JPH10218887A - Silicon-containing aromatic amine compound and photoelectrtic functional element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound, comprising a silicon-containing aromatic amine compound having a specific recurring unit, having excellent hole transport ability, excellent in film-forming properties and durability and useful as a hole transport material, etc., for an organic EL element, an electrophotographic photoreceptor, etc. SOLUTION: This new silicon-containing aromatic amine compound comprises a recurring unit represented by formula I [R1 and R2 are each a 1-20C alkyl, a 3-20C cycloalkyl, a 6-29C aryl, etc., which may be substituted, Ar1 is a (substituted) 6-24C arylene; Ar2 is a (substituted) 6-24C aryl, a group, etc., represented by formula II (Ar3 is the same kind as that of Ar1 ; R3 and R4 are each the same kind as that of R1 )] and a recurring unit represented by formula III (R7 and R8 are each the same kind as that of R1 ). When the ratios of the number of the respective recurring units to the sum total (n) of the numbers of units are respectively (z) and (1-z) and (n) are each 0.125<=(z)<=1 and 3<=(n)<=8. The aromatic compound has the aromatic compound groups in the side chain and the silicon atoms in the main chain are annularly connected. Furthermore, the aromatic compound has an excellent hole transport ability and is useful as an organic EL element, an electrophotographic photoreceptor, an organic photoconductor element, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicon-containing aromatic amine compound and a photoelectric functional device using the same, specifically, an organic electroluminescent device, an electrophotographic photosensitive member, and an organic photoconductor device.

[0002]

2. Description of the Related Art Conventionally, as a hole transporting material or an electron transporting material, an inorganic compound such as amorphous selenium is mainly used in view of the magnitude of the hole drift mobility or the electron drift mobility and durability. Have been. However,
These are the issues of disposal and pollution control. In addition, when amorphous selenium having a high hole drift mobility is used, it is necessary to form a thin film by a vacuum evaporation method or the like, which is inferior in productivity and causes an increase in production cost.

[0003] In recent years, amorphous silicon has attracted attention as an inorganic compound and a non-polluting hole transporting material or electron transporting material. However, amorphous silicon is excellent in hole drift mobility or electron drift mobility, but has a problem in productivity because a plasma CVD method is mainly used in forming a thin film.

On the other hand, most organic materials which transport only holes have the advantage of no pollution, can form a thin film by coating, and can be easily mass-produced. Therefore, it has the advantages that the production cost can be significantly reduced and that it can be processed into various shapes depending on the application, and many compounds have been proposed. For example, oxadiazole derivatives, oxazole derivatives, hydrazone derivatives, triarylpyrazoline derivatives, arylamine derivatives, stilbene derivatives, and the like have been reported.

One of the techniques using a hole transport material is an organic electroluminescence device (hereinafter referred to as an organic EL device).
It may be called an L element. ). In recent years, Ta
ng et al. prepared an organic EL device having a two-layer structure in which an organic fluorescent dye was used as a light-emitting layer and a hole transporting layer made of a triphenyldiamine derivative was stacked on the organic EL device. (Japanese Patent Application Laid-Open No. 59-1984)
-194393). Compared to inorganic EL devices, organic EL devices are characterized by low voltage driving, high luminance, and easy emission of many colors, so the device structure, organic fluorescent dye, and organic charge transport compound Many attempts have been reported (Japanese Journal of Applied Physics (Jan. J. App.
l. Phys. 27, L269 (1988), Journal of Applied Physics (Jan.
J. Appl. Phys. ) Volume 65, p. 3610 (1
989)).

Have reported an aromatic amine compound having a star-shaped molecular shape (Chemistry Letters 114).
5 pages (1989), The 61st Annual Meeting of the Chemical Society of Japan 3D3
37, 3D338 (1991)). These aromatic amine compounds have a high glass transition temperature and are reported to operate as p-type semiconductors. It is stated that these aromatic amine compounds are expected to be applied to a charge transport material such as an organic EL device (Advanced Materials (Advanced Materials)).
s) Vol. 3, No. 11, p. 549 (1991), Chemistry Letters 173
1 (1991) No. 10).

Further, as a technique utilizing a hole transport material, an electrophotographic photosensitive member can be mentioned. Conventionally, inorganic photoconductors such as selenium, selenium alloys, zinc oxide, cadmium sulfide, and tellurium have been used for electrophotography. These inorganic photoconductors have advantages such as high durability and a large number of printing presses, but problems such as high production cost, poor workability, and toxicity have been pointed out. . To overcome these drawbacks, organic photoconductors have been developed.However, conventional electrophotographic photoconductors that use organic conductive materials as hole transport materials have been developed for electrophotography such as chargeability, sensitivity and residual potential. At present, the properties are not always satisfactory, have excellent charge transport ability,
The development of a durable hole transport material has been desired.

Further, as a technique using a hole transport material, a photoconductive element can be cited. Hitherto, as a material replacing the inorganic photoconductor, it has been proposed to use a polysilane compound as a hole transporting material for an organic photoconductor layer of an image sensor (JP-A-2-155270). The organic photoconductor element used has not yet obtained sufficient sensitivity and response speed.

[0009]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel silicon-containing aromatic amine compound having an excellent hole transporting ability, excellent film-forming properties and durability, and said silicon-containing aromatic amine. An object of the present invention is to provide an organic EL device, an electrophotographic photoreceptor, and an organic photoconductor device having excellent electronic characteristics using a compound as a hole transport material.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a specific novel silicon-containing aromatic amine compound has excellent hole transporting ability, excellent film-forming properties and durability, and The present inventors have found that organic EL devices, electrophotographic photoreceptors, and organic photoconductor devices manufactured using the devices have excellent electronic characteristics, and have reached the present invention.

That is, the present invention relates to [1] a silicon-containing aromatic amine compound having an aromatic amine compound group in a side chain, wherein silicon atoms in the main chain are cyclically linked,

Embedded image [Wherein, R ₁ is an optionally substituted alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl having 6 to 24 carbon atoms. Group or an aralkyl group having 7 to 26 carbon atoms. R ₂ may be substituted, 1 to
An alkyl group having 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, or an aralkyl group having 7 to 26 carbon atoms is shown. Ar ₁ represents an optionally substituted arylene group having 6 to 24 carbon atoms. Ar ₂ is an aryl group having 6 to 24 carbon atoms which may be substituted, represented by the following general formula (2)

Embedded image (Wherein, Ar ₃ represents an arylene group having 6 to 24 carbon atoms which may be substituted. R ₃ and R ₄
Are each independently optionally substituted 1-20
An alkyl group having 3 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, or an aralkyl group having 7 to 26 carbon atoms. Or a group having an aromatic amine skeleton represented by the following general formula (3):

Embedded image (Wherein, Ar ₄ represents an optionally substituted arylene group having 6 to 24 carbon atoms. R ₅ and R _5
6 is each independently a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms, 3
Cycloalkyl groups having up to 20 carbon atoms, 6-2
An aryl group having 4 carbon atoms or an aralkyl group having 7 to 26 carbon atoms is shown. Ar ₅ represents an optionally substituted aryl group having 6 to 24 carbon atoms. ) Represents a group having an aromatic ethenylene skeleton. Further, between Ar ₁ and Ar ₂ , Ar ₁ and R
_{And a} ring may be formed between R ₂ and R ₂ and Ar ₂ . And a repeating structural unit represented by the following general formula (4)

Embedded image (Wherein, R ₇ and R ₈ are each independently an optionally substituted alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms,
Aryl groups having 6 to 24 carbon atoms or 7 to 2
Indicate an aralkyl group having 6 carbon atoms. ), And the ratio of the number of units of the repeating structural units (1) and (4) to the sum of the number of units of the repeating structural units (1) and (4) is z and 1-z, respectively.
Is 0.125 ≦ z ≦ 1, and when the sum of the number of units of the repeating structural units (1) and (4) is n,
It relates to a silicon-containing aromatic amine compound having an integer of 3 ≦ n ≦ 8.

The present invention also provides [2] an organic electroluminescent device having at least one layer containing an organic substance between a pair of anodes and cathodes, at least one of which is transparent or translucent. At least one of which is the silicon-containing aromatic amine compound according to [1].

Further, the present invention relates to [3] an electrophotographic photosensitive member using a charge generating material and a hole transporting material on a conductor support, wherein at least one of the hole transporting materials is used.
The present invention relates to the electrophotographic photoreceptor wherein the species is the silicon-containing aromatic amine compound described in [1].

Further, the present invention provides [4] an organic photoconductor element comprising at least a hole transport layer between a pair of transparent or translucent electrodes, wherein the hole transport layer comprises [ [1] An organic photoconductor element comprising the silicon-containing aromatic amine compound described in [1].

[0015]

Next, the present invention will be described in detail.
The silicon-containing aromatic amine compound of the present invention must have a cyclic skeleton.
Shown by the general formula (1) and the optional general formula (4)
Characterized by a repeating structural unit. General
In the formula (1), R₁Is optionally substituted 1
Alkyl groups having up to 20 carbon atoms, 3-20
6-24 cyclic cycloalkyl groups having carbon atoms
Or an aryl group having from 7 to 26 carbon atoms
It is an aralkyl group having an elementary atom. The alkyl group is
It may be linear or branched. The R ₁Is preferably
A straight chain having 1 to 10 carbon atoms which may be substituted
A chain or branched alkyl group having 3 to 10 carbon atoms
Cyclic cycloalkyl group, having 6 to 17 carbon atoms
Aryl groups having, or having 7 to 18 carbon atoms
Aralkyl group. Where it may be replaced
An alkyl group, a cycloalkyl group, an aryl group or
As a substituent of the aralkyl group, 1 to 6 carbon atoms
Having a linear or branched alkyl group or 3 to 6
A cyclic cycloalkyl group having a carbon atom;
You.

