JPH05105651A - Novel diamond compound and photosensitizer using the same - Google Patents

Abstract

PURPOSE:To provide a novel diamond compound suitably usable as an electric charge transport material for photosensitizers or electroluminescence elements. CONSTITUTION:A compound of formula I [Ar1 and Ar2 are each (substituted) alkyl, (substituted)aralkyl, (substituted)aryl, (substituted)biphenyl or (substituted) heterocyclic group; R1-R5 are each H, alkyl, alkoxy or halogen; X is O, S or formula II (R6 and R7 are each H, (substituted)alkyl or (substituted)aryl; (n) is 1-4)], e.g. a compound of formula II. This compound can be obtained by Ullmann reaction of a diamine compound of formula IV and respective iodides of formula V, formula VI, formula At1-I and formula Ar2-I in the presence of a basic compound or transition metal compound catalyst in an appropriate solvent. A photosensitizer having this compound applied to the electric charge transport layer is excellent in sensitivity, electric charge transport ability, initial surface potential and the beam attenuator characteristics in dark attenuation factor,. also being low in the light fatigue after repeated use.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel compound having a diamino structure. The diamino compound can be used as a light-sensitive material, and more specifically, can be used as a charge-transporting material for a photoconductor or an electroluminescence element.

[0002]

2. Description of the Related Art Conventionally, various organic compounds usable as a light-sensitive material or a charge-transporting material are known, such as anthracene derivative, anthraquinone derivative, imidazole derivative, carbazole derivative and styryl derivative.
JP-A-2-190864 discloses the following general formula:

[Chemical 5] An arylamine compound represented by the formula [wherein Ar _{1 to} ARr and R _{1 to} R ₂ are the same as those described in the above-mentioned publication] is disclosed in JP-A-2-59761 having the following general formula:

[Chemical 6] A triarylamine derivative represented by the formula [wherein Ar _{1 to} Ar ₄ and X _{1 to} X ₂ are as 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 represented arylamine compounds are disclosed.

However, the above-mentioned materials are basically required to have excellent photosensitivity or charge transportability when applied to, for example, a photoconductor, but further compatibility with other members and durability are required. However, weather resistance and the like are also required, and in reality, there are few materials that satisfy such characteristics.

[0004]

The present invention has been made in view of the above circumstances, and an object thereof is 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 photoconductor using the novel diamino compound. The present invention is
Another object of the present invention is to provide an electroluminescent device using the novel diamino compound in a charge transport layer.

[0005]

The present invention has the following general formula:
[I]:

[Chemical 7] A diamino compound represented by

In the general formula [I], Ar ₁ and Ar ₂ are each 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, and an aryl group such as a phenyl group. , A biphenyl group or a heterocyclic group such as a thienyl group, a furyl group, a pyrrolyl group or a pyridyl group. These groups may have a substituent such as an alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.) or an alkoxy group (methoxy group, etc.). Preferred Ar ₁ and Ar ₂ are phenyl group and biphenyl group. The biphenyl group further improves the charge mobility.

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each 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:

[Chemical 8] 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, and 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 formula.

[Chemical 9]

[0010]

[Chemical 10]

[0011]

[Chemical 11]

[0012]

[Chemical 12]

[0013]

[Chemical 13]

[0014]

[Chemical 14]

[0015]

[Chemical 15]

[0016]

[Chemical 16]

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] and [36] are particularly preferable.

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]:

[Chemical 17] [Wherein X, R ₂ , R ₃ and R ₃ have the same meanings as those in the general formula [I]], and a diamine compound represented by the following general formula [II]
I], [IV], [V] and [VI]:

[Chemical 18] [Wherein R ₁ and R ₅ , and Ar ₁ and Ar ₂ are the same as those in the general formula [I]] and an iodide represented by the formula [I] in the presence of a basic compound or a transition metal compound catalyst in a suitable solvent. , Ullmann
It can be synthesized by a reaction.

Also, after acetylating the compound represented by the general formula [II], the iodides of the general formulas [III] and [V] are condensed, and then deacetylated, and then the general formula [IV]. ], [VI] iodide may be condensed.

Further, the general formula [VII]:

[Chemical 19] [In the formula, R ₂ , R ₃ , R ₄ and X are the same as those in the general formula [I]] and the following general formula [VII]
I] and [IX]:

[Chemical 20] [Wherein R ₁ , R ₅ and Ar _{1 to} Ar ₂ have the same meanings as those in formula [I]] in a suitable solvent in the presence of a basic compound or a transition metal compound catalyst. At 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, alkali metal hydroxides, carbonates, hydrogen carbonates, alcoholates and the like are generally used, and quaternary ammonium compounds and fats. It is also possible to use organic bases such as group amines and aromatic amines.
Of these, alkali metal and quaternary ammonium carbonates and hydrogen carbonates are preferably used. Furthermore,
From the viewpoint of reaction rate and thermal stability, alkali metal carbonates and hydrogen carbonates are most preferable.

