JP3185279B2 - Novel diamino compound, photoreceptor and electroluminescent device using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel compound having a diamino structure. The diamino compound can be used as a photosensitive material, and more specifically, can be used as a charge transport material for a photoreceptor or an electroluminescent device.

[0002]

2. Description of the Related Art Conventionally, various organic compounds usable as photosensitive materials and charge transport materials have been known, such as anthracene derivatives, anthraquinone derivatives, imidazole derivatives, carbazole derivatives, and styryl derivatives.
JP-A-2-190864 discloses the following general formula:

Embedded image [Wherein Ar _{1 to} ARr and R _{1 to} R ₂ represent those described in the above publication], the arylamine compound represented by the following general formula is disclosed in JP-A-2-59761.

Embedded image A triarylamine derivative represented by the formula [where Ar _{1 to} Ar ₄ and X _{1 to} X ₂ are those described in the above publication] is disclosed. Also, following generally in JP 64-566 _{formula: A-CH 2 CH 2 -Ar} 2 -CH 2 CH 2 -A [ wherein, A and Ar ² are those described above publication 'in The disclosed arylamine compounds are disclosed.

However, when the above-mentioned materials are applied to, for example, a photoreceptor, they are basically required to be excellent in photosensitivity or charge transporting property. , Weather resistance and the like are required, and there is almost no material satisfying such characteristics.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a novel diamino compound which is different from any of the above structures. Another object of the present invention is to provide a photoreceptor using the novel diamino compound. The present invention
Another object of the present invention is to provide an electroluminescent device using the novel diamino compound for a charge transport layer.

[0005]

Means for Solving the Problems The present invention provides the following general formula:
[I]:

Embedded image A diamino compound represented by the formula:

In the general formula [I], Ar ₁ and Ar ₂ each represent an alkyl group such as a methyl group, an ethyl group or a propyl group, an aralkyl group such as a benzyl group or a phenethyl group, or an aryl group such as a phenyl group. , A biphenyl group or a heterocyclic group, for example, a thienyl group, a furyl group, a pyrrolyl group or a pyridyl group. These groups may have a substituent of an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group) or an alkoxy group (eg, methoxy group). Preferred Ar ₁ and Ar ₂ are a phenyl group and a biphenyl group. The mobility of charge is further improved by the biphenyl group.

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom, an alkyl group such as a methyl group, an ethyl group or a propyl group; an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group; , Halogen atom
(Fluorine atom, chlorine atom, bromine atom, etc.). An alkyl group is preferred from the viewpoint of compatibility with the resin.

X is -O-, -S-, or the following formula:

Embedded image Represents R ₆ and R _{7 in} Formula 1 each represent a hydrogen atom, an alkyl group such as a methyl group, an ethyl group or a propyl group, or an aryl group such as a phenyl group or a naphthyl group. n represents an integer of 1 to 4.

Specific examples of the compound having a diamino structure represented by the general formula [I] include those having the following structural formulas.

Embedded image

[0010]

Embedded image

[0011]

Embedded image

[0012]

Embedded image

[0013]

Embedded image

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image

In the above compound examples [2], [3], [4], [5],
[6], [7], [9], [10], [12], [13], [16],
[17], [18], [19], [22], [23], [30],
[32], [33], [34], [36] are particularly preferred.

The diamino compound represented by the general formula [I] is
It can be synthesized by a usual method. For example, the following general formula [II]:

Embedded image [Wherein X, R ₂ , R ₃ and R ₃ are the same as those of the general formula [I]] and a diamine compound represented by the following general formula [II
I], [IV], [V] and [VI]:

Embedded image [Wherein R ₁ and R ₅ , and Ar ₁ and Ar ₂ are the same as those of the general formula [I]] in an appropriate solvent in the presence of a basic compound or a transition metal compound catalyst. , Ullmann
It can be synthesized by a reaction.

Further, after the compound represented by the general formula [II] is acetylated, the iodides of the general formulas [III] and [V] are condensed, then deacetylated, and then the general formula [IV] ] And [VI] may be condensed.

In addition, the general formula [VII]:

Embedded image [Wherein R ₂ , R ₃ , R ₄ and X are the same as those in the general formula [I]] and the following general formula [VIII]
And [IX]:

Embedded image [Wherein R ₁ , R ₅ and Ar ₁ -Ar ₂ are the same as those in formula [I]] in a suitable solvent in the presence of a basic compound or a transition metal compound catalyst. Ull
It can also be synthesized by the mann reaction.