Specific examples of R ₁ include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, A heptyl group, an octyl group, etc., and the cycloalkyl group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.The aryl group is substituted with a methyl group, an ethyl group, or a propyl group. May be
Examples include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group and the like, and examples of the aralkyl group include a benzyl group and a phenethyl group which may be substituted with a methyl group, an ethyl group and a propyl group.

In the repeating structural unit represented by the general formula (1), Ar ₁ is an optionally substituted arylene group having 6 to 24 carbon atoms. Preferably,
An arylene group having 6 to 17 carbon atoms which may be substituted. Here, the substituent of the arylene group which may be substituted includes a linear or branched alkyl group having 1 to 6 carbon atoms, or a cyclic cycloalkyl having 3 to 6 carbon atoms. Groups. A
Specific examples of r ₁ include, but are not limited to, phenylene, naphthylene, anthrylene, and the like, which may be substituted with a methyl group, an ethyl group, or a propyl group.

In the general formula (1), the group R ₂ bonded to the nitrogen atom is an optionally substituted alkyl group having 1 to 20 carbon atoms and a cyclic group having 3 to 20 carbon atoms. A cycloalkyl group, an aryl group having 6 to 24 carbon atoms, or an aralkyl group having 7 to 26 carbon atoms. The alkyl group may be linear or branched. The R ₂ is preferably an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic cycloalkyl group having 3 to 10 carbon atoms, 6 An aryl group having from 17 to 17 carbon atoms, or an aralkyl group having from 7 to 18 carbon atoms, and more preferably an optionally substituted 6
Aryl groups having up to 17 carbon atoms. Here, as a substituent of the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group which may be substituted, a linear or branched alkyl group having 1 to 6 carbon atoms, or 3 to 6 carbon atoms. A cyclic cycloalkyl group having 6 carbon atoms is exemplified.

Specific examples of R ₂ include a phenyl group, which may be substituted with a methyl group, an ethyl group and a propyl group.
Examples include a naphthyl group, an anthryl group and a biphenyl group.

Ar ₂ bonded to a nitrogen atom of the general formula (1)
The optionally substituted aryl group is an aryl group having 6 to 24 carbon atoms which may be substituted, and preferably an aryl group having 6 to 17 carbon atoms which may be substituted. Group. Here, the substituent of the aryl group which may be substituted includes a linear or branched alkyl group having 1 to 6 carbon atoms, or 3
Cyclic cycloalkyl groups having up to 6 carbon atoms.

Specific examples of the optionally substituted aryl group of Ar ₂ include a phenyl group, a naphthyl group, an anthryl group and a biphenyl group which may be substituted with a methyl group, an ethyl group or a propyl group. Is done.

Ar ₃ in the group having an aromatic amine skeleton represented by the general formula (2) is an arylene group having 6 to 24 carbon atoms which may be substituted. An arylene group having 6 to 17 carbon atoms. Here, the substituent of the arylene group which may be substituted includes a linear or branched alkyl group having 1 to 6 carbon atoms, or a cyclic cycloalkyl having 3 to 6 carbon atoms. Group.

Specific examples of Ar ₃ include a phenylene group, a naphthylene group, an anthrylene group and a biphenylene group which may be substituted with a methyl group, an ethyl group or a propyl group.

In the group having an aromatic amine skeleton represented by the general formula (2), R ₃ and R ₄ each independently have 1 to 20 carbon atoms which may be substituted. Linear or branched alkyl group, or 3 to
A cyclic cycloalkyl group having 20 carbon atoms, 6
An aryl group having -24 carbon atoms, an aralkyl group having 7-26 carbon atoms, and preferably an optionally substituted linear or branched having 1-10 carbon atoms. An alkyl group, or a cyclic cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 17 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms, more preferably, An aryl group having 6 to 17 carbon atoms which may be substituted. Here, an alkyl group which may be substituted,
Examples of the substituent for the cycloalkyl group, the aryl group and the aralkyl group include a linear or branched alkyl group having 1 to 6 carbon atoms, or a cyclic cycloalkyl group having 3 to 6 carbon atoms. is there. Specific examples of R ₃ and R ₄ include, but are not limited to, a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group which may be substituted with a methyl group, an ethyl group, or a propyl group. Not something.

In the group having an aromatic ethenylene skeleton represented by the general formula (3), an arylene group Ar
₄ is an optionally substituted arylene group having 6 to 24 carbon atoms, preferably an optionally substituted arylene group having 6 to 17 carbon atoms. Here, the substituent of the arylene group which may be substituted includes a linear or branched alkyl group having 1 to 6 carbon atoms, or a cyclic cycloalkyl having 3 to 6 carbon atoms. Group. Specific examples of Ar ₄ include, but are not limited to, a phenylene group, a naphthylene group, and an anthrylene group that may be substituted with a methyl group, an ethyl group, or a propyl group.

The aromatic ether represented by the general formula (3)
Ar in a group having a nylene skeleton_FiveIs replaced
An aryl group having 6 to 24 carbon atoms
Yes _,Preferably, 6 to 17 optionally substituted
An aryl group having a carbon atom. Where is replaced
Examples of the substituent of the aryl group which may have 1 to 6
A linear or branched alkyl group having carbon atoms, or
A cyclic cycloalkyl group having 3 to 6 carbon atoms is
No. Ar_FiveSpecific examples of the methyl group, ethyl
Phenyl, which may be substituted with
Group, naphthyl group, anthryl group, biphenyl group, etc.
Is done.

R ₅ and R ₆ in the group having an aromatic ethenylene skeleton represented by the general formula (3) are each independently a hydrogen atom or may be substituted.
Alkyl groups having 1 to 20 carbon atoms, cyclic cycloalkyl groups having 3 to 20 carbon atoms, 6 to 24
Aryl groups having 7 carbon atoms and aralkyl groups having 7 to 26 carbon atoms. The alkyl group may be linear or branched. R ₅ and R ₆ are preferably each independently a hydrogen atom, or an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, or 3 to 10 A cyclic cycloalkyl group having carbon atoms, an aryl group having 6 to 17 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms, more preferably each independently a hydrogen atom or a substituted A linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 9 carbon atoms It is. Here, as a substituent of the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group which may be substituted, a linear or branched alkyl group having 1 to 6 carbon atoms, or 3 to 6 carbon atoms.
It is a cyclic cycloalkyl group having 6 carbon atoms.

Specific examples of R ₅ and R ₆ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a phenyl group which may be substituted with a methyl group, an ethyl group or a propyl group. . In the general formula (4), R ₇ and R ₈ may be each independently substituted.
Alkyl groups having 1 to 20 carbon atoms, cyclic cycloalkyl groups having 3 to 20 carbon atoms, 6 to 24
Or an aralkyl group having 7 to 26 carbon atoms. The alkyl group may be linear or branched. R ₇ and R ₈ are preferably each independently optionally substituted 1
A linear or branched alkyl group having 10 to 10 carbon atoms, a cyclic cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 17 carbon atoms, or 7 to 18 Is an aralkyl group having the carbon atom of
Here, as a substituent of the alkyl group, cycloalkyl group, aryl group or aralkyl group which may be substituted, a linear or branched alkyl group having 1 to 6 carbon atoms or 3 to 6 carbon atoms. A cyclic cycloalkyl group having 6 carbon atoms is exemplified. As specific examples of R ₇ and R ₈ , a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-
Butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like, and the cycloalkyl group includes cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group which may be substituted with a methyl group, an ethyl group, and a propyl group.As the aralkyl group, a methyl group, an ethyl group, Examples include a benzyl group and a phenethyl group which may be substituted with a propyl group.

The silicon-containing aromatic amine compound used as the hole transport material of the present invention has a repeating structural unit (1)
When the ratio of the number of units of the repeating structural units (1) and (4) to the total number of units of (1) and (4) is z and 1-z, respectively, 0.125 ≦ z ≦ 1, preferably 0.2 ≤z
≦ 1, and when the sum of the number of units of the repeating structural units (1) and (4) is n, it is an integer of 3 ≦ n ≦ 8, preferably an integer of 3 ≦ n ≦ 6.

When used as a hole transport material, the silicon-containing aromatic amine compound may be used alone or as a mixture of two or more. The silicon-containing aromatic amine compound of the present invention can be produced by a method known as the Kipping method, for example, a Journal of Organometallic Chemistry.
llic Chemistry) Vol. C27 (198
0) 198 pages or Journal of Polymer
Science, Polymer Chemistry Edition (Journal of Polymer Science)
ce: Polymer Chemistry Edit
ion), Vol. 22, (1984), p. 159.

That is, a dihalosilane monomer represented by the following general formula (5) or a dihalosilane monomer represented by the following general formula (5) under a high-purity inert atmosphere from which oxygen and moisture have been removed, for example, under a high-purity argon gas atmosphere: It is obtained by bringing a mixture of the dihalosilane monomer represented by 5) and the dihalosilane monomer represented by the following general formula (6) into contact with an alkali metal in an inert solvent to cause a condensation polymerization reaction.

