48 hours, but a sufficiently good result can be obtained in about 18 hours.
As described above, the silanamin derivative of the present invention can be produced by reacting the diarylamine represented by the general formula (II) with the halogenated silane represented by the general formula (III).

The silanamin derivative of the present invention thus produced can be easily purified as follows, for example. First, water is added to the reaction solution to terminate the reaction, and then extraction is performed with a solvent. At this time, toluene, methylene chloride, ethyl acetate or the like can be used as the extraction solvent, and methylene chloride is particularly preferable. After extraction, the extract is dried and the solvent is distilled off.

After that, the obtained residue is subjected to column chromatography to obtain the desired purified product. As a carrier for column chromatography, silica gel, alumina or the like can be used. Also,
As the developing solution, toluene, methylene chloride, chloroform or the like can be used. It should be noted that a substance that is difficult to extract with a solvent, that is, a substance that is hardly soluble in a solvent can be washed with heated pyridine to obtain a purified product.

Next, the organic EL device of the present invention will be described. The organic EL device of the present invention is, as described above, a compound layer having a single-layer structure or a multi-layer structure containing at least an organic light-emitting layer, and this compound layer. And a pair of electrodes for holding the compound, and at least one of the compound layers contains the above-mentioned silanamin derivative of the present invention.

The structure of the organic EL device is as follows: anode / organic light emitting layer / cathode, anode / hole transport layer / organic light emitting layer / cathode, anode / organic light emitting layer / electron injection layer / cathode, anode /
There is a hole transport layer / organic light emitting layer / electron injection layer / cathode, etc., but the organic EL device of the present invention is a compound layer sandwiched by a pair of electrodes (anode and cathode) (in the device having the above-mentioned constitution. Is an organic light emitting layer, a hole transport layer and an organic light emitting layer in the element having the above configuration, an organic light emitting layer and an electron injection layer in the element having the above configuration, a hole transport layer, an organic light emitting in the element having the above configuration Layer and electron injection layer)
As long as at least one layer of the above contains the above-mentioned silanamin derivative of the present invention, any of the above configurations may be adopted. In addition, it is preferable that all the organic EL elements having these configurations are supported by the substrate. There is no particular limitation on this substrate, and those commonly used in conventional organic EL devices, for example, those made of glass, transparent plastic, quartz or the like can be used.

The layer containing the silanamin derivative which is a characteristic part of the organic EL device of the present invention is preferably a hole transport layer or an organic light emitting layer, and particularly preferably a hole transport layer.

The hole-transporting layer containing the silanamine derivative may have a single-layer structure composed of only the silanamine derivative, or may be composed of a silanamine derivative layer and a layer of a substance conventionally used as a hole-transporting layer material for an organic EL device. It may have a multilayer structure. Further, it may have a single-layer structure or a multi-layer structure including a layer composed of a mixture of a silanamine derivative and a substance conventionally used as a hole transport layer material of an organic EL device. The hole-transporting layer containing a silanamin derivative can be formed by a vacuum vapor deposition method, a casting method, a coating method, a spin coating method or the like using the silanamin derivative and, if necessary, another hole-transporting layer material. . Further, it is also formed by a casting method using a solution in which a silanamin derivative is dispersed in a transparent polymer such as polycarbonate, polyurethane, polystyrene, polyarylate or polyester, a coating method or a spin coating method, and simultaneous vapor deposition with a transparent polymer. can do.

The organic light-emitting layer containing the silanamine derivative may have a single-layer structure composed of only the silanamine derivative, or may be composed of a silanamine derivative layer and a layer of a substance conventionally used as an organic light-emitting layer material of an organic EL device. It may have a multilayer structure. Furthermore, silanamin derivatives and organic E
It may have a single-layer structure or a multi-layer structure including a layer composed of a mixture with a substance that has been conventionally used as a material for an organic light emitting layer of an L element. The organic light-emitting layer containing the silanamin derivative can be formed by using the silanamin derivative and, if necessary, another organic light-emitting layer material by a vacuum deposition method, a casting method, a coating method, a spin coating method, or the like.

In the organic EL device of the present invention, the layers other than the layer containing the silanamin derivative can be formed by using the same material as the conventional organic EL device. For example, as the material of the anode, a metal having a large work function (4 eV or more),
Alloys, electrically conductive compounds or mixtures thereof are preferably used. As a specific example, a metal such as Au, CuI,
Dielectric transparent materials such as ITO, SnO ₂ and ZnO can be used. The anode can be manufactured by forming a thin film of the above material by a method such as a vapor deposition method or a sputtering method. When the light emitted from the organic light emitting layer is taken out from the anode, the transmittance of the anode is preferably higher than 10%. The sheet resistance of the anode is preferably several hundred Ω / □ or less. The thickness of the anode depends on the material, but is usually 10 nm to 1 μm, preferably 1
It is selected in the range of 0 to 200 nm.

Further, as the material of the cathode, a metal, an alloy, an electrically conductive compound having a small work function (4 eV or less), or a mixture thereof is preferably used. Specific examples include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, Al / Al ₂
Examples include O ₃ and indium. The cathode can be manufactured by forming a thin film of the above material by a method such as a vapor deposition method or a sputtering method. When the light emitted from the organic light emitting layer is taken out from the cathode, the transmittance of the cathode is preferably larger than 10%. The sheet resistance of the cathode is preferably several hundred Ω / □ or less. The thickness of the cathode depends on the material, but is usually 10
nm to 1 μm, preferably 50 to 200 nm. In order to efficiently extract the light emitted from the organic light emitting layer, it is preferable that at least one of the above-mentioned anode and the above-mentioned cathode is formed of a transparent or semitransparent substance.

Further, when the organic light emitting layer in the organic EL device of the present invention is formed of a silanamin derivative and another substance, or when formed only of a substance other than the silanamin derivative, an organic light emitting layer material other than the silanamin derivative is used. As, for example, polycyclic condensed aromatic compounds, fluorescent brightening agents such as benzoxazole-based, benzothiazole-based, benzimidazole-based compounds, metal chelated oxanoide compounds, and distyrylbenzene-based compounds, thin film forming properties It is possible to use a good compound.

Specific examples of the above polycyclic fused aromatic compound include condensed ring luminescent substances containing anthracene, naphthalene, phenanthrene, pyrene, chrysene, perylene skeleton, and 8 to 20, preferably 8 Other condensed ring luminescent substances containing a condensed ring may be mentioned.