As the basic compound used in the synthesis of the diamino compound of the present invention, hydroxides, carbonates, hydrogencarbonates, and alcoholates of alkali metals are generally used, and quaternary ammonium compounds and fatty acids are used. Organic bases such as aromatic amines and aromatic amines can also be used.
Of these, carbonates and bicarbonates of alkali metals and quaternary ammoniums are preferably used. Furthermore,
Most preferred are alkali metal carbonates and bicarbonates from the viewpoints of reaction rate and thermal stability.

The transition metal or transition metal compound used in the synthesis of the diamino compound of the present invention includes, for example, Cu,
Metals such as Fe, Co, Ni, Cr, V, Pd, Pt, and Ag and their compounds are used, but copper and palladium and their compounds are preferred from the viewpoint of yield. The copper compound is not particularly limited, and most copper compounds are used, but cuprous iodide, cuprous chloride, cuprous oxide, cuprous bromide, cuprous cyanide, cuprous sulfate , Cupric sulfate, cupric chloride, cupric hydroxide, cupric oxide, cupric bromide, cupric phosphate, cuprous nitrate, cupric nitrate, copper carbonate, primary acetic acid Copper, cupric acetate and the like are preferred. Among them, especially CuC
1, CuCl ₂ , CuBr, CuBr ₂ , CuI, CuO, Cu
₂ O, CuSO ₄ , and Cu (OCOCH ₃ ) ₂ are preferred in that they are easily available. As the palladium compound, halides, sulfates, nitrates, organic acid salts and the like can be used. The amount of the transition metal and its compound used is 0.5 to 500 mol% of the iodide to be reacted.

The solvent used in the synthesis may be any commonly used solvent, but aprotic polar solvents such as nitrobenzene, dimethylformamide, dimethylsulfoxide and N-methylpyrrolidone are preferably used.

The reaction is generally carried out under normal pressure at 100 to 250
The reaction is carried out at a temperature of ° C., but may be carried out under pressure. After the completion of the reaction, the solids deposited in the reaction solution are removed, and then the solvent is removed to obtain a product.

These diamino compounds may be used alone or in combination. It is also possible to use a mixture with another charge transporting substance, for example, a hydrazone compound.
The diamino compound represented by the general formula [I] is excellent in photosensitivity and charge transportability, can be used very effectively as a photoconductive material, and is particularly excellent in charge transportability.

The diamino compound represented by the general formula [I] of the present invention can be used as a photosensitive material for a photoreceptor, particularly as a charge transporting substance. Further, it can be used for a charge transporting layer of an electroluminescent element by utilizing its charge transporting property.

First, the case where the diamino compound represented by the general formula [I] is used as a charge transport material for a photoreceptor will be described. Various types of photoreceptors are known as photoreceptors, and the diamino compound of the present invention can be applied to any of these types of photoreceptors. For example, a single layer photoreceptor having a photosensitive layer formed by dispersing a charge generation material and a charge transport material in a binder resin on a support, or a charge generation layer containing a charge generation material as a main component on a support may be used. And a so-called laminated photoreceptor provided with a charge transport layer thereon. One or more diamino compounds of the present invention are used as a charge transport material. The diamino compound acts as a charge transporting substance, and can transport the charge carriers generated by absorbing light extremely efficiently. In particular, a photoconductor which greatly contributes to the improvement of charge mobility and has excellent high-speed response can be obtained.

Further, since the diamino compound of the present invention is excellent in ozone resistance and light stability, a photosensitive member excellent in durability can be obtained. Furthermore, the diamino compound of the present invention has good compatibility with the binder resin, hardly precipitates crystals, and contributes to improvement in sensitivity and repetition characteristics.

As the charge generating material, bisazo pigments,
Triarylmethane dyes, thiazine dyes, oxazine dyes, xanthene dyes, cyanine dyes, styryl dyes, pyrylium dyes, azo pigments, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments , Selenium alloys such as selenium, selenium / tellurium, selenium / arsenic, cadmium sulfide, cadmium selenide , Zinc oxide, and amorphous silicon. In addition, any material that absorbs light and generates charge carriers at an extremely high probability can be used.