[0032]

Embedded image (Wherein X represents a halogen atom, R ₁ , R ₂ , Ar
The definitions of ₁ and Ar ₂ are the same as those of the general formula (1). )

Embedded image (In the formula, X represents a halogen atom, and the definitions of R ₇ and R ₈ are the same as those of the general formula (4).)

Here, as the halogen element of the dihalosilane monomer, a bromine or iodine atom can be used in addition to the most common chlorine. As the alkali metal, lithium, sodium, potassium or an alloy containing them is used.
Alternatively, it is supplied to the reaction in a state of being dispersed in fine particles.

The inert solvent may be any solvent capable of dissolving the dihalosilane monomer and inert to the sodium metal and the dihalosilane monomer. For example, aromatic solvents such as toluene, xylene and benzene may be used. Hydrocarbons, dodecane, heptane, hexane, aliphatic hydrocarbons such as cyclohexane, diethyl ether, tetrahydrofuran,
Ether solvents such as diethylene glycol dimethyl ether tetrahydropyran can be used. The condensation reaction can be carried out at a temperature between room temperature and the boiling point of the solvent, and the reaction time is not particularly limited, and for example, is preferably in the range of 15 minutes to 24 hours.

The dihalosilane monomer that can be subjected to the Kipping method can be synthesized based on a known synthesis method. That is, it can be obtained by a Grignard reagent of an organic compound such as alkyltrichlorosilane or tetrachlorosilane produced industrially by a so-called direct method, a metathesis reaction using a lithium salt, or a hydrosilylation reaction of hydrosilane with an olefin or an acetylene compound.

Next, the organic EL device of the present invention will be described. The structure of the organic EL device is not particularly limited as long as the silicon-containing aromatic amine compound is contained in an organic compound layer provided between a pair of electrodes, at least one of which is transparent or translucent. A structure is adopted.

For example, a structure in which a light-emitting layer containing the silicon-containing aromatic amine compound or a light-emitting layer is laminated on a hole transport layer containing the silicon-containing aromatic amine compound, and a pair of electrodes are provided on both surfaces thereof, Further, an example in which an electron transporting layer containing an electron transporting material is laminated between the light emitting layer and the cathode is exemplified.

The present invention includes a case where the light emitting layer and the charge transport layer are a single layer and a case where a plurality of layers are combined. Further, a well-known charge transporting material described below, that is, an electron transporting material or a hole transporting material, may be mixed and used in the hole transporting layer as long as the action of the silicon-containing aromatic amine compound is not hindered. When the silicon-containing aromatic amine compound is mixed with another hole transporting material, the mixing ratio is preferably less than 100% by weight based on the silicon-containing aromatic amine compound. It is preferably at most 40% by weight, particularly preferably at most 20% by weight. When the electron transporting materials are mixed and used, the mixing ratio may be appropriately determined in consideration of the luminous efficiency.
Further, it may be a layer in which the silicon-containing aromatic amine compound is dispersed in a binder resin, and a layer in which the silicon-containing aromatic amine compound is mixed with a charge transport material described below and dispersed in a binder resin. You can also.

As the charge transporting material used alone or as a mixture in the organic EL device of the present invention, known materials can be used. Examples of the hole transporting material include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyl Diamine derivatives and the like, as an electron transport material, oxadiazole derivative, anthraquinodimethane or its derivative, benzoquinone or its derivative, naphthoquinone or its derivative, anthraquinone or its derivative, tetracyano anthraquinodimethane or its derivative, fluorenone Derivatives, diphenyldicyanoethylene or its derivatives, diphenoquinone derivatives, and metal complexes of 8-hydroxyquinoline or its derivatives are exemplified.

Specifically, JP-A-63-70257,
JP-A-63-175860, JP-A-2-135359
And JP-A-2-135361, JP-A-2-209988, JP-A-3-37992, and JP-A-3-152184. Of these, a hole transporting material is preferably a triphenyldiamine derivative, an electron transporting material is an oxadiazole derivative,
A metal complex of benzoquinone or a derivative thereof, anthraquinone or a derivative thereof, or 8-hydroxyquinoline or a derivative thereof. More preferably, the hole transporting material is 4,4'-bis (N (3-methylphenyl) -N-phenylamino) biphenyl, and the electron transporting material is 2- (4-biphenylyl) -5- ( 4
-T-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, and tris (8-quinolinol) aluminum. Of these, one or both of the electron transporting material and the hole transporting material may be used simultaneously. These may be used alone or as a mixture of two or more.

When an electron transporting layer is provided between the light emitting layer and the cathode and further in contact with the light emitting layer, the electron transporting layer may be formed using the above electron transporting material. In the case where a second hole transport layer is provided between the hole transport layer and the anode, the hole transport layer may be formed using the hole transport material.

When the charge transporting material is used in a mixture with the light emitting layer, the amount of the charge transporting material varies depending on the kind of the compound to be used. The range may be appropriately determined in consideration of the above. Usually, it is 1 to 40% by weight based on the luminescent material,
More preferably, it is 2 to 30% by weight.

Known light-emitting materials that can be used in the light-emitting layer of the organic EL device of the present invention include low molecular weight compounds such as naphthalene derivatives, anthracene or its derivatives, perylene or its derivatives, polymethine-based, xanthene-based, and coumarin-based materials. , Cyanine-based pigments, 8-
A metal complex of hydroxyquinoline or a derivative thereof, an aromatic amine, tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used. In particular,
For example, JP-A-57-51781 and JP-A-59-19439.
Known ones such as those described in Japanese Patent Publication No. 3 can be used.

Further, as the polymer compound, for example, a conjugated polymer such as poly (p-phenylene) or a derivative thereof, polyphenylenevinylene or a derivative thereof, polyfluorene or a derivative thereof, polyquinoline or a derivative thereof, or polyquinoxaline or a derivative thereof. Phosphors can be used. Specifically, for example, JP-A-5-202355, JP-A-5-320635
JP-A-7-97569, JP-A-7-147190
JP-A-7-278276, JP-A-7-30058
Known ones, such as those described in Japanese Patent Publication No. 0, can be used.

Next, a typical method for producing the organic EL device of the present invention will be described. The transparent or translucent electrode, which is a pair of electrodes composed of an anode and a cathode, includes a transparent or translucent electrode formed on a transparent substrate such as glass or transparent plastic.

As a material for the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, a film (such as NESA) formed using a conductive glass made of indium tin oxide (ITO), tin oxide, or the like, zinc sulfide, Au, Pt, Ag, Cu, or the like is used. As a manufacturing method, a vacuum evaporation method, a sputtering method, a plating method, or the like is used.

On this anode, a hole transport layer containing the above-mentioned aromatic amine compound containing silicon is formed as a hole transport material. Examples of the forming method include a spin coating method, a casting method, a dipping method, a bar coating method, a roll coating method, and the like using a melt, a solution or a mixture of the silicon-containing aromatic amine compound alone or a mixture with the charge transport material. Or a spin coating method using a solution or a mixed solution after mixing and dispersing a binder resin and the silicon-containing aromatic amine compound or a mixture of the charge transport material in a solution state or a molten state and then dispersing the mixture. And a coating method such as a casting method, a dipping method, a bar coating method, and a roll coating method.

The binder resin to be mixed is not particularly limited, but those that do not extremely impair the hole transporting property are preferable, and those that do not strongly absorb visible light are preferably used. For example, poly (N-vinylcarbazole), polyaniline or its derivative, polythiophene or its derivative, poly (phenylenevinylene) or its derivative, poly (2,5-thienylenevinylene) or its derivative, polycarbonate, polyacrylate, polymethyl Acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like are exemplified. Among these, poly (N-vinylcarbazole), polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride and polysiloxane are preferred.

The thickness of the hole transport layer is 0.5 nm to 10 μm.
m, preferably 1 nm to 1 μm. In order to increase the luminous efficiency by increasing the current density, it is more preferable that the
800 nm.

Next, a luminescent layer containing a luminescent material or a luminescent material and a charge transporting material is formed. As a formation method,
Examples thereof include a vacuum deposition method from a powder state of these materials, and a coating method such as a spin coating method, a casting method, a dipping method, a bar coating method, a roll coating method using a melt, a solution or a mixture of these materials. . Among these methods, when a low molecular compound is used, a vacuum evaporation method is preferable. When a polymer compound is used, a coating method such as a spin coating method, a casting method, a dipping method, a bar coating method, and a roll coating method using a solution or a mixed solution is preferable.

The thickness of the light emitting layer is 0.5 nm to 10 μm,
Preferably it is 1 nm to 1 μm. In order to increase the current density to increase the luminous efficiency, it is more preferably 10 to 500.
nm.

When the hole transport layer and the light-emitting layer are thinned by a coating method, the solvent is removed. , 30-300 ° C., preferably 60-300 ° C.
It is desirable to heat and dry at a temperature of 200 ° C.

When an electron transporting layer is further laminated on the light emitting layer, it is preferable to form the electron transporting layer on the light emitting layer after providing the light emitting layer by the above-described film forming method.

The method for forming the electron transporting layer is not particularly limited, but is a vacuum deposition method from a powder state, or a spin coating method after dissolving in a solution, a casting method, a dipping method, a bar coating method, a roll coating method. Or a coating method such as a spin coating method, a casting method, a dipping method, a bar coating method, a roll coating method or the like after mixing and dispersing a binder resin and a charge transport material in a solution state or a molten state and dispersing them. be able to.