Examples of the transition metal or transition metal compound used in the synthesis of the diamino compound of the present invention include 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 preferable 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, cupric nitrate, cupric nitrate, copper carbonate, acetic acid Copper, cupric acetate, etc. are preferred. Among them, especially CuC
l, CuCl ₂ , CuBr, CuBr ₂ , CuI, CuO, Cu
₂ O, CuSO ₄ , and Cu (OCOCH ₃ ) ₂ are preferable because 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 a commonly used solvent, but an aprotic polar solvent such as nitrobenzene, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone is preferably used.

The reaction is generally 100 to 250 under normal pressure.
It is carried out at a temperature of ℃, but of course it may be carried out under pressure. After the completion of the reaction, the solid matter that has broken out into the reaction solution can be removed, and then the solvent can be removed to obtain the product.

These diamino compounds may be used alone or in combination. It is also possible to use it as a mixture with another charge transport material, 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 light-sensitive material for a photoconductor, particularly as a charge transport substance. Further, it can be used for the charge transport layer of an electroluminescence device by utilizing its charge transport property.

First, the case where the diamino compound represented by the general formula [I] is used as the charge transport material of the photoconductor will be described. Various types of photoconductors are known as photoconductors, and the diamino compound of the present invention can be applied to any form of the photoconductor. For example, a single-layer photoconductor in which a charge generation material and a photosensitive layer in which a charge transport material is dispersed in a binder resin are provided on a support, or a charge generation layer containing a charge generation material as a main component on a support are used. There is a so-called laminated type photoconductor in which a charge transport layer is provided on the photoconductor. One or more diamino compounds of the present invention are used as a charge transport material. The diamino compound acts as a charge transport material and can transport charge carriers generated by absorbing light very efficiently. In particular, it is possible to make a photoreceptor that contributes significantly to the improvement of charge mobility and is excellent in high-speed response.

Further, since the diamino compound of the present invention has excellent ozone resistance and light stability, a photoreceptor having excellent durability can be obtained. Furthermore, the diamino compound of the present invention has good compatibility with the binder resin and is less likely to precipitate crystals, which contributes to improvement in sensitivity and repeatability.

As the charge generating material, a bisazo pigment,
Triarylmethane dye, thiazine dye, oxazine dye, xanthene dye, cyanine dye, styryl dye, pyrylium dye, azo pigment, quinacridone pigment, indigo pigment, perylene pigment, polycyclic quinone pigment , Bisbenzimidazole-based pigments, indusulon-based pigments, squalium salt-based pigments, azulene-based pigments, phthalocyanine-based pigments and other organic substances, selenium, selenium / tellurium, selenium / arsenic and other selenium alloys, cadmium sulfide, cadmium selenide Inorganic substances such as zinc oxide and amorphous silicon. Other than this, any material can be used as long as it absorbs light and generates charge carriers with an extremely high probability.

Examples of suitable binder resins include, but are not limited to, saturated polyester resins, polyamide resins, acrylic resins, ethylene-vinyl acetate resins, ionically cross-linked 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 resins such as thermosetting acrylic resins; photocurable resins; photoconductive resins such as polyvinylcarbazole, polyvinylpyrene, polyvinylanthracene, and polyvinylpyrrole. These can be used alone or in combination. These electrically insulating resins are individually measured to be 1 × 10
It is desirable to have a volume resistance of ¹² Ω · cm or more.

In order to prepare 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
The thickness is 0 μm, preferably 5 to 20 μm. If the amount of the charge generating material used is too small, the sensitivity will be poor, and if it is too large, the charging property will be poor, or the mechanical strength of the photosensitive layer will be weakened. On the other hand, 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 the charge transport material is 0.01 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, and more preferably 1 part by weight of the binder resin. It is 0.2 to 1.2 parts by weight. 0.
When the amount is less than 01 parts by weight, the sensitivity is poor, and when the amount is more than 2 parts by weight, the film formability is poor and the mechanical strength of the photosensitive layer is weakened.

In order to prepare a laminated type photoreceptor, a charge generating material is vacuum-deposited on a conductive support, or is dissolved in an appropriate solvent and applied, or a pigment is added in an appropriate solvent or necessary. For example, it can be obtained by coating and drying a coating solution prepared by dispersing it in a solution in which a binder resin is dissolved, and then coating 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, preferably 5 to 30 μm. The ratio of the charge transport material in the charge transport layer is 0.2 to 1 part by weight of the binder resin.
2 parts by weight, preferably 0.3 to 1.3 parts by weight.