Examples of suitable binder resins include, but are not limited to, saturated polyester resins, polyamide resins, acrylic resins, ethylene-vinyl acetate resins, ionically crosslinked olefin copolymers (ionomers), styrene −
Thermoplastic resins such as butadiene block copolymer, polycarbonate, vinyl chloride-vinyl acetate copolymer, cellulose ester, polyimide, styrene resin; epoxy resin, urethane resin, silicone resin, phenol resin, melamine resin, xylene resin, alkyd resin Thermosetting resin such as thermosetting acrylic resin; photocurable resin; and photoconductive resin such as polyvinyl carbazole, polyvinyl pyrene, polyvinyl anthracene, and polyvinyl pyrrole. These can be used alone or in combination. These electrically insulating resins were measured alone to be 1 × 10
It is desirable to have a volume resistance of ¹² Ω · cm or more.

In order to manufacture a single-layer type photoreceptor, fine particles of a charge generating material are dispersed in a resin solution or a solution in which a charge transporting material and a resin are dissolved, and this is coated on a conductive support and dried. Good. At this time, the thickness of the photosensitive layer is 3 to 3
0 μm, preferably 5 to 20 μm. If the amount of the charge generating material used is too small, the sensitivity is poor, and if the amount is too large, the chargeability is deteriorated and the mechanical strength of the photosensitive layer is reduced, so that the proportion in the photosensitive layer is 1 part by weight of the resin. The range is 0.01 to 2 parts by weight, preferably 0.2 to 1.2 parts by weight. The diamino compound represented by the general formula [I] as a charge transporting material is used in an amount of 0.01 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, more preferably 1 part by weight of the binder resin. 0.2 to 1.2 parts by weight. 0.
If the amount is less than 01 parts by weight, the sensitivity is poor, and if it is more than 2 parts by weight, the film forming property is poor and the mechanical strength of the photosensitive layer is also weak.

In order to prepare a laminated type photoreceptor, a charge generation material is vacuum-deposited on a conductive support, or dissolved in an appropriate solvent and applied, or a pigment is applied to an appropriate solvent or a necessary solvent. For example, it is obtained by applying and drying a coating solution prepared by dispersing in a solution in which a binder resin is dissolved, and then applying and drying a solution containing a charge transport material and a binder resin thereon. At this time, the thickness of the charge generation layer is 4 μm or less, preferably 2 μm or less, and the thickness of the charge transport layer is 3 to 50 μm.
μm, preferably 5 to 30 μm. The ratio of the charge transporting material in the charge transporting layer is 0.2 to 1 part by weight of the binder resin.
It is 2 parts by weight, preferably 0.3 to 1.3 parts by weight.

The photoreceptor of the present invention can be used together with a binder resin together with a plasticizer such as halogenated paraffin, polychlorinated biphenyl, dimethylnaphthalene, dibutyl phthalate, O-terphenyl, chloranyl, tetracyanoethylene, 2,4,7.
An electron-withdrawing sensitizer such as trinitrofluorenone, 5,6-dicyanobenzoquinone, tetracyanoquinodimethane, tetrachlorophthalic anhydride, 3,5-dinitrobenzoic acid, methyl violet, rhodamine B, cyanine dye, pyrylium salt And sensitizers such as thiapyrylium salts. As the electrically insulating binder resin used in the present invention, a binder such as a thermoplastic resin or a thermosetting resin, a photocurable resin, or a photoconductive resin known per se, which is electrically insulating, can be used. . As the conductive support used in the photoreceptor of the present invention, a foil or plate of copper, aluminum, silver, iron, nickel or the like in the form of a sheet or a drum is used, or these metals are used as a plastic film. Vacuum evaporation, electroless plating, etc., or conductive polymer, indium oxide,
A layer obtained by applying or depositing a layer of a conductive compound such as tin oxide on a support such as paper or a plastic film is also used.