The binder resin to be mixed is not particularly limited, but those which do not extremely inhibit charge transport are preferable, and those which do not strongly absorb visible light are suitably used.

For example, poly (N-vinylcarbazole), polyaniline or its derivative, polythiophene or its derivative, poly (p-phenylenevinylene) or its derivative, poly (2,5-thienylenevinylene) or its derivative, polycarbonate, Examples thereof include polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane. In the case where a polymer compound is used, it is preferable to use a coating method in that a film can be easily formed.

The thickness of the electron transporting layer is required to be at least such that no pinholes are generated. However, if the thickness is too large, the resistance of the device increases and a high driving voltage is required, which is not preferable. Therefore, the thickness of the charge transport layer is preferably 0.5 nm to 10 μm, more preferably 1 nm to
It is 1 μm, particularly preferably 5 to 200 nm.

Next, an electrode is provided on the light emitting layer or the electron transport layer. This electrode becomes an electron injection cathode. The material is not particularly limited, but a material having a small ionization energy is preferable. For example, Al, In, Mg, C
a, Li, Mg-Ag alloy, In-Ag alloy, Mg-I
n alloy, Mg-Al alloy, Mg-Li alloy, Al-Li
An alloy, a graphite thin film or the like is used. As a method for manufacturing the cathode, a vacuum evaporation method, a sputtering method, or the like is used.

Next, the electrophotographic photosensitive member of the present invention will be described. The electrophotographic photoreceptor can be applied to a lamination type electrophotographic photoreceptor or a single-layer dispersion type electrophotographic photoreceptor. For example, as shown in FIG. 1, a charge generation layer 2 is formed on a conductive support 1, and a hole transport layer 3 containing the silicon-containing aromatic amine compound is provided on the charge generation layer 2. it can. Alternatively, as shown in FIG. 2, a hole transport layer 3 made of the silicon-containing aromatic amine compound is provided on the conductive support 1, and a charge generation layer 2 is provided on the hole transport layer 3. You can also. Further, as shown in FIG. 3, a photosensitive layer 4 is obtained by dispersing a charge generating substance 2 ′ in a hole transporting material 3 ′ containing the silicon-containing aromatic amine compound on a conductive support 1. Can also be provided.

Examples of the charge generating material include selenium, selenium-tellurium, amorphous silicon, pyrylium salts, azo pigments, bisazo pigments, ansanceron pigments, phthalocyanine pigments, indigo pigments, slen pigments, and toluidine. Pigments, pyrazoline pigments, perylene pigments, quinacridone pigments and the like are exemplified, and one kind or a mixture of two or more kinds can be used so as to have sensitivity in a desired wavelength range.

When used as a laminated electrophotographic photoreceptor, a method for forming the charge generating layer includes a method of depositing the charge generating material in a layer by vacuum evaporation or the like, and a method of dispersing the charge generating material in a binder resin. And a method of forming a film by coating in a layered form.

The coating liquid for forming the charge generating layer by coating is prepared by mixing a charge generating substance, a binder resin and a solvent, and then subjecting the mixture to a conventionally known method, for example, a roll mill, a ball mill, an attritor, a paint shaker or an ultrasonic disperser. Can be dispersed and adjusted. The charge generation layer is formed by applying the coating solution by a conventionally known coating method, for example, a dipping method, a spray coating method, a wire bar method, a doctor blade method, a roll coating method, a spin coating method, or the like. After the formation of the charge generation layer, the pressure is preferably reduced to 30 to 3 under an inert atmosphere.
It is preferable to heat and dry at a temperature of 00C, more preferably 60 to 200C.

Various resins can be used as the binder resin for dispersing the charge generating substance, such as polycarbonate resin, polyarylate resin, polysulfone resin, and the like.
Styrene polymer, acrylic polymer, styrene-acrylic copolymer, ethylene-vinyl acetate copolymer, polypropylene resin, olefin polymer, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer, polyester resin Various polymers such as alkyd resin, polyamide resin, polyurethane resin, epoxy resin, diallyl phthalate resin, silicone resin, ketone resin, polyvinyl butyral resin, polyether resin, phenol resin and photo-curable resin such as epoxy acrylate resin Is exemplified. These binder resins can be used alone or in combination of two or more.

As a solvent used for preparing a coating solution for forming a charge generation layer, a binder resin may be dissolved, and various organic solvents can be used. For example, alcohols such as methanol, ethanol, isopropanol and butanol, aliphatic hydrocarbons such as n-hexane, octane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene Such as halogenated hydrocarbons, dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether,
Ethers such as diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, ketones such as cyclohexane, ethyl acetate, esters such as methyl acetate,
Solvents such as dimethylformamide and dimethylsulfoxide are exemplified, and these may be used alone or as a mixture of two or more. In the laminated photoreceptor shown in FIG. 1 or FIG. 2, the thickness of the charge generation layer 2 is preferably 0.01 to 0.5 μm.

When used as a laminated electrophotographic photoreceptor, the hole transport layer can be formed by dissolving the silicon-containing aromatic amine compound in a solvent and coating it to form a layer, or by using a binder resin. And a method in which the silicon-containing aromatic amine compound is dispersed and formed into a layer by coating.

As the method, a conventionally known coating method,
For example, a dipping method, a spray coating method, a wire bar method, a doctor blade method, a roll coating method, a spin coating method and the like can be mentioned. After the formation of the hole transport layer, the pressure is preferably reduced or under an inert atmosphere.
It is desirable to heat and dry at a temperature of 0 to 300 ° C, more preferably 60 to 200 ° C. At this time, the thickness of the hole transport layer is preferably from 10 to 40 μm, and particularly preferably from 15 to 30 μm.

Various resins can be used as the binder resin in which the silicon-containing aromatic amine compound is dispersed.
For example, polycarbonate resin, polyarylate resin,
Polysulfone resin, styrene polymer, acrylic polymer, styrene-acrylic copolymer, ethylene-vinyl acetate copolymer, polypropylene resin, olefin polymer, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer , Polyester resin, alkyd resin, polyamide resin, polyurethane resin, epoxy resin, diallyl phthalate resin, silicone resin, ketone resin, polyvinyl butyral resin, polyether resin, phenol resin, photo-curable resin such as epoxy acrylate resin, etc. Polymers are exemplified. These binder resins can be used alone or in combination of two or more.

As the solvent used for preparing the coating solution for forming the hole transport layer, the silicon-containing aromatic amine compound, or the silicon-containing aromatic amine compound and the binder resin may be dissolved. Organic solvents can be used. Examples thereof include aromatic solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether and tetrahydrofuran, and halogen solvents such as chloroform.

When used as a single-layer type electrophotographic photoreceptor, a single-layer type photosensitive layer is formed by coating the silicon-containing aromatic amine compound with the charge-generating substance in a layered form. A method of forming a film and a method of forming a film by coating in a form in which the silicon-containing aromatic amine compound and the charge generating substance are dispersed in a binder resin.

A coating solution for forming a single-layer type photosensitive layer by coating may be prepared by coating the silicon-containing aromatic amine compound and the charge generating substance, or further with a binder resin, by a conventionally known method, for example, a roll mill. , A ball mill, an attritor, a paint shaker or an ultrasonic disperser. Alternatively, the charge generation material and a solvent are mixed, or the binder resin is further mixed, and the charge generation material is dispersed using a conventionally known method, for example, a roll mill, a ball mill, an attritor, a paint shaker or an ultrasonic disperser. Prepared solution,
A coating solution can be prepared by dissolving the silicon-containing aromatic amine compound in this solution. At this time, the mixing ratio of the charge generating substance is preferably 1 to 15% by weight, more preferably 5 to 10% by weight, based on the silicon-containing aromatic amine compound in the coating solution.

The single-layer type photosensitive layer is formed by applying the coating solution by a conventionally known coating method, for example, a dipping method, a spray coating method, a wire bar method, a doctor blade method, a roll coating method, a spin coating method or the like.
After the formation of the single-layer type photosensitive layer, the pressure is reduced or under an inert atmosphere, preferably 30 to 300 ° C., more preferably 6 to 30 ° C.
It is desirable to heat and dry at a temperature of 0 to 200 ° C. At this time, the thickness of the single-layer type photosensitive layer is preferably 10 to 40.
μm, and more preferably 15 to 30 μm.

Various resins can be used as the binder resin in which the charge generating substance and the silicon-containing aromatic amine compound are dispersed, and examples thereof include a polycarbonate resin, a polyarylate resin, a polysulfone resin, a styrene polymer, and an acrylic polymer. Coalescence, styrene-acrylic copolymer, ethylene-vinyl acetate copolymer, polypropylene resin, olefin polymer, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer, polyester resin, alkyd resin, polyamide resin, polyurethane Various polymers such as a resin, an epoxy resin, a diallyl phthalate resin, a silicone resin, a ketone resin, a polyvinyl butyral resin, a polyether resin, a phenol resin, and a photocurable resin such as an epoxy acrylate resin are exemplified. These binder resins can be used alone or in combination of two or more.

As a solvent used for preparing a coating solution for forming a single-layer type photosensitive layer, the silicon-containing aromatic amine compound, or the silicon-containing aromatic amine compound and a binder resin may be dissolved. Organic solvents can be used. For example, aromatic solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether and tetrahydrofuran, and halogen solvents such as chloroform are exemplified, and these may be used alone or in combination of two or more.