Examples of the benzoxazole-based, benzothiazole-based, and benzimidazole-based fluorescent whitening agents include those disclosed in JP-A-59-194393. As a typical example,
2,5-bis (5,7-di-t-pentyl-2-benzoxazolyl) -1,3,4-thiadiazole, 4,
4'-bis (5,7-t-pentyl-2-benzoxazolyl) stilbene, 4,4'-bis (5,7-di-
(2-Methyl-2-butyl) -2-benzoxazolyl) stilbene, 2,5-bis (5,7-di-t-pentyl-2-benzoxazolyl) thiophene, 2,5-
Bis (5- (α, α-dimethylbenzyl) -2-benzoxazolyl) thiophene, 2,5-bis (5,7-di- (2-methyl-2-butyl) -2-benzoxazolyl ) -3,4-diphenylthiophene, 2,5-bis (5-methyl-2-benzoxazolyl) thiophene,
4,4'-bis (2-benzoxazolyl) biphenyl, 5-methyl-2- (2- (4- (5-methyl-2-
Benzoxazoles such as benzoxazolyl) phenyl) vinyl) benzoxazole and 2- (2- (4-chlorophenyl) vinyl) naphtho (1,2-d) oxazole, 2,2 ′-(p-phenylenedivinylene) ) -Bisbenzothiazole and other benzothiazoles, 2- (2-
(4- (2-benzimidazolyl) phenyl) vinyl)
Fluorescent brighteners such as benzimidazole compounds such as benzimidazole and 2- (2- (4-carboxyphenyl) vinyl) benzimidazole can be mentioned.

As the metal chelated oxanoide compound, for example, those disclosed in JP-A-63-295695 can be used. Typical examples thereof are tris (8-quinolinol) aluminum, bis (8-quinolinol) magnesium, bis (benzo (f) -8-quinolinol) zinc, bis (2-methyl-).
8-quinolinolate) aluminum oxide, tris (8-quinolinol) indium, tris (5-methyl-8-quinolinol) aluminum, 8-quinolinol lithium, tris (5-chloro-8-quinolinol) gallium, bis (5-chloro-). 8-quinolinol) calcium, poly (zinc (II) -bis (8-hydroxy-5-
Examples thereof include 8-hydroxyquinoline-based metal complexes such as quinolinonyl) methane) and dilithium epindridione.

Further, as the distyrylbenzene compound, for example, those disclosed in European Patent No. 0373582 can be used. As typical examples thereof, 1,4-bis (2-methylstyryl) benzene, 1,4-bis (3-methylstyryl) benzene,
1,4-bis (4-methylstyryl) benzene, distyrylbenzene, 1,4-bis (2-ethylstyryl) benzene, 1,4-bis (3-ethylstyryl) benzene, 1,4-bis (2 -Methylstyryl) -2-methylbenzene, 1,4-bis (2-methylstyryl) -2-
Examples include ethylbenzene and the like.

The distyrylpyrazine derivative disclosed in JP-A-2-252793 can also be used as a material for the organic light emitting layer. As a typical example,
2,5-bis (4-methylstyryl) pyrazine, 2,5
-Bis (4-ethylstyryl) pyrazine, 2,5-bis [2- (1-naphthyl) vinyl] pyrazine, 2,5-bis (4-methoxystyryl) pyrazine, 2,5-bis [2- (4 -Biphenyl) vinyl] pyrazine, 2,5-
Examples thereof include bis [2- (1-pyrenyl) vinyl] pyrazine.

In addition, the dimethylidene derivative disclosed in European Patent No. 0388768 or JP-A-3-231970 can be used as a material for the organic light emitting layer. Typical examples thereof are 1,4-phenylenedimethylidyne, 4,4'-phenylenedimethylidin,
2,5-xylylene dimethylidene, 2,6-naphthylene dimethylidene, 1,4-biphenylene dimethylidene, 1,4-p-terephenylene dimethylidene, 9,
10-anthracene diyl dimethylidin, 4,4'-
(2,2-di-t-butylphenylvinyl) biphenyl, 4,4 ′-(2,2-diphenylvinyl) biphenyl and the like, and derivatives thereof.

Furthermore, the coumarin derivative disclosed in Japanese Patent Application Laid-Open No. 2-191694, Japanese Patent Application Laid-Open No. 2-1968.
No. 85, a perylene derivative disclosed in Japanese Patent Application Laid-Open No. Hei 2
Naphthalene derivatives disclosed in JP-A-255789, JP-A-2-289676 and JP-A-2-886
The phthaloperinone derivative disclosed in JP-A No. 89, the styrylamine derivative disclosed in JP-A-2-250292, and the like can also be used as the material of the organic light emitting layer. The above-mentioned organic light emitting layer material can be appropriately selected according to the desired emission color, performance, and the like.

The organic light emitting layer in the organic EL device of the present invention may be formed by adding a fluorescent substance as disclosed in US Pat. No. 4,769,292. At this time, the base substance may be a silanamin derivative or an organic light emitting layer material other than the silanamin derivative. Further, it may be a mixture of a silanamine derivative and an organic light emitting layer material. When the organic light emitting layer is formed by adding the fluorescent substance, the addition amount of the fluorescent substance is preferably several mol% or less. Since the fluorescent substance emits light in response to the recombination of electrons and holes, it plays a part of the light emitting function.

As the organic light emitting layer material, a compound having no thin film property can be used. Specific examples include 1,4-diphenyl-1,3-butadiene, 1,
1,4,4-tetraphenyl-1,3-butadiene, tetraphenylcyclopentadiene and the like can be mentioned. However, the organic EL device using these materials having no thin film property has a shortcoming that the life of the device is short.

In the organic EL device of the present invention, the hole transport layer, which is provided if necessary, may be a layer containing a silanamin derivative or may be a layer containing a silanamine derivative as long as the organic light emitting layer contains the silanamin derivative. There may be no layer. As the hole transport layer material other than the silanamine derivative, various substances conventionally used as the hole transport layer material of the organic EL device can be used.

When a layer containing a silanamine derivative is provided as a hole transporting layer provided as necessary in the organic EL device of the present invention, this hole transporting layer is composed only of the silanamine derivative as described above. Single-layer structure, multi-layer structure of a silanamin derivative layer and a layer of a substance conventionally used as a hole transport layer material of an organic EL device, or a silanamin derivative and a hole transport layer material of an organic EL device conventionally used It may have either a single-layer structure or a multi-layer structure containing a layer composed of a mixture with the substance. The preferred layer structure in this case is a single layer structure consisting of only a silanamin derivative, or a layer of a silanamin derivative and a layer of a porphyrin compound (disclosed in JP-A-63-295695) or an organic semiconductor oligomer. It is a multilayer structure with a layer of a certain p-type thiophene-containing oligomer.

Typical examples of the porphyrin compound include porphine, 5,10,15,20-tetraphenyl-21H, 23H-porphine copper (II), 5,10, and
15,20-Tetraphenyl-21H, 23H-porphine zinc (II), 5,10,15,20-tetrakis (pentafluorophenyl) -21H, 23H-porphine, silicon phthalocyanine oxide, aluminum phthalocyanine chloride, phthalocyanine (metal-free ),
Examples thereof include dilithium phthalocyanine, copper tetramethylphthalocyanine, copper phthalocyanine, chromium phthalocyanine, zinc phthalocyanine, lead phthalocyanine, titanium phthalocyanine oxide, magnesium phthalocyanine, and copper octamethylphthalocyanine.