FIGS. 1 to 5 schematically show examples of the constitution of a photoreceptor using the diamino compound of the present invention. Figure 1 shows the substrate
(1) A photosensitive member in which a photosensitive layer (4) in which a charge generating material (3) and a charge transporting material (2) are mixed with a binder is formed, and the diamino compound of the present invention is used as the charge transporting material. Have been. FIG. 2 shows a function-separated type photoreceptor having a charge generation layer (6) as a photosensitive layer and a charge transport layer (5).
The charge transport layer (5) is formed on the surface of (6). The charge transport layer (5) contains the diamino compound of the present invention. FIG. 3 shows a function-separated type photoreceptor having a charge generation layer (6) and a charge transport layer (5) as in FIG. 2, but the charge transfer layer (5) has a surface opposite to FIG. A generation layer (6) is formed. FIG. 4 shows a surface protective layer on the surface of the photoreceptor of FIG.
(7), and the photosensitive layer (4) is a charge generating layer (6).
And a function-separated type photoconductor having a charge transport layer (5). FIG. 5 shows an intermediate layer between the substrate (1) and the photosensitive layer (4).
(8), the intermediate layer (8) has improved adhesion,
It can be provided to improve coatability, protect the substrate, and improve charge injection from the substrate to the photosensitive layer.

As the material used for the intermediate layer, polyimide, polyamide, nitrocellulose, polyvinyl butyral, polyvinyl alcohol, aluminum oxide and the like are suitable, and the film thickness is desirably 1 μm or less.

The diamino compound represented by the general formula [I] of the present invention can be applied to a charge transport layer of an electroluminescence device by utilizing its charge transport property. Hereinafter, a case where the diamino compound of the present invention is applied to a charge transport layer of an electroluminescent device will be described.

The organic electroluminescent element is composed of at least an organic light emitting layer and a charge transport layer containing a diamino compound between electrodes. FIG. 6 schematically shows a cross section of the electroluminescent element. In the figure, (11) is an anode, on which a charge transport layer (12) and an organic light emitting layer (13)
And a cathode (14) are sequentially laminated,
The charge transport layer contains the diamino compound represented by the general formula [I]. By applying a voltage to the anode (11) and the cathode (14), the organic light emitting layer (13) develops color.

Anode of organic electroluminescence element
As the conductive material used as (11), those having a work function of more than 4 eV are preferable, and carbon, aluminum, vanadium, iron, cobalt, nickel, copper, zinc,
Tungsten, silver, tin, gold and their alloys,
Tin oxide and indium oxide are used. The metal forming the cathode 14 preferably has a work function of less than 4 eV, and magnesium, calcium, titanium, yttrium, lithium, gadolinium, ytterbium, ruthenium, manganese, and alloys thereof are used.

In the organic electroluminescence element, at least the anode (11) or the cathode (14) is a transparent electrode so that light emission can be seen. At this time, if a transparent electrode is used for the cathode, the transparency is likely to be impaired. Therefore, it is preferable to use the anode as the transparent electrode. In the case of forming a transparent electrode, a conductive material as described above may be formed on a transparent substrate by means of vapor deposition, sputtering, or the like so as to secure a desired light-transmitting property. As a transparent substrate, it has a moderate strength, when producing an electroluminescent element,
It is not adversely affected by heat due to vapor deposition and the like, and is not particularly limited as long as it is transparent.Examples of such a material include a glass substrate and a transparent resin such as polyethylene, polypropylene, polyether sulfone, and polyether ether ketone. It is also possible to use. As a transparent electrode formed on a glass substrate, commercially available products such as ITO and NESA are known, and those may be used.

The charge transport layer (12) is made of the above-mentioned general formula [I]
May be formed by vapor deposition of the diamino compound represented by the formula or by spin-coating an appropriate solution or resin solution of the diamino compound. When formed by the vapor deposition method, the thickness is usually 0.01 to 0.3 μm. When formed by the spin coating method, the content of the diamino compound is about 20 to 500% by weight based on the binder resin. The thickness may be about 0.05 to 1.0 μm.