For the purpose of improving the sensitivity, reducing the residual potential, or reducing the fatigue at the time of repetitive use, the electron-accepting layer is formed on the laminated photosensitive layer comprising the charge generating layer and the hole transporting layer and the single-layered photosensitive layer. Active substance can be contained. Such electron accepting substances include, for example, succinic anhydride, maleic anhydride, dibromosuccinic anhydride, phthalic anhydride,
Tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, pyromellitic anhydride, melitic anhydride, tetradianoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m -Dinitrobenzene, 1,3,5-trinitrobenzene, p-nitrobenzonitrile, bicyclyl chloride, quinone chlorimide, chloranil, bromanyl, dichlorodicyano p-benzoquinone, anthraquinone, dinitroanthraquinone, 9-fluorenylidene malono Dinitrile, polynitro-9-fluorenylidenemalonodinitrile, picric acid, o-nitrobenzoic acid,
p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-
Examples thereof include dinitrosalicylic acid, phthalic acid, melitic acid, and other compounds having a high electron affinity. The addition ratio of the electron accepting substance is preferably 0.01 to 200% by weight, more preferably 0.1 to 100% by weight, based on the charge generating substance.

The laminated photosensitive layer comprising the charge generating layer and the hole transporting layer and the single-layered photosensitive layer described above have storability,
For the purpose of improving durability and environmental resistance, a deterioration inhibitor such as an antioxidant and a light stabilizer can be contained. Compounds used for such purposes include, for example, chromanol derivatives or etherified compounds thereof, chromanol derivatives or esterified compounds, polyarylalkane compounds, hydroquinone derivatives or monodietherified compounds thereof, hydroquinone derivatives or dietherified compounds thereof , Benzophenone derivatives, benzotriazole derivatives, thioether compounds, phosphonic acid esters, phosphite esters, phenylenediamine derivatives, phenol compounds, hindered phenol compounds, linear amine compounds, or cyclic amine compounds are effective.

As the conductive support, various conductive materials can be used. For example, aluminum, copper, tin,
Platinum, gold, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, indium, stainless steel, brass and other simple metals, or plastic materials on which the above metals are deposited, sputtered or laminated, aluminum iodide, tin oxide, Glass coated with indium oxide, indium tin oxide (ITO), or the like can be given.

Next, the organic photoconductive element of the present invention will be described. The organic photoconductor element can be applied to a laminated or single-layer organic photoconductor element. For example,
As shown in FIG. 4, a charge generation layer 2 is formed on a lower electrode 5, a hole transport layer 3 containing the silicon-containing aromatic amine compound is provided on the charge generation layer 2, An electrode 6 can be provided. Or conversely, as shown in FIG. 5, a hole transport layer 3 containing the silicon-containing aromatic amine compound is provided on the lower electrode 5, a charge generation layer 2 is provided on the hole transport layer 3, An upper electrode 6 can be provided thereon. The hole transport layer 3 and the charge generation layer 2 form a laminated organic conductor layer 7. Further, as shown in FIG. 6, a single layer organic photoconductor obtained by dispersing a charge generating substance 2 'in a hole transporting material 3' containing the silicon-containing aromatic amine compound is provided on a lower electrode 5. It is also possible to provide a single layer as the layer 8 and further provide the upper electrode 6 thereon.

Examples of the charge generating substance include selenium, selenium-tellurium, amorphous silicon, pyrylium salts, azo pigments, disazo pigments, ansanceron pigments, phthalocyanine pigments, indigo pigments, slen pigments, and toluidine. Pigments, pyrazoline pigments, perylene pigments, quinacridone pigments and the like are exemplified, and one kind or a mixture of two or more kinds can be used so as to have sensitivity in a desired wavelength range.

As a method for forming the charge generation layer of the laminated organic photoconductor layer, a method in which the charge generation material is deposited in a layer by a vacuum deposition method or the like, or a method in which the charge generation material is dispersed in a binder resin. There is a method of forming a film in a layer by coating.

The coating solution for forming the charge generation layer by coating is prepared by mixing a charge generation material, a binder resin and a solvent, and then subjecting the mixture to a conventionally known method, for example, a roll mill, a ball mill, an attritor, a paint shaker or an ultrasonic disperser. And can be prepared by dispersion. The charge generation layer is formed by applying the coating solution by a conventionally known coating method, for example, a dipping method, a spray coating method, a wire bar method, a doctor blade method, a roll coating method, a spin coating method, or the like. After the formation of the charge generation layer, the pressure is preferably reduced to 30 to 3 under an inert atmosphere.
It is desirable to heat and dry at a temperature of 00 ° C, more preferably 60 to 200 ° C.

Various resins can be used as the binder resin for dispersing the charge generating substance, such as polycarbonate resin, polyarylate resin, polysulfone resin, and the like.
Styrene polymer, acrylic polymer, styrene-acrylic copolymer, ethylene-vinyl acetate copolymer, polypropylene resin, olefin polymer, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer, polyester resin Various polymers such as alkyd resin, polyamide resin, polyurethane resin, epoxy resin, diallyl phthalate resin, silicone resin, ketone resin, polyvinyl butyral resin, polyether resin, phenol resin and photo-curable resin such as epoxy acrylate resin Illustrated,
These binder resins can be used alone or in combination of two or more. As a solvent used for preparing a coating solution for forming a charge generation layer, a binder resin may be dissolved, and various organic solvents can be used.
For example, methanol, ethanol, isopropanol,
Alcohols such as butanol, n-hexane, octane, aliphatic hydrocarbons such as cyclohexane, benzene,
Aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride and chlorobenzene, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, cyclohexane, etc. Ketones, esters such as ethyl acetate and methyl acetate, and solvents such as dimethylformamide and dimethylsulfoxide. These are used alone or in combination of two or more.

In the laminated type photoreceptor shown in FIG. 4 or FIG.
The thickness of the charge generation layer 2 is preferably 0.01 to 0.5 μm.

As a method for forming the hole transporting layer of the laminated organic photoconductor layer, a method in which the silicon-containing aromatic amine compound is dissolved in a solvent and coated to form a layered film, or a method in which the binder resin is used to form a layered film. A method in which a silicon aromatic amine compound is dispersed to form a film by coating in a layered form is exemplified.

As the method, a conventionally known coating method,
For example, it is applied and formed by a dipping method, a spray coating method, a wire bar method, a doctor blade method, a roll coating method, a spin coating method, or the like. After the formation of the hole transporting layer, the pressure is preferably reduced to 30 to 300 ° C., more preferably 60 to 200 ° C. or under an inert atmosphere.
It is desirable to heat and dry at a temperature of ° C. At this time, the thickness of the hole transport layer is preferably 0.05 to 50 μm, and more preferably 0.1 to 10 μm.

Various resins can be used as the binder resin in which the silicon-containing aromatic amine compound is dispersed.
For example, polycarbonate resin, polyarylate resin,
Polysulfone resin, styrene polymer, acrylic polymer, styrene-acrylic copolymer, ethylene-vinyl acetate copolymer, polypropylene resin, olefin polymer, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer , Polyester resin, alkyd resin, polyamide resin, polyurethane resin, epoxy resin, diallyl phthalate resin, silicone resin, ketone resin, polyvinyl butyral resin, polyether resin, phenol resin, photo-curable resin such as epoxy acrylate resin, etc. Polymers are exemplified. These binder resins can be used alone or in combination of two or more.

The solvent used for preparing the coating solution for forming the hole transporting layer may be a compound containing a silicon-containing aromatic amine compound or a compound containing a silicon-containing aromatic amine compound and a binder resin. Can be used. Examples thereof include aromatic solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether and tetrahydrofuran, and halogen solvents such as chloroform.

As a method for forming the single-layer type organic photoconductor layer, a method in which the charge generating substance is dispersed in the silicon-containing aromatic amine compound to form a film in a layer form by coating, A method in which the silicon-containing aromatic amine compound and the charge-generating substance are dispersed and formed into a layer by coating is used.

A coating solution for forming a single-layer type photosensitive layer by coating is prepared by mixing the silicon-containing aromatic amine compound and the charge generating substance, or further a binder resin with a conventionally known method, for example, a roll mill or a ball mill. , An attritor, a paint shaker or an ultrasonic disperser. Alternatively, the charge generation material and a solvent are mixed, or the binder resin is further mixed, and the charge generation material is dispersed using a conventionally known method, for example, a roll mill, a ball mill, an attritor, a paint shaker or an ultrasonic disperser. A coating solution can be prepared by preparing a solution that has been made to dissolve the silicon-containing aromatic amine compound in this solution. At this time, the mixing ratio of the charge generating substance is preferably 1 to 15% by weight, more preferably 5 to 10% by weight, based on the silicon-containing aromatic amine compound in the coating solution.

The single-layer type organic photoconductor layer is formed by applying the coating solution by a conventionally known coating method such as a dipping method, a spray coating method, a wire bar method, a doctor blade method, a roll coating method, and a spin coating method. Is done. After the formation of the single-layer organic photoconductor layer, it is desirable to heat and dry under reduced pressure or an inert atmosphere, preferably at a temperature of 30 to 300 ° C, more preferably 60 to 200 ° C. At this time, the thickness of the single-layer type organic photoconductor layer is preferably in the range of 0.05 to 50 μm, and particularly preferably in the range of 0.1 to 10 μm.