As the p-type thiophene-containing oligomer, the following formula

[Chemical 7] (Where, k = 1, 2 or 3, m = 1, 2 or 3, n
= 1, 2 or 3, and k + m + n ≧ 5,
R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a cyclohexyl group).

In the organic EL device of the present invention, the electron injection layer (electron injection / transport layer) provided as required may have a function of transferring the electrons injected from the cathode to the organic light emitting layer. As the material, any one of conventionally known electron transfer compounds can be selected and used.

Preferred specific examples of the electron transfer compound include the following formulas (1) to (5)

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12] The compound represented by

The electron injecting layer is a layer having any of the electron injecting property, the electron transporting property and the obstacle property, and is represented by the above formula (1)
In addition to the compound (5), a crystalline or non-crystalline material such as Si-based, SiC-based, CdS-based can be used.

The organic EL device of the present invention comprises the above-mentioned anode,
In addition to the cathode, the organic light emitting layer, the hole transport layer provided as necessary, and the electron injection layer provided as necessary,
It may have a layer for improving adhesion between layers.
Specific examples of the material of such a layer, for example, tris (8-quinolinol) aluminum, tris (8-quinolinol) indium, and the like are specific examples of the material of the layer for improving the adhesion between the organic light emitting layer and the cathode. Quinolinol metal complex system.

The organic EL device of the present invention described above can be manufactured, for example, in the following manner depending on its structure. (A) Production of organic EL device having constitution of anode / organic light-emitting layer (including silanamin derivative) / cathode-1-First, a thin film made of a desired electrode substance, for example, an anode substance, having a thickness of 1 μm or less is formed on a suitable substrate. Preferably 10-200
The anode is formed by a method such as vapor deposition or sputtering so as to have a film thickness in the range of nm. Next, an organic light emitting layer is provided by forming a thin film of the silanamin derivative represented by the general formula (I) on this anode. The thin film of the silanamin derivative is formed by a vacuum vapor deposition method, a spin coating method,
Although it can be performed by a method such as a casting method, the vacuum vapor deposition method is preferable because it is easy to obtain a uniform film and pinholes are not easily generated.

When a vacuum vapor deposition method is used for thinning the silanamin derivative, the vapor deposition conditions vary depending on the type of the silanamin derivative used, the crystal structure or association structure of the target organic light emitting layer, etc. Temperature 50 to 400 ° C., vacuum degree 10 ⁻⁵ to 10 ⁻³ Pa, vapor deposition rate 0.01 to 50 nm / sec, substrate temperature −50 to +30.
It is preferable to select appropriately in the range of 0 ° C. and the film thickness of 5 nm to 5 μm.

After forming the organic light emitting layer, a thin film made of a cathode material is formed on the organic light emitting layer to a thickness of 1 μm or less, preferably 10
A cathode is formed by forming the film so as to have a film thickness in the range of up to 200 nm by a method such as vapor deposition or sputtering. As a result, the target organic EL device is obtained. In the manufacture of this organic EL element, the manufacturing order is reversed,
It is also possible to fabricate in the order of cathode / organic light emitting layer / anode on the substrate.

(B) Manufacture of an organic EL device having a structure of anode / organic light-emitting layer (including silanamin derivative) / cathode-2-First, an anode is formed on a suitable substrate in the same manner as in the case of (A). Create. Then, on this anode, a hole transport layer material,
Organic light emission is obtained by forming a thin film by applying a solution containing an organic light emitting layer material, an electron injection layer material, a binder (polyvinylcarbazole, etc.), or by forming a thin film from this solution by a dip coating method. Provide layers. After that, a thin film made of a cathode material is formed on the organic light emitting layer in the same manner as in the case (A) to prepare a cathode. As a result, the target organic EL device is obtained.

The organic light-emitting layer may have a multi-layer structure by forming a thin film of a desired organic light-emitting layer material on the layer formed as described above by a vacuum deposition method or the like. Alternatively, the organic light emitting layer may be formed by co-evaporating the organic light emitting layer material together with the hole transport layer material and the electron injection layer material.

(C) Manufacture of organic EL device having a structure of anode / hole transport layer (including silanamin derivative) / organic light emitting layer / cathode First, on a suitable substrate, in the same manner as in the case of the above (A), Make an anode. Next, a hole transport layer is provided by forming a thin film of the silanamin derivative represented by the general formula (I) on this anode. The formation of this hole transport layer is the same as described in (A) above.
It can be carried out in the same manner as the formation of the organic light emitting layer (including the silanamine derivative) in.

Next, an organic light emitting layer is provided on the hole transport layer by using a desired organic light emitting layer material. The organic light emitting layer can be formed by thinning the organic light emitting layer material by a method such as a vacuum vapor deposition method, a spin coating method, or a casting method, but a uniform film is easily obtained and pinholes are generated. From the viewpoint of difficulty and the like, it is preferable to form by a vacuum vapor deposition method.

After that, a thin film made of the cathode material is formed in the above (A).
In the same manner as in the above case, the cathode is formed on the organic light emitting layer. As a result, the target organic EL device is obtained. Also in the production of this organic EL element, the production order is reversed, and the cathode / organic light emitting layer / hole transport layer / hole transport layer / on the substrate.
It is possible to manufacture in the order of the anode.

(D) Manufacture of organic EL device having a structure of anode / hole transport layer (including silanamin derivative) / organic light emitting layer / electron injection layer / cathode First, on a suitable substrate, the case of the above (C) Similarly, an anode, a hole transport layer (including a silanamin derivative) and an organic light emitting layer are formed. After forming the organic light emitting layer, a thin film made of a desired electron injection layer material is formed on the organic light emitting layer by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 5 to 100 nm. Thus, the electron injection layer is formed.

After that, a thin film made of a cathode material is formed in the above (C).
In the same manner as in the above case, the cathode is formed on the electron injection layer. As a result, the target organic EL device is obtained. Also in the production of this organic EL element, the production order is reversed and the cathode / electron injection layer / organic light emitting layer / organic light emitting layer / on the substrate.
It is possible to fabricate the hole transport layer / anode in this order.

The organic EL device of the present invention, which can be manufactured as described above, emits light by applying a DC voltage of 5 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Even if a voltage is applied with the opposite polarity, no current flows and no light emission occurs. When an AC voltage is applied, light emission occurs only when the anode has a positive polarity and the cathode has a negative polarity. When an AC voltage is applied, the AC waveform may be arbitrary.

In the organic EL device of the present invention, at least one compound layer having a single-layer structure or a multi-layer structure containing at least an organic light-emitting layer contains a silanamin derivative represented by the general formula (I). Since the ionization potential of this silanamin derivative is as low as 5.5 to 5.6 eV, the organic EL device of the present invention can be driven at a low voltage.