An organic light emitting layer is formed on the thus formed charge transport layer (12). As the organic light-emitting material used for the organic light-emitting layer, known materials can be used. For example, epidolidine, 2,5-bis [5,7-di-t-pentyl-2-benzoxazolyl] thiophene, 2,2′- (1,
4-phenylenedivinylene) bisbenzothiazole, 2,
2 ′-(4,4′-biphenylene) bisbenzothiazole,
5-methyl-2- {2- [4- (5-methyl-2-benzoxazolyl) phenyl] vinyl} benzoxazole,
5-bis (5-methyl-2-benzoxazolyl) thiophene, anthracene, naphthalene, phenanthrene, pyrene, chrysene, perylene, perinone, 1,4-diphenylbutadiene, tetraphenylbutadiene, coumarin,
Macridine stilbene, 2- (4-biphenyl) -6-phenylbenzoxazole, aluminum trisoxine, magnesium bisoxin, bis (benzo-8-quinolinol) zinc, bis (2-methyl-8quinolinolate) aluminum oxide, indium tris Oxine, aluminum tris (5-methyloxin), lithium oxine, gallium trioxin, calcium bis
(5-chlorooxin), polyzinc-bis (8-hydroxy-5-quinolinonyl) methane) dilithium epindridione, zinc bisoxin, 1,2-phthaloperinone,
Examples thereof include 2-naphthaloperinone. Also, common fluorescent dyes such as fluorescent coumarin dye, fluorescent perylene dye, fluorescent pyran dye, fluorescent thiopyran dye,
Fluorescent polymethine dyes, fluorescent merocyanine dyes, fluorescent imidazole dyes and the like can also be used. Among them, particularly preferred are chelated oxinoid compounds. The organic light-emitting layer may have a single-layer structure of the above-described light-emitting substance, or in order to adjust characteristics such as the color of light emission and the intensity of light emission,
It may have a multilayer structure. Next, the above-described cathode is formed on the organic light emitting layer.

As described above, the charge transport layer (12) is provided on the anode (11).
The case where the light emitting layer (13) and the cathode (14) are sequentially laminated to form an organic luminescence element has been described.
A light emitting layer (13), a charge transport layer (12) and an anode may be sequentially laminated on (14).

One set of transparent electrodes is connected to each electrode with a suitable lead wire (15) such as a nichrome wire, a gold wire, a copper wire, a platinum wire, etc.
The organic luminescence element emits light when an appropriate voltage (Vs) is applied to both electrodes.

The organic electroluminescent device of the present invention is applicable to various display devices, display devices, and the like. Hereinafter, the present invention will be described with reference to specific examples. In the following examples, “parts” means
Unless otherwise specified, it means “parts by weight”.

Synthesis Example Synthesis of diamino compound [7] 2.92 g (0.01 mol) of a diamino compound represented by the following formula

Embedded image p-iodobiphenyl 14.6 g (0.06 mol), potassium carbonate 14 g (0.12 mol), copper powder 4 g (0.06 mol)
4 mol) and 100 g of nitrobenzene were charged into a 500 ml four-necked flask equipped with a reflux condenser, and charged under a nitrogen stream.
The reaction was stirred at 0 ° C. for 30 hours. After completion of the reaction, nitrobenzene was distilled off by steam distillation, 200 g of tetrahydrofuran was added, and the solid was filtered. After the filtrate was separated by silica gel column chromatography, the separated product was recrystallized in toluene and purified to obtain 5.8 g of pale yellowish white crystals. The results of the elemental analysis are as shown in Table 1 below (C ₆₆
As H ₄₈ N ₂ O _2).

[0046]

[Table 1]

Example 1 Application of Photosensitive Material to Charge Transporting Material Example 1 Bisazo compound represented by the following general formula [A]

Embedded image 0.45 part of a polyester resin (Vylon 200; manufactured by Toyobo Co., Ltd.) and 0.45 part of the resin were dispersed together with 50 parts of cyclohexanone by a sand grinder. The obtained dispersion of the bisazo compound was applied on a 100-μm-thick aluminized mylar using a film applicator so that the dry film thickness became 0.3 g / m ^2, and then dried.

On the charge generation layer thus obtained, 70 parts of a diamino compound [2] and a polycarbonate resin
(Panlite K-1300; manufactured by Teijin Chemicals Ltd.)
-A solution dissolved in 400 parts of dioxane was dried to a film thickness of 16
It was applied to a thickness of μm and dried to form a charge transport layer. Thus, an electrophotographic photoreceptor having two photosensitive layers was obtained.

The photoreceptor thus obtained was applied to a commercially available electrophotographic copying machine (EP-470Z, manufactured by Minolta Camera Co., Ltd.).
Corona charging at −6 Kv, initial surface potential V ₀ (V), exposure amount E _1/2 (lux · se
c) Decay rate DD of initial potential when left in the dark for 1 second
R ₁ (%) was measured.