Various resins can be used as the binder resin for dispersing the charge generating substance and the silicon-containing aromatic amine compound. Examples of the resin include a polycarbonate resin, a polyarylate resin, a polysulfone resin, a styrene polymer, and an acrylic polymer. Coalescence, styrene-acrylic copolymer, ethylene-vinyl acetate copolymer, polypropylene resin, olefin polymer, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer, polyester resin, alkyd resin, polyamide resin, polyurethane Various polymers such as a resin, an epoxy resin, a diallyl phthalate resin, a silicone resin, a ketone resin, a polyvinyl butyral resin, a polyether resin, a phenol resin, and a photocurable resin such as an epoxy acrylate resin are exemplified. These binder resins can be used alone or in combination of two or more.

As a solvent used for preparing a coating solution for forming a single-layer type photosensitive layer, the silicon-containing aromatic amine compound or the silicon-containing aromatic amine compound and a binder resin may be dissolved. Organic solvents can be used. For example, aromatic solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether and tetrahydrofuran, and halogen solvents such as chloroform are exemplified, and these may be used alone or in combination of two or more.

For the purpose of improving the sensitivity and the stability, a dye sensitizer or a dye sensitizer may be added to the laminated organic photoconductor layer comprising the charge generation layer and the hole transport layer and the single-layer organic photoconductor layer. A chemical sensitizer can be contained. Examples of the dye sensitizer include malachite green, crystal violet, methyl violet, night blue, Victoria blue, rhodamine B, capri blue, methylene blue, fuchsin, rose bengal, folimethine dye, and thioxanthine pigment. .

Examples of the chemical sensitizer include acetic anhydride, succinic anhydride, maleic anhydride, dibromosuccinic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, 4-
Acid anhydrides such as nitrophthalic anhydride, pyromellitic anhydride, melitic anhydride, tetracarboxylic anhydride, p-benzoquinone, 2,5-dichlorobenzoquinone, benzophenonetetracarboxylic acid, 2,6-dichlorobenzoquinone,
Chloranil, dichlordicyano-p-benzoquinone,
Quinones such as anthraquinone, 2-methylanthraquinone, dinitroanthraquinone, phenanthrene-quinone, acenaphthenequinone, pyranthrenequinone, chrysene-quinone, thio-naphthene-quinone, and triphthaloyl-
Benzene, 4-nitrobenzaldehyde, 2,6-dichlorobenzaldehyde anthracene-9-aldehyde, pyridine-2,6-dialdehyde, vinphenyl-
Aldehydes such as 4-aldehyde, organic phosphonic acids such as 4-chloro-3-nitrobenzene-phosphonic acid, nitrophenols such as 4-nitrophenol, aluminum chloride, zinc chloride, ferric chloride, tetrachloride Metal halides such as tin, antimony pentachloride, magnesium chloride, magnesium bromide, calcium bromide, manganese chloride, cobaltous chloride, and cobaltic chloride; boron halides such as boron trifluoride and boron trichloride Compound, acetophenone, benzobenone, 2-
Ketones such as acetyl-naphthalene, benzyl, benzoin, 5-benzoyl-acenaphthene, 9-acetyl-anthracene, 9-benzoyl-anthracene, acenaphthenequinone-dichloride, anisyl, 2,2-pyridyl and furyl; tetradianoethylene , Tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, p-nitrobenzonitrile, bicyclyl chloride, quinone chlorimide, chloranil, bromanyl, 9-fluorenylidene malono Dinitrile, polynitro-9-fluorenylidenemalonodinitrile, picric acid, o-nitrobenzoic acid,
p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-
Examples thereof include dinitrosalicylic acid, phthalic acid, and melitic acid. The proportion of the dye sensitizer or the chemical sensitizer to be added is preferably 0.01 to 200% by weight, more preferably 0.1 to 100% by weight, based on the charge generating substance.

Further, the above-mentioned laminated organic photoconductor layer composed of the charge generation layer and the hole transport layer and the single-layer organic photoconductor layer have the object of improving storage stability, durability and environmental resistance. Can contain a deterioration inhibitor such as an antioxidant or a light stabilizer. Compounds used for such purposes include, for example, chromanol derivatives or etherified compounds thereof, chromanol derivatives or esterified compounds thereof, polyarylalkane compounds, hydroquinone derivatives or monoetherified compounds thereof, hydroquinone derivatives or dietherified compounds thereof , Benzophenone derivatives, benzotriazole derivatives, thioether compounds, phosphonic acid esters, phosphite esters, phenylenediamine derivatives, phenol compounds, hindered phenol compounds, linear amine compounds, or cyclic amine compounds are effective.

At least one of the lower electrode and the upper electrode of the organic photoconductor element must be transparent or translucent. If both are opaque, irradiating the device with light does not show an electrical response, which is not preferable.

As the material of the lower electrode, various conductive materials can be used. For example, aluminum, copper,
Tin, platinum, gold, silver, vanadium, molybdenum, chromium,
A single metal such as cadmium, titanium, nickel, indium, stainless steel, brass, or the like, or the above-mentioned metal thin film formed on a glass or plastic material is used. Alternatively, a thin film of a conductive polymer such as polyaniline or polyacetylene can be used.

When the lower electrode is a transparent or translucent electrode, a conductive metal oxide film, a translucent thin film of the above-mentioned metal, or the like is used. Specifically, indium tin
A film (eg, NESA) formed using conductive glass made of oxide (ITO), tin oxide, or the like; aluminum, copper, tin, platinum, gold, silver, vanadium, molybdenum,
Chrome, cadmium, titanium, nickel, indium,
Metals such as stainless steel and brass are used. Examples of the method for producing a thin film include a vacuum deposition method, a sputtering method, and a plating method.

As the material for the upper electrode, various conductive materials can be used. For example, aluminum, copper,
Tin, platinum, gold, silver, vanadium, molybdenum, chromium,
Cadmium, titanium, nickel, indium, or the like is used after being formed on a thin film. Alternatively, a thin film of a conductive polymer such as polyaniline or polyacetylene can be used.

When the upper electrode is a transparent or translucent electrode, a conductive metal oxide film, a translucent thin film of the above-mentioned metal, or the like is used. Specifically, indium tin oxide (ITO), tin oxide, aluminum,
Copper, tin, platinum, gold, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, indium, or the like is used. Examples of a method for producing a thin film include a vacuum deposition method, a sputtering method, and a plating method.

[0100]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 [Synthesis of oligocyclo (ethyl (4- (N, N-diphenylamino) phenyl) silane)] 0.7 g of metal sodium cut out in a dry 50 ml three-necked flask under a dry nitrogen atmosphere and dry toluene 16 ml were added.
This flask was set in an ultrasonic disperser, and 100 to 10
At 5 ° C., metallic sodium was dispersed to an average particle size of 30 μm. After the dispersion, the flask was allowed to stand, and the excess toluene (12 ml) in the supernatant was removed with a syringe to obtain a sodium metal suspension.

A magnetic stir bar, a thermocouple, and a rubber septum were attached to a 50 ml three-necked flask that had been dried in the same manner, and 4.9 g of ethyl (4- (N, N-diphenylamino) phenyl) dichlorosilane and 4 ml of dry toluene were attached. Was added to obtain a solution. After the temperature of the flask was raised to 80 ° C., the above-mentioned metal sodium suspension was added to a Teflon cannula for about 10 minutes.
It was added dropwise over a period of minutes. The temperature in the flask was temporarily increased to 120 ° C. by the dropping. The reaction was performed for 4 hours after the start of the dropwise addition, and toluene and isopropyl alcohol were added.
The reaction was stopped and excess sodium metal was deactivated.

The precipitate was separated by centrifugation, washed twice with toluene, and the soluble matter was recovered as a toluene solution. After washing the toluene solution with water and drying over anhydrous magnesium sulfate,
The solvent was distilled off to obtain a resinous substance. This resinous material was made into a tetrahydrofuran solution, reprecipitated with isopropyl alcohol, and purified repeatedly to remove the polymer to obtain 3.2 g of a cyclic product.

From ¹ HNMR, no peak of Si—H or Si—OCH (CH ₃ ) ₂ corresponding to a linear terminal was observed, and the obtained compound was oligocyclo (ethyl) having a cyclic silane compound skeleton. (4- (N, N-diphenylamino) phenyl) silane).

The molecular weight distribution of GPC is from 600 to 20.
At 00, the ring size was found to be 3-6. In the FD-MS spectrum, a peak corresponding to a 3- to 6-membered ring was observed. The yield was 85% (3.2 g).

Example 2 [Oligocyclo (ethyl (4- (N- (4 ′-(2 ″),
Synthesis of 2 "-diphenylethenyl) phenyl) -N-phenylamino) phenyl) silane)] Attach a rubber septum and a gas inlet tube to a 50 ml three-necked flask dried at 200 ° C., evacuate and fill with dry argon. The flask was charged with 0.26 g of metallic sodium in a dry nitrogen atmosphere, dried over metallic sodium, and added with 25 ml of toluene distilled immediately before. Set in a vessel and irradiate ultrasonic waves while heating to 98-105 ° C,
Sodium metal was dispersed to an average particle size of 10 μm to obtain a sodium metal suspension.