Further, the thin film of the silanamin derivative represented by the general formula (I) is slower to recrystallize with time than the thin film of the conventional amine-based material (for example, TPD). Therefore, according to the present invention, it becomes easier to obtain an organic EL device in which the device life is less likely to deteriorate as compared with the case where an amine-based material is used.

[0061]

EXAMPLES Examples of the present invention will be described below. Example 1 (Production of Silanamine Derivative) 2.00 g (5.9
5 mmol) of N, N′-diphenyl-benzidine [diarylamine shown in FIG. 9 (1); manufactured by Tokyo Kasei] was added, and this N, N′-diphenyl-benzidine was distilled from a sodium line under an argon stream. 200 ml TH
After dissolving with F, 10 ml (about 16 mmol) of a hexane solution of n-butyllithium was added to this solution. 50 this
After heating at 0 ° C for 0.5 hour, 3.98 g (1
3.5 mmol) of triphenylchlorosilane [Fig. 12
Halogenated silane shown in (1); manufactured by Shin-Etsu Chemical Co., Ltd.]
A solution dissolved in 0 ml of THF (distilled from sodium wire under an argon stream) was slowly added dropwise using a dropping funnel. After that, the reaction is carried out at room temperature, and after 18 hours, 1
The reaction was terminated by adding 00 ml of water.

The liquid after completion of the reaction was extracted twice with 200 ml of methylene chloride, the extract was dried over anhydrous sodium sulfate, and the solvent was distilled off with an evaporator to obtain white crystals. The white crystals were purified by column chromatography using Wakogel C-200 [trade name, silica gel type carrier manufactured by Hiroshima Wako Pure Chemical Industries] as a carrier and toluene as a developing solution, and the solvent was distilled off with an evaporator. As a result, 0.79 g of white crystals were obtained.

The melting point of the white crystal thus obtained was 209 ° C., and the NMR measurement (H: 400 MHz, TH
The result of F-d8) was as shown in FIG. Also F
As a result of measuring D-MS (Field Desorption Mass Spectroscopy), a parent peak of 852 mass spectrum was observed for C ₆₀ H ₄₈ N ₂ Si ₂ = 852.
Furthermore, when IR (infrared absorption spectrum) was measured, 1600, 1500, 1280 and 900 (cm
^-1 ) absorption was observed. From these measurement results, it was confirmed that the obtained white crystals were the silanamin derivative shown in FIG. 1 (1) (hereinafter abbreviated as Sil-1) (yield 16%).

Example 2 (Production of Silanamine Derivative) 2.00 g (6.92 mmol) of N, N'-diphenyl-1,4-benzenediamine [diarylamine shown in FIG. 9 (2); manufactured by Kanto Chemical Co., Inc.] And 10 ml (about 16 mmol) of n-butyllithium in hexane, 4.0
In the same manner as in Example 1, 1 g (13.6 mmol) of triphenylchlorosilane [halogenated silane shown in FIG. 12 (1); manufactured by Shin-Etsu Chemical Co., Ltd.] was reacted. After the reaction was completed, the produced crystals were filtered out, washed with a hot pyridine solution and then dried to obtain 0.88 g of white crystals.

The melting point of the white crystal thus obtained was 300 ° C. or higher. Further, as a result of FD-MS measurement, a parent peak of the 776 mass spectrum was observed for C ₅₄ H ₄₄ N ₂ Si ₂ = 776. Furthermore, when IR was measured, 1600, 1500, 1280 and 900
Absorption was observed at (cm ^-1 ). From these measurement results, it was confirmed that the obtained white crystal was a silanamin derivative (hereinafter abbreviated as Sil-2) shown in FIG. 1 (2) (yield 16%).

Example 3 (Production of Silanamine Derivative) 2.02 g (5.61 mmol) of N, N'-di- (2
-Naphthyl) -1,4-benzenediamine [Fig. 9 (3)]
And a hexane solution of n-butyllithium 10 ml (about 16 mmol).
And 3.98 g (13.5 mmol) of triphenylchlorosilane [halogenated silane shown in FIG. 12 (1); manufactured by Shin-Etsu Chemical Co., Ltd.] were reacted in the same manner as in Example 1.
After the reaction was completed, the produced crystals were filtered out, washed with a hot pyridine solution and then dried to obtain 1.39 g of white crystals.

The melting point of the white crystal thus obtained was 300 ° C. or higher. Further, as a result of measuring FD-MS, a parent peak of the masquerad of 876 was observed for C ₆₂ H ₄₈ N ₂ Si ₂ = 876. Furthermore, when IR was measured, 1600, 1490, 1280 and 920
Absorption was observed at (cm ^-1 ). From these measurement results, it was confirmed that the obtained white crystals were the silanamin derivative shown in FIG. 1 (3) (hereinafter abbreviated as Sil-3) (yield 28%).

Example 4 (Production of Silanamine Derivative) (1) Production of Diarylamine A raw material diarylamine was produced as follows.
12.24 g (82.1
mmol) p-tolylacetanilide (manufactured by Hiroshima Wako Pure Chemical Industries, Ltd.), 10.03 g (32.1 mmol) of 4,4 ′.
-Dibromobiphenyl (Hiroshima Wako Pure Chemical Industries, Ltd.), 20.2.
2 g (145 mmol) anhydrous potassium carbonate, 1.0 g
(15.6 mmol) copper powder, and 0.12 g (0.
Iodine (9 mmol) was added, and the mixture was suspended in 200 ml of DMSO and reacted at 200 ° C. for 48 hours. afterwards,
A solution prepared by dissolving 20 g of KOH in 50 ml of water was added, and hydrolysis was carried out at 80 ° C. for 5 hours. After the reaction, the inorganic substances were removed by filtration, the mixture was extracted with ethyl acetate, and then the solvent was distilled off with an evaporator. Then, it was purified by column chromatography to obtain 7.01 g of white crystals.

The melting point of the white crystals thus obtained was 252 to 255 ° C. The NMR measurement results are
δ: 7.59 to 7.40 (dd, 8H), 7.10
7.02 (dd, 8H), 3.49 (s, 6H), 2.
It was 32 (s, 2H). Furthermore, as a result of measuring FD-MS, a parent peak of the 364 mass spectrum was observed for C ₂₆ H ₂₄ N ₂ = 364. From these measurement results, the obtained white crystal was obtained by using the diarylamine [N, N′-di- (p-tolyl) -benzidine] shown in FIG. 9 (4).
Was confirmed (yield 60%).

(2) Preparation of silanamin derivative N, N'-di- (p-tolyl) -obtained in the above (1)
2.00 g (5.49 mmol) of benzidine and n-
10 ml of hexane solution of butyl lithium (about 16 mmo
1) and 4.02 g (13.7 mmol) of triphenylchlorosilane [halogenated silane shown in FIG. 12 (1); manufactured by Shin-Etsu Chemical Co., Ltd.] were reacted in the same manner as in Example 1. After completion of the reaction, extraction with a solvent and purification by column chromatography were performed in the same manner as in Example 1,
1.01 g of white crystals were obtained.