Examples 2 to 4 In the same manner as in Example 1, but having the same constitution, except that diamino compound [3], [4], [5] was used instead of diamino compound [2] used in Example 1. Were prepared respectively. V ₀ , E _1/2 , and DDR ₁ of the photoreceptor thus obtained were measured in the same manner as in Example 1.

Example 5 A bisazo compound represented by the following general formula [B]:

Embedded image 0.45 parts, polystyrene resin (molecular weight 40000)
45 parts were dispersed together with 50 parts of cyclohexanone by a sand grinder.

The obtained dispersion of the bisazo compound was applied to a thickness of 1
Using a film applicator, the film was coated on a 00 μm aluminized mylar using a film applicator to a dry film thickness of 0.3 g / m ² and then dried. A solution prepared by dissolving 70 parts of a diamino compound [6] and 70 parts of a polyarylate resin (U-100; manufactured by Unitika Ltd.) in 400 parts of 1,4-dioxane is obtained on the thus obtained charge generating layer. It was applied to a thickness of 16 μm and dried to form a charge transport layer. Thus, an electrophotographic photosensitive member having a two-layer photosensitive layer was produced.

Examples 6 to 8 In the same manner as in Example 5, but having the same constitution, except that diamino compound [7], [9], [10] is used instead of diamino compound [6] used in Example 5. Were prepared respectively.
V ₀ , E _1/2 , and DDR ₁ of the photoreceptor thus obtained were measured in the same manner as in Example 1.

Example 9 Polycyclic quinone pigment represented by the following general formula [C]:

Embedded image 0.45 parts, polycarbonate resin (Panlite K-1
3000: Teijin Chemicals Ltd.) 0.45 part of dichloroethane 5
It was dispersed by a sand mill together with 0 parts. The resulting dispersion of the polycyclic quinone pigment was applied onto a 100-μm-thick aluminized mylar using a film applicator so that the dry film thickness was 0.4 g / m ^2, and then dried. A diamino compound is placed on the charge generation layer thus obtained.
[11] A solution prepared by dissolving 60 parts of polyarylate resin (U-100; manufactured by Unitika) in 50 parts of 400 parts of 1,4-dioxane so as to have a dry film thickness of 18 μm is dried, and then dried for charge transport. A layer was formed. Thus, an electrophotographic photosensitive member having a two-layer photosensitive layer was produced.

Examples 10 to 11 In the same manner as in Example 9, except that the diamino compounds [12] and [13] are used in place of the diamino compound [11] used in Example 9, respectively. The body was made. V ₀ , E _1/2 , and DDR ₁ of the photoreceptor thus obtained were measured in the same manner as in Example 1.

Example 12 A perylene pigment represented by the following general formula [D]

Embedded image 0.45 part of butyral resin (BX-1; manufactured by Sekisui Chemical Co., Ltd.) was dispersed in a sand mill together with 50 parts of dichloroethane. The resulting perylene pigment dispersion was applied on a 100 μm-thick aluminized mylar using a film applicator so that the dry film thickness was 0.4 g / m ^2, and then dried. A solution prepared by dissolving 50 parts of a diamino compound [16] and 50 parts of a polycarbonate resin (PC-Z; manufactured by Mitsubishi Gas Chemical Company) in 400 parts of 1,4-dioxane was dried on the charge generation layer thus obtained. Coating was performed so that the film thickness became 18 μm to form a charge transport layer. Thus, an electrophotographic photosensitive member having a two-layer photosensitive layer was produced.

Examples 13 and 14 The same method as in Example 12, except that diamino compounds [17] and [18] were used in place of diamino compound [16] used in Example 12, respectively. The body was made. V ₀ , E _1/2 , and DDR ₁ of the photoreceptor thus obtained were measured in the same manner as in Example 1.

Example 15 0.45 part of titanyl phthalocyanine, butyral resin
0.45 part (BX-1; manufactured by Sekisui Chemical Co., Ltd.) was dispersed together with 50 parts of dichloroethane by a sand mill. Using a film applicator, the obtained dispersion of the phthalocyanine pigment was put on an aluminized mylar having a thickness of 100 μm.
The coating was applied so that the dry film thickness became 0.3 g / m ^2, and then dried. On the charge generation layer thus obtained, 50 parts of a diamino compound [19] and a polycarbonate resin (PC
-Z; manufactured by Mitsubishi Gas Chemical Company) 50 parts with 1,4-dioxane 4
The solution dissolved in 00 parts was applied to a dry film thickness of 18 μm to form a charge transport layer. Thus, 2
An electrophotographic photoreceptor having a photosensitive layer composed of layers was prepared.