In the photoreceptor of the present invention, a plasticizer such as halogenated paraffin, polychlorinated biphenyls, dimethylnaphthalene, dibutyl phthalate and O-terphenyl, chloranil, tetracyanoethylene, 2,4,7 together with a binder resin are used.
-Trinitrofluorenone, 5,6-dicyanobenzoquinone, tetracyanoquinodimethane, tetrachlorophthalic anhydride, electron withdrawing sensitizer such as 3,5-dinitrobenzoic acid, methyl violet, rhodamine B, cyanine dye, pyrylium salt A sensitizer such as thiapyrylium salt may be used. As the electrically insulating binder resin used in the present invention, a known electrically insulating thermoplastic resin or a binder such as a thermosetting resin, a photocurable resin or a photoconductive resin 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 a sheet shape or a drum shape is used, or these metals are used as a plastic film. Vacuum-deposited, electroless plated, conductive polymer, indium oxide, etc.
A layer in which a conductive compound layer such as tin oxide is provided by coating or vapor deposition on a support such as paper or a plastic film is also used.

An example of the constitution of a photoreceptor using the diamino compound of the present invention is schematically shown in FIGS. Figure 1 shows the substrate
A photoreceptor having (1) a photosensitive layer (4) in which a charge generating material (3) and a charge transporting material (2) are mixed with a binder, and the diamino compound of the present invention is used as the charge transporting material. Has been. FIG. 2 shows a function separation type photoreceptor having a charge generation layer (6) and a charge transport layer (5) as a photosensitive layer.
The charge transport layer (5) is formed on the surface of (6). The diamino compound of the present invention is incorporated in the charge transport layer (5). Similar to FIG. 2, FIG. 3 shows a function-separated type photoreceptor having a charge generation layer (6) and a charge transport layer (5). Contrary to FIG. 2, charges are formed on the surface of the charge transport layer (5). A generation layer (6) is formed. FIG. 4 shows a surface protective layer on the surface of the photoreceptor of FIG.
(7) is provided, and the photosensitive layer (4) is a charge generation layer (6).
And a function-separated type photoreceptor having a charge transport layer (5). FIG. 5 shows an intermediate layer between the substrate (1) and the photosensitive layer (4).
(8) is provided, and the intermediate layer (8) has improved adhesiveness,
It can be provided in order to improve the coating property, protect the substrate, and improve the charge injection property from the substrate to the photosensitive layer.

Suitable materials for the intermediate layer are polyimide, polyamide, nitrocellulose, polyvinyl butyral, polyvinyl alcohol, aluminum oxide and the like, and the film thickness is preferably 1 μm or less.

The diamino compound represented by the general formula [I] of the present invention can be applied to the charge transport layer of an electroluminescent device by utilizing its charge transport property. Hereinafter, the case where the diamino compound of the present invention is applied to the charge transport layer of an electroluminescence 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) are provided.
And the cathode (14) are sequentially laminated,
The charge transport layer contains the diamino compound represented by the above 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 electroluminescent device
As the conductive substance used as (11), those having a work function larger than 4 eV are preferable, and carbon, aluminum, vanadium, iron, cobalt, nickel, copper, zinc,
Tungsten, silver, tin, gold etc. and their alloys,
Tin oxide and indium oxide are used. The metal forming the cathode 14 preferably has a work function smaller than 4 eV, and magnesium, calcium, titanium, yttrium, lithium, gadolinium, ytterbium, ruthenium, manganese, and alloys thereof are used.

In the organic electroluminescence device, 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, so the anode is preferably a transparent electrode. When the transparent electrode is formed, the conductive material as described above may be formed on the transparent substrate by means of vapor deposition, sputtering or the like so as to ensure a desired light-transmitting property. As a transparent substrate, it has an appropriate strength, and when manufacturing an electroluminescence element,
It is not particularly limited as long as it is transparent and is not adversely affected by heat due to vapor deposition and the like, and examples thereof include a glass substrate, a transparent resin such as polyethylene, polypropylene, polyether sulfone, and polyether ether ketone. It is also possible to use. Commercially available products such as ITO and NESA are known as those having a transparent electrode formed on a glass substrate, and these may be used.

The charge transport layer (12) has the above-mentioned general formula [I].
It may be formed by vapor deposition of a diamino compound represented by, or may be formed by spin coating an appropriate solution or resin solution of the diamino compound. When it is formed by a vapor deposition method, its thickness is usually 0.01 to 0.3 μm, and when it is formed by a spin coating method, the content of the diamino compound is about 20 to 500% by weight with respect to the binder resin. So that the thickness is about 0.05 to 1.0 μm.