The melting point of the white crystals thus obtained was 300 ° C. or higher. Further, as a result of measuring FD-MS, a parent peak of the 880 mass spectrum was observed for C ₆₂ H ₅₂ N ₂ Si ₂ = 880. Furthermore, when IR was measured, 1600, 1500, 1280 and 910
Absorption was observed at (cm ^-1 ). From these measurement results, it was confirmed that the obtained white crystal was a silanamine derivative (hereinafter abbreviated as Sil-4) shown in FIG. 1 (4) (yield 21%).

Example 5 (Production of Silanamine Derivative) (1) Production of Diarylamine A raw material diarylamine was produced as follows.
5.01 g (20.9 mmol) of 3,3 ', 5,5'
-Tetramethylbenzidine (manufactured by Tokyo Kasei) and 8.0 g
(60 mmol) acetic anhydride was dissolved in 50 ml methylene chloride, and one drop of concentrated sulfuric acid was added thereto. The mixture was allowed to stand at room temperature for 8 hours and then extracted with methylene chloride. After extraction, the solvent and acetic anhydride were distilled off under reduced pressure, and the residue was purified by column chromatography. The obtained purified product was used in an amount of 6.0 g instead of 4,4'-dibromobiphenyl.
1.44 in the same manner as in Example 4 (1) except that (38 mmol) benzene bromide (manufactured by Tokyo Kasei) was reacted.
White crystals of g were obtained.

FD- of the white crystals thus obtained
As a result of measuring MS, 3 was obtained for C ₂₈ H ₂₈ N ₂ = 392.
A parent peak of 92 mass spectra was observed. From the results of this measurement, the obtained white crystals were the diarylamine [N, N'-diphenyl-3,3 ', 5, shown in Fig. 9 (5).
5'-tetramethylbenzidine] was confirmed (yield 18%).

(2) Production of silanamine derivative N, N'-diphenyl-3, obtained in the above (1),
2.00 g of 3 ', 5,5'-tetramethylbenzidine
(5.10 mmol), 10 ml (about 16 mmol) of a hexane solution of n-butyllithium, and 3.98 g (1
3.5 mmol) of triphenylchlorosilane [Fig. 12
Halogenated silane shown in (1); manufactured by Shin-Etsu Chemical Co., Ltd.,
Reaction was carried out in the same manner as in Example 1. After completion of the reaction, extraction with a solvent and purification by column chromatography were carried out in the same manner as in Example 1 to obtain 0.37 g of pale pink crystals.

The melting point of the pale pink crystals thus obtained was 300 ° C. or higher. Further, as a result of FD-MS measurement, a parent peak of the 908 mass spectrum was observed for C ₆₈ H ₆₄ N ₂ Si ₂ = 908. Furthermore, when IR was measured, 1590, 1500, 1300 and 90
Absorption was observed at 0 (cm ^-1 ). From these measurement results, it was confirmed that the obtained pale pink crystals were the silanamin derivative shown in FIG. 1 (5) (hereinafter abbreviated as Sil-5) (yield 8%).

Example 6 (Production of Silanamine Derivative) 2.01 g (5.98 mmol) of N, N'-diphenyl-benzidine [diarylamine shown in FIG. 9 (1);
Manufactured by Tokyo Kasei], 10 ml (about 16 mmol) of a hexane solution of n-butyllithium, and 5.01 g (14.9).
mmol) of tri- (p-tolyl) chlorosilane [Fig. 1
2 (2); halogenated silane; manufactured by Shin-Etsu Chemical Co., Ltd.] in the same manner as in Example 1. After completion of the reaction, extraction with a solvent and purification by column chromatography were performed in the same manner as in Example 1 to obtain 1.40 g of white crystals.

The melting point of the white crystal thus obtained was 300 ° C. or higher. In addition, as a result of FD-MS measurement, a parent peak of the mass spectrum of 936 was observed for C ₆₆ H ₆₀ N ₂ Si ₂ = 936. Furthermore, when IR was measured, 1600, 1510, 1280 and 900
Absorption was observed at (cm ^-1 ). From these measurement results, it was confirmed that the obtained white crystals were the silanamin derivative shown in FIG. 1 (6) (hereinafter abbreviated as Sil-6) (yield 25%).

Example 7 (Production of Silanamine Derivative) (1) Production of Diarylamine A raw material diarylamine was produced as follows.
15.80 g (85.4
mmol) 1-acetylaminonaphthalene (Kanto Chemical Co., Inc.), 13.51 g (33.3 mmol) 4,4 ′.
-Diiododiphenyl (Hiroshima Wako Pure Chemical Industries, Ltd.), 14.9
8 g (109 mmol) anhydrous potassium carbonate, 1.0 g
Add the copper powder from the above and suspend it in 200 ml of DMSO.
The reaction was carried out at 00 ° C for 48 hours. Next, a solution prepared by dissolving 6.4 g of potassium hydroxide in 50 ml of water was added to this reaction solution, 100 ml of THF was added, and hydrolysis was carried out at 80 ° C. for 5 hours. After the reaction, the inorganic substances were removed by filtration, the mixture was extracted with ethyl acetate, and then the solvent was distilled off with an evaporator. Then, it was purified by column chromatography to obtain 3.56 g of white crystals.

The melting point of the white crystals thus obtained was 246 to 248 ° C. The NMR measurement results are
δ 8.10 to 7.82 (m, 4H), 7.58 to 7.3
6 (m, 16H), 7.08 to 6.99 (m, 2H),
It was 2.36 (s, 2H) ppm. Furthermore, FD-
As a result of measuring MS, 4 was obtained for C ₃₂ H ₂₄ N ₂ = 436.
36 parent peaks of the mass spectrum were observed.

From the results of these measurements, the obtained white crystals were the diarylamine [N, N 'shown in FIG. 11 (34).
-Di- (1-naphthyl) -benzidine] was confirmed (yield 25%).

(2) Production of Siranamine Derivative N, N′-di- (1-naphthyl) obtained in the above (1)
-2.03 g (4.66 mmol) of benzidine, n
-Butyllithium hexane solution 10 ml (about 16 mm
ol) and 3.87 g (13.1 mmol) of triphenylchlorosilane [halogenated silane shown in FIG. 12 (1); manufactured by Shin-Etsu Chemical Co., Ltd.] were reacted in the same manner as in Example 1. After completion of the reaction, extraction with a solvent and purification by column chromatography were performed in the same manner as in Example 1,
3.28 g of white crystals were obtained.

The melting point of the white crystals thus obtained was 300 ° C. or higher. Further, as a result of measuring FD-MS, a parent peak of a mass spectrum of 952 was observed for C ₆₈ H ₅₂ N ₂ Si ₂ = 952. Furthermore, when IR was measured, 1600, 1500, 1280, 890
Absorption was observed at (cm ^-1 ). From these measurement results, it was confirmed that the obtained white crystals were the silanamin derivative shown in FIG. 8 (43) (hereinafter abbreviated as Sil-7) (yield 74%).