The above-mentioned metal sodium suspension was transferred to a similarly dried 300 ml three-necked flask using a Teflon cannula, fitted with a magnetic stirrer, a thermocouple, and a rubber septum, and heated to 95 ° C. . At the same time as the internal temperature of the flask was stabilized, ethyl (4- (N- (4 ′-(2 ″),
20 ml of a dry toluene solution of 2.8 g of 2 "-diphenylethenyl) phenyl) -N-phenylamino) phenyl) dichlorosilane was added dropwise using a dropping funnel over about 30 minutes. After the addition, the reaction solution was concentrated to 10 ml. After the addition of 1 ml of tetrahydrofuran, the temperature of the flask was raised to 85 ° C. by the heat of the reaction, and the reaction was carried out at 80 ° C. for 2 hours after completion of the addition.

After the completion of the reaction, 1 ml of isopropyl alcohol was added to the flask under an argon atmosphere to deactivate excess sodium metal. The precipitate was separated by centrifugation, washed twice with toluene, and the soluble matter was collected as a toluene solution. After the toluene solution was washed with water and dried over anhydrous magnesium sulfate, the solvent was distilled off to obtain 1.59 g of a resinous substance.

The operation of dissolving the obtained resinous substance in tetrahydrofuran and reprecipitating with isopropyl alcohol was repeated to remove the polymer, thereby obtaining 0.85 g of a cyclic substance. ¹ HN
From MR, no peak of Si—H or Si—OCH (CH ₃ ) ₂ corresponding to the linear terminal was observed, and the obtained compound was oligocyclo (ethyl (4- ( (N- (4 '-(2 ", 2" -diphenylethenyl) phenyl) -N-phenylamino) phenyl) silane).

The molecular weight distribution of GPC is 1000-1000.
At 3000, the ring size was found to be 3-6. The yield was 39% (0.85 g).

Example 3 [Oligocyclo (ethyl (4- (N- (4 '-(4 "-
(N ', N'-diphenylamino)) biphenyl) -N
Synthesis of -phenylamino) phenyl) silane)] In the same manner as in Example 1, 0.37 g of metallic sodium was placed in a dry 50 ml three-necked flask under a dry nitrogen atmosphere.
25 ml of dry toluene was added. This flask was set in an ultrasonic disperser under a flow of dry argon,
Ultrasonic waves were irradiated while heating to 5 ° C. to disperse the metallic sodium. After the dispersion, the flask was allowed to stand, and 15 ml of the excess toluene in the supernatant was removed with a syringe, and 1.5 ml of diethylene glycol dimethyl ether was added to obtain a sodium metal suspension.

A magnetic stirrer, a thermocouple and a rubber septum were attached to a 300 ml three-necked flask dried in the same manner, and ethyl (4- (N- (4 '-(4 "-(N', N'-diphenyl)) was added. 4.8 g of amino) biphenyl) -N-phenylamino) phenyl) dichlorosilane and 10 m of dry toluene
was added to obtain a solution. After the temperature of the flask was raised to 95 ° C., the above-mentioned metal sodium suspension was dropped over 10 minutes using a Teflon cannula. After the dropwise addition, the temperature rose to 115 ° C. due to the heat of reaction. After the completion of the dropwise addition, the reaction was performed at 105 ° C. for 30 minutes.

After completion of the reaction, 3 ml of isopropyl alcohol was added to the flask under an argon atmosphere to deactivate the excess metal sodium. The precipitate was separated by a centrifugal separator, washed twice with toluene, and the soluble matter was collected as a toluene solution. After the toluene solution was washed with water and dried over anhydrous magnesium sulfate, the solvent was distilled off to obtain 4.4 g of a resinous substance. The operation of dissolving the obtained resinous substance in tetrahydrofuran and reprecipitating with isopropyl alcohol was repeated to remove the polymer, and 2.74 g of a cyclic product was obtained.

From ¹ HNMR, no peak of Si—H or Si—OCH (CH ₃ ) ₂ corresponding to a linear terminal was observed, and the obtained compound was oligocyclo (ethyl) having a cyclic silane compound skeleton. (4- (N- (4'-
(4 "-(N ', N'-diphenylamino)) biphenyl) -N-phenylamino) phenyl) silane).

The molecular weight distribution of GPC is 1500-4.
At 000, the ring size was found to be 3-7.
The yield was 70% (2.74 g).

Example 4 [Production and evaluation of organic EL device]
On a glass substrate provided with an ITO film having a thickness of 300 nm, 2.0 g of the silicon-containing aromatic amine compound obtained in Example 1 was added.
50% by weight by spin coating using a toluene solution of
The film was formed with a thickness of nm. After drying this at 120 ° C. for 1 hour under reduced pressure, tris (8-quinolinol) aluminum (Alq ₃ ) was used as an electron transporting layer at 0.1 to 0.2 nm.
/ Nm at a rate of 70 nm / s. Finally, an aluminum-lithium alloy (Al: Li = about 20
(0: 1 weight ratio) was evaporated to 100 nm to produce an organic EL device. The degree of vacuum at the time of vapor deposition is all 1 × 10 ^-5 Torr
r or less.

This device has a luminance of 1 at an applied voltage of 4.0 V.
cd / m ² or more and current density of 8.3 mA at 6.0 V
/ Cm ² , and uniform green EL emission with a luminance of 165 cd / m ² was observed. The luminous efficiency at this time is
It was 1.99 cd / A. The brightness was almost proportional to the current density. In addition, the EL spectrum has a peak at 526 nm, and almost coincides with the fluorescence spectrum of the Alq ₃ thin film. Thus, EL emission from Alq ₃ was confirmed. When the applied voltage was further increased, the maximum luminance reached 7938 cd / m ² at 9.2 V.

Further, titanyl phthalocyanine is dispersed in polycarbonate to prepare a coating solution containing a charge generating substance. A charge generation layer is formed by a bar coating method using the above-mentioned coating solution for a charge generation substance on a conductive support on which aluminum is deposited on a Mylar film by a vacuum deposition method. A hole transport layer is formed thereon by a bar coating method using a toluene solution of the silicon-containing aromatic amine compound synthesized in Example 1. This is dried under reduced pressure to obtain an element for evaluating the characteristics of an electrophotographic photosensitive member. This element for evaluating the characteristics of an electrophotographic photosensitive member exhibits excellent electrophotographic photosensitive member characteristics.

Further, a charge generation layer in which metal selenium was deposited on a glass substrate with ITO was formed, and a toluene solution of the product 1 containing the silicon-containing aromatic amine compound synthesized in Example 1 was formed thereon. The hole transport layer is formed by spin coating. Further, a gold electrode is vapor-deposited thereon by a vacuum vapor deposition method to obtain an organic photoconductor element. This organic photoconductor element shows excellent characteristics in photocurrent density / dark current density ratio, photosensitivity, and photoresponse characteristics.

Example 5 [Production and evaluation of organic EL device] The procedure was carried out except that the silicon-containing aromatic amine compound obtained in Example 2 was used in place of the silicon-containing aromatic amine compound obtained in Example 1. An organic EL device was produced in the same manner as in Example 4. This element
At an applied voltage of 3.3 V, the luminance reaches 1 cd / m ² or more,
At 6.0 V, a current having a current density of 44.0 mA / cm ² flowed, and green uniform EL emission with a luminance of 952 cd / m ² was observed. The luminous efficiency at this time was 2.16 cd / A. The brightness was almost proportional to the current density. Also, EL
The spectrum has a peak at 526 nm, and almost coincides with the fluorescence spectrum of the Alq ₃ thin film.
EL emission than q ₃ has been confirmed. When the applied voltage is further increased, the maximum luminance is 12198 cd / m ^{2 at} 8.3V.
Reached.

Example 6 [Preparation and evaluation of organic EL device] The procedure was the same as in Example 1, except that the silicon-containing aromatic amine compound obtained in Example 3 was used instead of the silicon-containing aromatic amine compound obtained in Example 1. An organic EL device was produced in the same manner as in Example 4. This element
With an applied voltage of 3.5 V, the luminance reaches 1 cd / m ² or more,
A current having a current density of 18.3 mA / cm ² flowed at 6.0 V, and uniform green EL light emission with a luminance of 469 cd / m ² was observed. The luminous efficiency at this time was 2.56 cd / A. The brightness was almost proportional to the current density. Also, EL
The spectrum has a peak at 526 nm, and almost coincides with the fluorescence spectrum of the Alq ₃ thin film.
EL emission than q ₃ has been confirmed. When the applied voltage is further increased, the maximum luminance is 14980 cd / m ^{2 at} 9.2 V.
Reached.

Example 7 [Synthesis of oligocyclo (ethyl (4- (N, N-diphenylamino) phenyl) silane-co-dimethylsilane)] A 100 ml three-necked flask dried at 200 ° C was placed under a dry nitrogen atmosphere. 0.69 metal sodium cut out
g and 30 ml of dry toluene were added. This flask was set in an ultrasonic disperser under a flow of dry argon, and
At ~ 105 ° C, metallic sodium was dispersed to an average particle size of 5 µm. After the dispersion, the flask was allowed to stand, and the excess toluene (16 ml) in the supernatant was removed with a syringe to obtain a metallic sodium suspension. Similarly, 2.43 g of ethyl (4- (N, N-diphenylamino) phenyl) dichlorosilane, 0.86 g of dimethyldichlorosilane, and 13 ml of dry toluene were added to a 200 ml three-necked flask dried in the same manner. A mechanical stirring blade, a thermocouple, and a rubber septum were attached thereto, and the above-described metal sodium suspension was dropped using a Teflon cannula over about 50 minutes. The reaction was carried out for 7 hours after the start of the dropping, and toluene and isopropyl alcohol were added to stop the reaction and deactivate the excess metal sodium.