An organic light emitting layer is formed on the charge transport layer 12 thus formed. As the organic light-emitting body used in the organic light-emitting layer, known ones can be used. For example, epidrizine, 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, 2,
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 bisoxine, bis (benzo-8-quinolinol) zinc, bis (2-methyl-8quinolinolato) aluminum oxide, indium tris Oxine, aluminum tris (5-methyloxine), lithium oxine, gallium trioxine, calcium bis
(5-chlorooxine), polyzinc-bis (8-hydroxy-5-quinolinonyl) methane) dilithium epinedridione, zinc bisoxine, 1,2-phthaloperinone, 1,
2-naphthaloperinone etc. can be mentioned. In addition, general fluorescent dyes such as fluorescent coumarin dyes, fluorescent perylene dyes, fluorescent pyran dyes, fluorescent thiopyran dyes,
A fluorescent polymethine dye, a fluorescent merocyanine dye, a fluorescent imidazole dye and the like can also be used. Among these, a chelated oxinoid compound is particularly preferable. The organic light-emitting layer may have a single-layer structure of the above-mentioned light-emitting substance, or in order to adjust characteristics such as emission color and emission intensity,
It may have a multilayer structure. Next, the above-mentioned cathode is formed on the organic light emitting layer.

As described above, the charge transport layer (12) 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).

A pair of transparent electrodes is connected to each electrode by a suitable lead wire (15) such as a nichrome wire, a gold wire, a copper wire, a platinum wire,
The organic luminescence element emits light by applying an appropriate voltage (Vs) to both electrodes.

The organic electroluminescent element of the present invention can be applied to various display devices or display devices. The present invention will be described below with reference to specific examples. In the following examples, "part" means
Unless otherwise specified, it means "parts by weight".

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

[Chemical 21] 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 are charged into a 500 ml four-necked flask equipped with a reflux condenser and placed under a nitrogen stream for 20 minutes.
The mixture was reacted with stirring 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 then the solid product was filtered. The filtrate was separated by silica gel column chromatography, and the separated product was recrystallized in toluene for purification to obtain 5.8 g of pale yellowish white crystals. The results of elemental analysis are shown in Table 1 below (C ₆₆
H ₄₈ N ₂ O ₂ ).

[0046]

[Table 1]

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

[Chemical formula 22] 0.45 parts and 0.45 parts of polyester resin (Vylon 200; manufactured by Toyobo Co., Ltd.) were dispersed with 50 parts of cyclohexanone by a sand grinder. The resulting dispersion of the bisazo compound was applied onto a 100 μm thick aluminized mylar using a film applicator so that the dry film thickness would be 0.3 g / m ^2, and then dried.

70 parts of a diamino compound [2] and a polycarbonate resin were formed on the charge generation layer thus obtained.
(Panlite K-1300; Teijin Chemicals) 70 parts 1,4
A solution of 400 parts dioxane dissolved in a dry film having a thickness of 16
It was coated so as to have a thickness of μm and dried to form a charge transport layer. Thus, an electrophotographic photosensitive member having a photosensitive layer composed of two layers was obtained.

The thus-obtained photosensitive member was used in a commercially available electrophotographic copying machine (Minolta Camera Co .; EP-470Z).
Exposure amount E _1/2 (lux · se) required to halve the initial surface potential V ₀ (V) and the initial potential by corona charging at −6 Kv
c) Attenuation rate DD of initial potential when left in the dark for 1 second
R ₁ (%) was measured.

Examples 2 to 4 have the same constitution as in Example 1 except that the diamino compound [2] used in Example 1 was replaced by diamino compounds [3], [4] and [5]. A photoconductor using each of the above was prepared. With respect to the photoconductor thus obtained, V ₀ , E _1/2 and DDR ₁ were measured in the same manner as in Example 1.

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

[Chemical formula 23] 0.45 parts, polystyrene resin (molecular weight 40,000) 0.
45 parts were dispersed with a sand grinder together with 50 parts of cyclohexanone.

The dispersion of the obtained bisazo compound was made to a thickness of 1
A film applicator was used to apply a dry film thickness of 0.3 g / m ² on 00 μm aluminized mylar, 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 was dried on the charge generation layer thus obtained. The charge transport layer was formed by applying the solution so as to have a thickness of 16 μm and drying it. In this way, an electrophotographic photosensitive member having a photosensitive layer composed of two layers was produced.