Example 8 (Production of Silanamine Derivative) (1) Production of Diarylamine 5.0 g (19 mmol) of 4,4′-diaminoterphenylene was placed in a reaction vessel and dissolved in 500 ml of THF, and 13 ml thereof was added thereto. Acetic anhydride was gradually added. After reacting for 12 hours at room temperature, it was separated by filtration and washed with THF to obtain 10.83 g of a white powder. 10.02 g (29.0 mm) of this compound was placed in a reaction vessel in which the atmosphere was replaced with argon.
ol) and 14.92 g (73.1 mmol) of iodobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 14.78 g (107 mm).
ol) anhydrous potassium carbonate and 1.0 g of copper powder are added, and 2
It was suspended in 00 ml of DMSO and reacted at 200 ° C. for 48 hours. Next, 21 g of potassium hydroxide dissolved in 50 ml of water was added to this reaction solution, and 100 ml was added.
THF was added and hydrolysis was performed at 80 ° C. for 5 hours.
After the reaction, the inorganic substances were removed by filtration, the mixture was extracted with ethyl acetate, and then the solvent was distilled off with an evaporator. Then, it was purified by column chromatography to obtain 5.62 g of white crystals.

The melting point of the white crystals thus obtained was 238 to 240 ° C. The NMR measurement results are
[delta] 7.62 to 7.46 (m, 10H), 7.29 to 6.
It was 94 (m, 12H) and 2.10 (s, 2H) ppm. Furthermore, as a result of measuring FD-MS, C ₃₀ H ₂₄ N
A parent peak of the mass spectrum of 412 was observed for ₂ = 412. From these measurement results, the obtained white crystal was obtained by using the diarylamine [N,
N'-diphenyl-4,4'-diaminoterphenylene] was confirmed (yield 47%).

(2) Production of Silanamine Derivative N, N′-diphenyl-4,4 ′ obtained in the above (1)
-2.30 g of diaminoterphenylene (5.58 mm
ol) and 10 ml of hexane solution of n-butyllithium
(About 16 mmol) and 4.29 g (14.5 mmo
In the same manner as in Example 1, 1) triphenylchlorosilane [halogenated silane shown in FIG. 12 (1); manufactured by Shin-Etsu Chemical Co., Ltd.] was reacted. After completion of the reaction, extraction with a solvent and purification by column chromatography were performed in the same manner as in Example 1 to obtain 0.38 g of white crystals.

The melting point of the white crystal thus obtained was 300 ° C. or higher. Further, as a result of measuring FD-MS, a parent peak of a mass spectrum of 928 was observed for C ₆₆ H ₅₂ N ₂ Si ₂ = 928. Furthermore, when IR was measured, 1600, 1500, 1280, 900
Absorption was observed at (cm ^-1 ). From these measurement results, it was confirmed that the obtained white crystals were the silanamin derivative shown in FIG. 8 (44) (hereinafter abbreviated as Sil-8) (yield 7%).

Example 9 (Silanamine Derivative) (1) Production of Diarylamine A raw material diarylamine was produced as follows.
15.04 g (101 m
mol) m-acetotoluide (Hiroshima Wako Pure Chemical Industries, Ltd.),
15.71 g (38.7 mmol) of 4,4′-diiododiphenyl (Hiroshima Wako Pure Chemical Industries, Ltd.), 20.31 g (1
Anhydrous potassium carbonate (47 mmol) and 1.0 g of copper powder were added, suspended in 200 ml of DMSO, and reacted at 200 ° C. for 48 hours. Next, to this reaction solution was added 20 g of potassium hydroxide dissolved in 50 ml of water, and 1
00 ml of THF was added and hydrolysis was carried out at 80 ° C. for 5 hours. After the reaction, the inorganic substances were removed by filtration, the mixture was extracted with ethyl acetate, and then the solvent was distilled off with an evaporator. After that, purification by column chromatography was performed to obtain 5.1.
1 g of white crystals was obtained.

The melting point of the white crystals thus obtained was 155 to 157 ° C. The NMR measurement results are
δ 7.80 to 7.04 (m, 16H), 2.52 (s,
2H) and 2.32 (s, 6H) ppm. Furthermore, as a result of measuring FD-MS, C ₂₆ H ₂₄ N ₂ = 364
On the other hand, the parent peak of the mass spectrum of 364 was observed. From these measurement results, the obtained white crystals are shown in FIG.
0 (12) diarylamine [N, N′-di-
(M-tolyl) -benzidine] was confirmed (yield 36%).

(2) Production of Silanamine Derivative N, N'-di- (m-tolyl) -obtained in the above (1)
2.17 g (5.96 mmol) of benzidine and n-
10 ml of hexane solution of butyl lithium (about 16 mmo
1) and 4.35 g (14.7 mmol) of triphenylchlorosilane [halogenated silane shown in FIG. 12 (1); manufactured by Shin-Etsu Chemical Co., Ltd.] were reacted in the same manner as in Example 1. After completion of the reaction, extraction with a solvent and purification by column chromatography were performed in the same manner as in Example 1,
2.03 g of white crystals were obtained.

The melting point of the white crystals thus obtained was 300 ° C. or higher. Further, as a result of measuring FD-MS, a parent peak of a mass spectrum of 880 was observed for C ₆₂ H ₅₂ N ₂ Si ₂ = 880. Furthermore, when IR was measured, 1600, 1500, 1280, 900
Absorption was observed at (cm ^-1 ). From these measurement results, it was confirmed that the obtained white crystal was a silanamin derivative shown in FIG. 3 (13) (hereinafter abbreviated as Sil-9) (yield 39%).

Measurement of Ionization Potential The ionization potential of each of the silanamine derivatives obtained in Examples 1 to 9 was measured using a surface analyzer A manufactured by Riken Keiki Co., Ltd.
It was measured by C-1 (trade name). Also, as a comparison,
The ionization potential of hexaphenylcyclodisilazane, which is one of the cyclodisilazanes, and TPD [N, N'-bis- (m-tolyl)-, which is one of the amine materials,
The ionization potential of [N, N'diphenyl-1,1'-biphenyl] was measured in the same manner. The results are shown in Table 1.

[0092]

[Table 1]

As is clear from Table 1, the ionization potentials of the respective silanamine derivatives obtained in Examples 1 to 9 are 5.5 to 5.6 eV, which is equal to or slightly higher than that of TPD. Although high, the ionization potential of hexaphenylcyclodisilazane 5.7
lower than eV. From this, it is understood that the respective silanamine derivatives obtained in Examples 1 to 9 have a feature that holes are more easily injected than hexaphenylcyclodisilazane.