The precipitate was separated by centrifugation, washed twice with toluene, and the soluble matter was recovered as a toluene solution. After washing the toluene solution with water and drying over anhydrous magnesium sulfate,
The solvent was distilled off to obtain a resinous substance. This resinous material was converted to a tetrahydrofuran solution, reprecipitated with isopropyl alcohol, and purified to remove the polymer, thereby obtaining 0.45 g of a cyclic substance. In the FD-MS spectrum, oligocyclo (ethyl (4- (N, N-diphenylamino)) having a 4- to 6-membered ring
A peak corresponding to (phenyl) silane-co-dimethylsilane) and a peak corresponding to tetracyclo (ethyl (4- (N, N-diphenylamino) phenyl) silane) were observed.

Example 8 [Synthesis of oligocyclo (ethyl (4- (N, N-diphenylamino) phenyl) silane-co-propylmethylsilane)] A rubber septum and a gas were placed in a 100 ml three-necked flask dried at 200 ° C. The vessel was fitted with an introduction tube, and cooled while repeating evacuation and filling with dry argon. This flask was charged with metallic sodium 1.11 under a dry nitrogen atmosphere.
g, dried over metallic sodium and added with 30 ml of toluene distilled immediately before. This flask was set in an ultrasonic disperser under a flow of dry argon,
Ultrasonic waves were irradiated while heating to ° C. to disperse the metallic sodium to an average particle size of 10 μm. After dispersion, the flask was allowed to stand, and 6 ml of the excess toluene in the supernatant was removed with a syringe to obtain a metallic sodium suspension.

A mechanical stirring blade, a thermocouple, and a rubber septum were attached to a 200 ml three-necked flask that had been dried in the same manner. The above sodium metal suspension was transferred using a Teflon cannula, and the temperature was raised to 80 ° C. . At the same time when the internal temperature of the flask is stabilized, 5 ml of a dry toluene solution of 1.32 g of ethyl (4- (N, N-diphenylamino) phenyl) dichlorosilane and 3.05 g of propylmethyldichlorosilane is used for about 10 minutes using a dropping funnel. It dripped over. The temperature in the flask was temporarily increased to 90 ° C. by dropping. Since the viscosity of the reaction solution was too high, 20 ml of toluene was added on the way. The reaction was performed for 9 hours after the start of the dropwise addition, and toluene and isopropyl alcohol were added to stop the reaction and deactivate the excess metal sodium.

The precipitate was separated by centrifugation, washed twice with toluene, and the soluble matter was recovered as a toluene solution. After washing the toluene solution with water and drying over anhydrous magnesium sulfate,
The solvent was distilled off to obtain a resinous substance. This resinous material was made into a tetrahydrofuran solution, reprecipitated with isopropyl alcohol, and purified repeatedly to remove the polymer.
I got In the FD-MS spectrum, 4-membered oligocyclo (ethyl (4- (N, N-diphenylamino))
Phenyl) silane-co-propylmethylsilane). The yield was 73% (2.00
g).

Comparative Example 1 [Production and Evaluation of Organic EL Device] The same IT as in Example 4
4,4'-bis (N (3-methylphenyl) -N-phenylamino) biphenyl (TP
A film was formed by spin coating using a 2.0% by weight toluene solution of D). The film was cloudy. Except for this, an organic EL device was produced in the same manner as in Example 4. When voltage was applied to this device, stable EL light emission was not observed due to short circuit.

Comparative Example 2 [Production and Evaluation of Organic EL Device] An organic EL device was produced in the same manner as in Example 4 except that polymethylphenylsilane was used in place of the product 1. This device has a high driving voltage and a luminance of 1 cd / m ² up to an applied voltage of 10.0 V.
Did not cross. Current density of 7.8 mA / c at 18.0 V
A current of m ² flowed, and green uniform EL emission with a luminance of 205 cd / m ² was observed. The instantaneous value of the luminous efficiency at this time was 2.63 cd / A. However, the luminous efficiency of this device declined in a very short time. The brightness was almost proportional to the current density. The EL spectrum is 526n.
Since m has a peak and almost coincides with the fluorescence spectrum of the Alq ₃ thin film, EL emission from Alq ₃ was confirmed. Even when the applied voltage was further increased, the maximum luminance only reached 785 cd / m ² at 25.0 V.

[0128]

According to the present invention, it is possible to obtain a silicon-containing aromatic amine compound having excellent hole transporting ability, excellent film forming properties and excellent durability. By using the compound provided by the present invention, an organic electroluminescent device having excellent electronic properties as compared with conventional ones, an electrophotographic photosensitive member,
Since an organic photoconductor element can be obtained, it has great industrial value.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a schematic structure of a laminated electrophotographic photosensitive member according to the present invention.

FIG. 2 is a cross-sectional view illustrating a schematic structure of a laminated electrophotographic photosensitive member according to the present invention.

FIG. 3 is a cross-sectional view illustrating a schematic structure of a single-layer type electrophotographic photosensitive member according to the present invention.

FIG. 4 is a sectional view showing a schematic structure of a stacked organic photoconductor element according to the present invention.

FIG. 5 is a sectional view showing a schematic structure of a stacked organic photoconductor element according to the present invention.

FIG. 6 is a sectional view showing a schematic structure of a single-layer type organic photoconductor element according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Conductive support 2 ... Charge generation layer 2 '... Charge generation substance 3 ... Hole transport layer 3' ... Hole transport material 4 ... Single layer type photosensitive layer 5 ... Lower electrode 6 ... Upper electrode 7 ... Laminated organic photoconductor layer 8 ... Single layer organic photoconductor layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H05B 33/22

Claims (6)

[Claims] 1. A silicon-containing aromatic amine compound having an aromatic amine compound group in a side chain, wherein silicon atoms in the main chain are cyclically linked, wherein the compound is represented by the following general formula (1): [Wherein, R ₁ is an optionally substituted alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl having 6 to 24 carbon atoms. Group or an aralkyl group having 7 to 26 carbon atoms. R ₂ may be substituted, 1 to
An alkyl group having 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, or an aralkyl group having 7 to 26 carbon atoms is shown. Ar ₁ represents an optionally substituted arylene group having 6 to 24 carbon atoms. Ar ₂ is an optionally substituted aryl group having 6 to 24 carbon atoms, represented by the following general formula (2): (Wherein, Ar ₃ represents an arylene group having 6 to 24 carbon atoms which may be substituted. R ₃ and R ₄
Are each independently optionally substituted 1-20
An alkyl group having 3 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, or an aralkyl group having 7 to 26 carbon atoms. Or a group having an aromatic amine skeleton represented by the following general formula (3): (Wherein, Ar ₄ represents an optionally substituted arylene group having 6 to 24 carbon atoms. R ₅ and R _5
6 is each independently a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms, 3
Cycloalkyl groups having up to 20 carbon atoms, 6-2
An aryl group having 4 carbon atoms or an aralkyl group having 7 to 26 carbon atoms is shown. Ar ₅ represents an optionally substituted aryl group having 6 to 24 carbon atoms. ) Represents a group having an aromatic ethenylene skeleton. Further, between Ar ₁ and Ar ₂ , Ar ₁ and R
_{And a} ring may be formed between R ₂ and R ₂ and Ar ₂ . And a repeating structural unit represented by the following general formula (4): (Wherein, R ₇ and R ₈ are each independently an optionally substituted alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms,
Aryl groups having 6 to 24 carbon atoms or 7 to 2
Indicate an aralkyl group having 6 carbon atoms. ), And the ratio of the number of units of the repeating structural units (1) and (4) to the sum of the number of units of the repeating structural units (1) and (4) is z and 1-z, respectively.
Is 0.125 ≦ z ≦ 1, and when the sum of the numbers of the repeating structural units (1) and (4) is n, 3
A silicon-containing aromatic amine compound, wherein s is an integer of ≦ n ≦ 8. 2. An organic electroluminescence device having at least one layer containing an organic substance between a pair of anodes and cathodes, at least one of which is transparent or translucent, wherein at least one of the organic substances is at least one. An organic electroluminescent device, which is the silicon-containing aromatic amine compound described in the above. 3. An organic electroluminescence device having a layer containing a hole transporting material adjacent to the light emitting layer between the anode and the light emitting layer, wherein at least one of the hole transporting materials is according to claim 1. 3. The organic electroluminescent device according to claim 2, wherein the organic electroluminescent device is a silicon-containing aromatic amine compound. 4. The organic electroluminescent device according to claim 2, further comprising a layer containing an electron transport material between the cathode and the light emitting layer, adjacent to the light emitting layer. 5. An electrophotographic photosensitive member using a charge generation material and a hole transport material on a conductor support, wherein at least one of the hole transport materials is the silicon-containing aromatic compound according to claim 1. An electrophotographic photoreceptor, which is an aromatic amine compound. 6. An organic photoconductor device comprising at least one hole-transporting layer between a pair of transparent or translucent electrodes, wherein the hole-transporting layer is a silicon-containing aromatic compound according to claim 1. An organic photoconductor device comprising a group III amine compound.