Examples 16 to 17 In the same manner as in Example 15, except that the diamino compound [22] and [23] were used instead of the diamino compound [19] used in Example 15, respectively. The body was made. V ₀ , E _1/2 , and DDR ₁ of the photoreceptor thus obtained were measured in the same manner as in Example 1.

Example 18 50 parts of copper phthalocyanine and 0.2 parts of tetranitro copper phthalocyanine were dissolved in 500 parts of 98% concentrated sulfuric acid with sufficient stirring, and the mixture was poured into 5000 parts of water. After precipitating the conductive material composition, it was filtered, washed with water, and dried at 120 ° C. under reduced pressure. 10 parts of the photoconductive composition thus obtained were mixed with 22.5 parts of a thermosetting acrylic resin (Acrydic A405; manufactured by Dainippon Ink) and a melamine resin (Super Beckamine J).
820; manufactured by Dainippon Ink and the like) 7.5 parts, diamino compound
[34] 15 parts were placed in a ball mill pot together with 100 parts of a mixed solvent obtained by mixing methyl ethyl ketone and xylene in the same amount, and dispersed for 48 hours to prepare a photosensitive coating solution. The coating solution was applied on an aluminum substrate and dried. About 15μ thick
A photosensitive layer of m was formed to produce a photosensitive member. The photoreceptor thus obtained was subjected to the same method as in Example 1, except that corona charging was performed at +6 Kv, and V ₀ , E _1/2 , and DDR ₁ were measured.

Examples 19 to 21 In the same manner as in Example 18, but having the same constitution, except that the diamino compound [34] used in Example 18 was replaced with diamino compounds [30], [32] and [36] Were prepared respectively. Example 1 of the photoreceptor thus obtained was used.
V ₀ , E _1/2 , and DDR ₁ were measured in the same manner as in Example 8.

Comparative Examples 1 to 4 In the same manner as in Example 18 and having the same constitution, except that the diamino compound used in Example 18 was replaced by the following compound
Example 18 except that [E], [F], [G], and [H] were used.
A photoreceptor was produced in exactly the same manner as described above.

Embedded image With respect to the photoreceptor thus obtained, V ₀ , E _1/2 , and DDR ₁ were measured in the same manner as in Example 18.

Comparative Examples 5 to 7 In the same manner as in Example 18, but having the same constitution, except that the diamino compound [34] used in Example 18 was replaced by the following compounds [I], [J] and [K] A photoconductor was prepared in the same manner as in Example 18, except that each was used.

Embedded image In Comparative Examples 1 to 7, compounds [G], [H] and [I]
It was observed that, in the photosensitive coating solution using No. 4, some crystals were precipitated during the coating of the photosensitive layer. The thus obtained photosensitive member, V _0, E _1/2 in the same manner as in Example 15,
DDR ₁ was measured. Examples 1 to 21, are summarized in Table 2 and Table 3 the results of measurement of Comparative Example 1 to 7 V ₀ obtained _{photoreceptor, E 1/2, DDR 1} .

[0064]

[Table 2]

[0065]

[Table 3]

As can be seen from Tables 2 and 3, the photoreceptor of the present invention has a sufficient charge retention ability and a small dark decay rate as a photoreceptor, regardless of whether it is a laminated type or a single layer type. And the sensitivity is excellent. Furthermore, a commercially available electrophotographic copying machine (Minolta Camera Co., Ltd .; EP-350Z)
Was performed on the photoreceptor of Example 18 by using the photoreceptor of Example 18. However, even when 1000 copies were made, the initial and final images had excellent gradation, no change in sensitivity, and a clear image was obtained. This indicates that the photoreceptor of the present invention has stable repetition characteristics.

[0067]

The present invention has provided a novel diamino compound. The diamino compound provided by the present invention can be used for a photoreceptor and a charge transport layer of an electroluminescent device. The photoreceptor to which the diamino compound of the present invention is applied to the charge transport layer has excellent photoreceptor characteristics such as sensitivity, charge transportability, initial surface potential, and dark decay rate, and has less light fatigue upon repeated use.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a dispersion type photoreceptor obtained by laminating a photosensitive layer on a conductive support.