Comparative Example 1 (Production of 4,4'-di-t-butyl-triphenylamine) 22.5 g (0.08 mol) of 4,4'-di-t-butyldiphenylamine, 32.6 g ( 0.16 mol) iodobenzene, 16.6 g (0.12 mol) anhydrous potassium carbonate, and 0.5 g (8 mmol) copper powder were mixed and reacted with DMSO as a solvent at 200 to 230 ° C. for 5 hours. Let When 200 ml of toluene was added after the completion of the reaction, the product was dissolved, but the inorganic salt remained as a solid substance, so that purification was difficult unlike in the cases of Examples 1 to 9. It also required treatment of copper salt effluent.

Example 10 (Production of Organic EL Element) Glass substrate [manufactured by HOYA Corporation, 25 mm × 75 mm × 1 m
m; ITO film (corresponding to anode) on product name NA40]
The transparent support substrate was formed to a thickness of 00 nm.
The transparent support substrate was ultrasonically cleaned in isopropyl alcohol for 5 minutes, blown with dry nitrogen, dried, and further cleaned with a UV ozone cleaning device (trade name: UV300, manufactured by Samco International) for 10 minutes.

The transparent supporting substrate after cleaning was attached to a substrate holder of a vacuum vapor deposition apparatus [manufactured by Nippon Vacuum Technology Co., Ltd.], and the inside of the vacuum chamber was evacuated to 1 × 10 ⁻⁴ Pa. Prior to exhaust, the silanamine derivative (Sil-
1) A resistance heating boat made of molybdenum containing 200 mg and 4,4'-bis- which is a dimethylidene-based luminescent material.
A resistance heating boat made of molybdenum containing (2,2-diphenylvinyl) -1,1′-biphenyl (hereinafter abbreviated as DPVBi) and tris (8-quinolinol) aluminum (which is an electron transporting adhesion improving substance) Below, Alq
A resistance heating boat made of molybdenum containing 200 mg was attached to each energizing terminal block. After the exhaust
The boat containing Sil-1 was heated to 270 ° C., and Si was deposited on the ITO film at a vapor deposition rate of 0.4 to 0.6 nm / sec.
1-1 was vapor-deposited to provide a Sil-1 layer (corresponding to a hole transport layer) having a film thickness of 60 nm.

Next, the boat containing the DPVBi was heated to Sil-1 at the vapor deposition rate of 0.4 to 0.6 nm / sec.
DPVBi is vapor-deposited on the layer to form a 40 nm-thick DPV
A Bi layer (corresponding to an organic light emitting layer) was provided. Next, the boat containing Alq is heated to vapor deposition rate of 0.1 to 0.3 nm.
Alq is vapor-deposited on the DPVBi layer at a film thickness of 2 / sec.
A 0 nm Alq layer (corresponding to the adhesion improving layer) was provided.

After that, the vacuum chamber was opened, and a molybdenum-containing boat containing magnesium and a tungsten-containing filament boat containing silver were newly attached to the energizing terminal block. Further, a vapor deposition mask was attached on the glass substrate / ITO film / Sil-1 layer / DPVBi layer / Alq layer prepared above. Then, the vacuum chamber was evacuated to 1 × 10 ⁻⁴ Pa again, and then a filament boat containing silver was first energized to vapor deposit silver at a vapor deposition rate of 0.09 to 0.1 nm / sec and, at the same time, magnesium containing The boat was energized to deposit magnesium at a vapor deposition rate of 1.4 to 1.7 nm / sec. By this two-source simultaneous vapor deposition, a film thickness of 150 is formed on the Alq layer.
nm magnesium-silver layer (corresponding to the cathode) was formed. An organic EL device was obtained by providing the cathode on the glass substrate as described above.

8. The magnesium-silver layer of the organic EL device thus obtained was used as a cathode and the ITO film was used as an anode.
When a voltage of 5 V was applied, blue emission of 114 cd / m ² was observed. Table 2 shows the current density, luminance, luminous efficiency, and luminous color at this time. The maximum emission brightness of this organic EL device was 10,000 cd / m ² .

Example 11 (Production of Organic EL Element) Copper phthalocyanine (hereinafter referred to as Cu) was used as a material for the hole transport layer.
Pc) (abbreviated as Pc) and Sil-1 were used to obtain an organic EL device in the same manner as in Example 10. The hole transport layer was formed by heating a molybdenum boat containing CuPc and depositing CuPc on the ITO film at a deposition rate of 0.2 to 0.4 nm / sec to form a CuPc layer having a thickness of 20 nm. , Sil-1 in molybdenum boat 27
Heating up to 0 ° C, evaporation rate 0.4 ~ 0.6nm / se
Sil-1 is vapor-deposited on the CuPc layer by c to obtain a film thickness of 40n.
m Sil-1 layer is provided to form a two-layer structure.

When a voltage of 10 V was applied to the thus obtained organic EL device in the same manner as in Example 10,
A blue emission of 440 cd / m ² was observed. Table 2 shows the current density, luminance, luminous efficiency, and luminous color at this time.

Example 12 (Production of Organic EL Element) An organic EL element was prepared in the same manner as in Example 11 except that the silanamine derivative (Sil-3) obtained in Example 3 was used instead of Sil-1. Obtained. When a voltage of 9 V was applied to the organic EL device thus obtained in the same manner as in Example 11, blue emission of 150 cd / m ² was observed.
Table 2 shows the current density, luminance, luminous efficiency, and luminous color at this time.

Example 13 (Production of Organic EL Element) An organic EL element was prepared in the same manner as in Example 11 except that the silanamine derivative (Sil-4) obtained in Example 4 was used instead of Sil-1. Obtained. When a voltage of 9.5 V was applied to the organic EL device thus obtained in the same manner as in Example 11, blue emission of 1000 cd / m ² was observed. Table 2 shows the current density, luminance, luminous efficiency, and luminous color at this time.

Example 14 (Production of Organic EL Element) α-Sexithiophene (hereinafter abbreviated as T ₆ ) which is one of the organic semiconductor oligomers as a material for the hole transport layer.
And an Sil-1 were used to obtain an organic EL device in the same manner as in Example 10. The hole transport layer was formed by heating a boat made of molybdenum containing T ₆ to obtain a vapor deposition rate of 0.1.
After depositing T ₆ on the ITO film at a thickness of ˜0.3 nm / sec to form a T ₆ layer having a film thickness of 20 nm, the boat made of molybdenum containing Sil-1 is heated to 270 ° C. and the deposition rate is 0. 4～0.6Nm / by depositing Sil-1 to T ₆ layers on provided Sil-1 layer having a film thickness of 40nm at sec, was formed by a two-layer structure.

When a voltage of 8 V was applied to the thus obtained organic EL device in the same manner as in Example 10, 2
A blue emission of 50 cd / m ² was observed. Table 2 shows the current density, luminance, luminous efficiency, and luminous color at this time.

Example 15 (Production of Organic EL Device) Instead of T ₆ , 4,4′-bis-dithiophenyl-1,1′-biphenyl (hereinafter abbreviated as BTBIBT) which is one of the organic semiconductor oligomers. An organic EL device was obtained in the same manner as in Example 14 except that When a voltage of 9 V was applied to the organic EL device thus obtained in the same manner as in Example 14, blue emission of 700 cd / m ² was observed. Table 2 shows the current density, luminance, luminous efficiency, and luminous color at this time.

Example 16 (Production of Organic EL Element) An organic EL element was obtained in the same manner as in Example 11 except that the silanamine derivative (Sil-7) obtained in Example 7 was used instead of Sil-1. It was Organic EL obtained in this way
When a voltage of 10 V was applied to the device in the same manner as in Example 10, blue light emission of 100 cd / m ² was obtained. Table 2 shows the current density, luminance, luminous efficiency and luminous color at this time.

Example 17 (Production of Organic EL Element) An organic EL element was obtained in the same manner as in Example 11 except that the silanamine derivative (Sil-8) obtained in Example 8 was used instead of Sil-1. It was Organic EL obtained in this way
When a voltage of 11 V was applied to the device as in Example 10, blue light emission of 120 cd / m ² was obtained. Table 2 shows the current density, luminance, luminous efficiency and luminous color at this time.

Example 18 (Production of Organic EL Element) An organic EL element was obtained in the same manner as in Example 11 except that the silanamine derivative (Sil-9) obtained in Example 9 was used instead of Sil-1. It was Organic EL obtained in this way
When a voltage of 12 V was applied to the device in the same manner as in Example 10, blue light emission of 140 cd / m ² was obtained. Table 2 shows the current density, luminance, luminous efficiency and luminous color at this time.

Comparative Example 2 (Production of Organic EL Element) An organic EL element was obtained in the same manner as in Example 10 except that hexaphenylcyclodisilazane was used as the material for the hole transport layer. A voltage of 13 V was applied to the organic EL device thus obtained in the same manner as in Example 10.
A blue emission of 00 cd / m ² was observed. Table 2 shows the current density, luminance, luminous efficiency, and luminous color at this time.

[0111]

[Table 2]

As is clear from Table 2, each of the organic EL devices obtained in Examples 10 to 18 exhibits practically sufficient performance under a low driving voltage of 8 to 12 V, and its luminous efficiency is It is as high as 0.66 to 1.2 lm / W. On the other hand, the organic EL device of Comparative Example 2 can only obtain a brightness of 100 cd / m ² even under a relatively high driving voltage of 13V. This is because the ionization potential of hexaphenylcyclodisilazane is as high as 5.7 eV, so that voltage is consumed for hole injection.

Evaluation of Thin Film Maintainability A glass substrate [manufactured by HOYA Co., Ltd .; product name NA40] with an ITO film having a thickness of 100 nm was ultrasonically cleaned, dried, and dried in the same manner as in Example 10. After UV ozone cleaning, ITO was used in the same manner as in Example 10.
A Sil-1 layer having a film thickness of 60 nm was provided on the film. This product was exposed to the air for 1 month, and then recrystallized to produce Sil.
The presence or absence of breakage of the -1 layer was observed with an optical microscope. As a result, destruction of the Sil-1 layer due to recrystallization was not observed under an optical microscope. From this, it is understood that Sil-1 has a good ability to maintain a thin film. On the other hand, when a similar test was performed on TPD, recrystallization observed under an optical microscope occurred after one month. From this, it is understood that the thin film maintaining ability of TPD is inferior to that of Sil-1.

[0114]

As described above, according to the present invention,
It is possible to provide a new silanamine derivative which is easy to purify, slow in recrystallization with time when formed into a thin film, and has a low ionization potential. Further, it becomes possible to provide a new organic EL element that can be driven at a low voltage.

[Brief description of drawings]

FIG. 1 is a structural formula showing a specific example of the silanamin derivative of the present invention.

FIG. 2 is a structural formula showing another specific example of the silanamin derivative of the present invention.

FIG. 3 is a structural formula showing another specific example of the silanamin derivative of the present invention.

FIG. 4 is a structural formula showing another specific example of the silanamin derivative of the present invention.

FIG. 5 is a structural formula showing another specific example of the silanamin derivative of the present invention.

FIG. 6 is a structural formula showing another specific example of the silanamin derivative of the present invention.

FIG. 7 is a structural formula showing another specific example of the silanamin derivative of the present invention.

FIG. 8 is a structural formula showing another specific example of the silanamin derivative of the present invention.

FIG. 9 is a structural formula showing a specific example of a diarylamine used in the method of the present invention.

FIG. 10 is a structural formula showing another specific example of the diarylamine used in the method of the present invention.

FIG. 11 is a structural formula showing another specific example of the diarylamine used in the method of the present invention.

FIG. 12 is a structural formula showing a specific example of a halogenated silane used in the method of the present invention.

FIG. 13: NM of siranamine derivative obtained in Example 1
It is an R chart.

Claims (4)

[Claims] 1. A compound represented by the general formula (I): (In the formula, Ar ¹ is (i) an aryl group having 6 to 20 carbon atoms, or (ii) an alkyl group having 1 to 6 carbon atoms;
6-20 nuclear carbon atoms substituted with an alkoxy group, a phenoxy group, an alkyl-substituted phenoxy group or a vinyl group
Is an aryl group of, Ar ² is (i) an arylene group having 6 to 20 carbon atoms,
Or (ii) an arylene group having 6 to 20 nuclear carbon atoms substituted with an alkyl group having 1 to 6 carbon atoms, Ar ³ is (i) an aryl group having 6 to 12 carbon atoms, or (ii) A silanamin derivative represented by (an aryl group having 6 to 12 nuclear carbon atoms substituted with an alkyl group having 1 to 3 carbon atoms). 2. A compound represented by the general formula (II): (In the formula, Ar ¹ is (i) an aryl group having 6 to 20 carbon atoms, or (ii) an alkyl group having 1 to 6 carbon atoms;
6-20 nuclear carbon atoms substituted with an alkoxy group, a phenoxy group, an alkyl-substituted phenoxy group or a vinyl group
Is an aryl group of, Ar ² is (i) an arylene group having 6 to 20 carbon atoms,
Or (ii) an arylene group having 6 to 20 nuclear carbon atoms substituted with an alkyl group having 1 to 6 carbon atoms) and a general formula (III) (Ar ³ ) ₃ SiX (III) (In the formula, Ar ³ is (i) an aryl group having 6 to 12 carbon atoms, or (ii) an aryl group having 6 to 12 nuclear carbon atoms substituted with an alkyl group having 1 to 3 carbon atoms, X is a halogen atom) and the halogenated silane represented by these are made to react, The manufacturing method of the silanamine derivative of Claim 1 characterized by the above-mentioned. 3. A compound layer having a single-layer structure or a multilayer structure containing at least an organic light-emitting layer, and a compound layer sandwiching the compound layer.
An organic EL element comprising a pair of electrodes, wherein at least one of the compound layers contains the silanamin derivative according to claim 1. 4. The organic EL device according to claim 3, wherein the layer containing the silanamine derivative is a hole transport layer or an organic light emitting layer.