FIG. 2 is a schematic cross-sectional view of a function-separated type photoconductor in which a charge generation layer and a charge transport layer are laminated on a conductive support.

FIG. 3 is a schematic cross-sectional view of a function-separated type photoconductor in which a charge transport layer and a charge generation layer are laminated on a conductive support.

FIG. 4 is a schematic sectional view of a photoconductor in which a photosensitive layer and a surface protective layer are formed on a conductive support.

FIG. 5 is a schematic cross-sectional view of a photoconductor in which an intermediate layer and a photoconductive layer are formed on a conductive support.

FIG. 6 shows a schematic sectional view of an electroluminescent device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Charge transport material 3 Charge generation material 4 Photosensitive layer 5 Charge transport layer 6 Charge generation layer 7 Surface protective layer 8 Intermediate layer 11 Anode 12 Charge transport layer 13 Organic light emitting layer 14 Cathode

Continuation of the front page (51) Int.Cl. ⁷ identification code FI G03G 5/06 312 G03G 5/06 312 H05B 33/14 H05B 33/14 (58) Fields investigated (Int.Cl. ⁷ , DB name) C07C 211/00 C07C 217/00 C07C 323/00 C07D 333/00 C09K 11/06 G03G 5/06 H05B 33/14 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. The following general formula [I]: Wherein, Ar ₁ and Ar _2, methylation group, an alkyl group selected from ethyl or propyl group, an aralkyl group selected from benzyl group or a phenethyl group, a phenyl group, a biphenyl group or a thienyl group, a furyl group, a pyrrolyl a heterocyclic group selected from the group or a pyridyl group and <br/> shown, each of these groups, a methyl group, an ethyl group, flop
Substitution selected from ropyl, butyl or methoxy
May have a _{group; R 1, R 2, R} 3, R 4 and _{R 5} are each a hydrogen atom, an alkyl group selected from methyl group, an ethyl group or a propyl group, a methoxy group, ethoxy group or propoxy group X represents -O-, -S- or a formula represented by the following formula: (Wherein R ₆ and R ₇ are each a hydrogen atom, a methyl group,
Represents an alkyl group selected from an ethyl group or a propyl group, or an aryl group selected from a phenyl or naphthyl group; n represents an integer of 1 to 4). 2. On a conductive support, the following general formula [I]: Wherein, Ar ₁ and Ar _2, methylation group, an alkyl group selected from ethyl or propyl group, an aralkyl group selected from benzyl group or a phenethyl group, a phenyl group, a biphenyl group or a thienyl group, a furyl group, a pyrrolyl a heterocyclic group selected from the group or a pyridyl group and <br/> shown, each of these groups, a methyl group, an ethyl group, flop
Substitution selected from ropyl, butyl or methoxy
May have a _{group; R 1, R 2, R} 3, R 4 and _{R 5} are each a hydrogen atom, an alkyl group selected from methyl group, an ethyl group or a propyl group, a methoxy group, ethoxy group or propoxy group X represents -O-, -S-, or a compound represented by the following formula: (Wherein R ₆ and R ₇ are each a hydrogen atom, a methyl group,
Represents an alkyl group selected from an ethyl group or a propyl group, or an aryl group selected from a phenyl or naphthyl group; n represents an integer of 1 to 4)]. . 3. The following general formula [I]: Wherein, Ar ₁ and Ar _2, methylation group, an alkyl group selected from ethyl or propyl group, an aralkyl group selected from benzyl group or a phenethyl group, a phenyl group, a biphenyl group or a thienyl group, a furyl group, a pyrrolyl a heterocyclic group selected from the group or a pyridyl group and <br/> shown, each of these groups, a methyl group, an ethyl group, flop
Substitution selected from ropyl, butyl or methoxy
May have a _{group; R 1, R 2, R} 3, R 4 and _{R 5} are each a hydrogen atom, an alkyl group selected from methyl group, an ethyl group or a propyl group, a methoxy group, ethoxy group or propoxy group X represents -O-, -S-, or a compound represented by the following formula: (Wherein R ₆ and R ₇ are each a hydrogen atom, a methyl group,
Represents an alkyl group selected from an ethyl group or a propyl group or an aryl group selected from a phenyl or naphthyl group; n represents an integer of from 1 to 4)]. Luminescent element.