Examples 6 to 8 have the same constitution as in Example 5, except that the diamino compound [6] used in Example 5 is replaced by diamino compounds [7], [9] and [10]. A photoconductor using each of the above was prepared.
With respect to the photoconductor thus obtained, V ₀ , E _1/2 and DDR ₁ were measured in the same manner as in Example 1.

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

[Chemical formula 24] 0.45 parts, polycarbonate resin (Panlite K-1
3000: Teijin Chemicals Ltd.) 0.45 parts dichloroethane 5
It was dispersed by a sand mill together with 0 part. The obtained polycyclic quinone pigment dispersion 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. The diamino compound is formed on the charge generation layer thus obtained.
[11] A solution prepared by dissolving 60 parts and 50 parts of polyarylate resin (U-100; manufactured by Unitika Ltd.) in 400 parts of 1,4-dioxane was applied to a dry film thickness of 18 μm, dried and subjected to charge transport. Layers were formed. In this way, an electrophotographic photosensitive member having a photosensitive layer composed of two layers was produced.

Examples 10 to 11 Photosensitizers having the same structure and the same method as in Example 9, except that diamino compounds [12] and [13] were used instead of the diamino compound [11] used in Example 9, respectively. The body was made. With respect to the photoconductor thus obtained, V ₀ , E _1/2 and DDR ₁ were measured in the same manner as in Example 1.

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

[Chemical 25] 0.45 parts and 0.45 parts of butyral resin (BX-1; manufactured by Sekisui Chemical Co., Ltd.) were dispersed by a sand mill together with 50 parts of dichloroethane. The obtained dispersion of perylene-based pigment was applied onto aluminized mylar having a thickness of 100 μm 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 the diamino compound [16] and 50 parts of a polycarbonate resin (PC-Z; manufactured by Mitsubishi Gas Chemical Co., Inc.) in 400 parts of 1,4-dioxane was dried on the charge generation layer thus obtained. The charge transport layer was formed by coating so as to have a film thickness of 18 μm. In this way, an electrophotographic photosensitive member having a photosensitive layer composed of two layers was produced.

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

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

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

Example 18 50 parts of copper phthalocyanine and 0.2 part of tetranitrocopper phthalocyanine were dissolved in 500 parts of 98% concentrated sulfuric acid with sufficient stirring, and this was poured into 5000 parts of water, and photoconductivity of copper phthalocyanine and tetranitrocopper phthalocyanine. After depositing the 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 used for 22.5 parts of a thermosetting acrylic resin (Acridic A405; manufactured by Dainippon Ink and Chemicals), and melamine resin (Super Beckamine J
820; Dainippon Ink and Chemicals, Inc.) 7.5 parts, diamino compound
[34] Fifteen parts were placed in a ball mill pot together with 100 parts of a mixed solvent of methyl ethyl ketone and xylene in the same amount and dispersed for 48 hours to prepare a photosensitive coating liquid, which was coated on an aluminum substrate and dried. And the thickness is about 15μ
A photosensitive layer of m was formed to prepare 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 Compounds having the same structure and the same method as in Example 18, except that the diamino compound [34] used in Example 18 was replaced by diamino compounds [30], [32] and [36]. A photoconductor using each of the above was prepared. Regarding the photoreceptor thus obtained, Example 1
V ₀ , E _1/2 and DDR ₁ were measured in the same manner as in Example 8.

Comparative Examples 1 to 4 Compounds having the same structure and the same method as in Example 18, except that the following compound was used instead of the diamino compound used in Example 18.
Example 18 except that [E], [F], [G], and [H] are used, respectively.
A photoconductor was prepared in exactly the same manner as in.

[Chemical formula 26] With respect to the thus obtained photoreceptor, V ₀ , E _1/2 and DDR ₁ were measured in the same manner as in Example 18.

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

[Chemical 27] In Comparative Examples 1 to 7, compounds [G], [H] and [I]
Regarding the photosensitive coating liquid using, it was observed that 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 photoconductor of the present invention has a sufficient charge retention ability in both the laminated type and the single layer type, and the dark decay rate is small enough to be used as a photoconductor. , Also excellent in sensitivity. Furthermore, a commercially available electrophotographic copying machine (Minolta Camera Co .; EP-350Z)
A repeated actual-photographing test was conducted on the photoconductor of Example 18 by positive charging. However, even after 1,000 copies were made, excellent gradation was obtained in the initial and final images, and there was no sensitivity change and clear images were obtained. It can be seen that the photoreceptor of the present invention has stable repeatability.

[0067]

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

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a dispersion type photoconductor in which a photosensitive layer is laminated on a conductive support.

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

FIG. 4 is a schematic cross-sectional view of a photoconductor in which a photoconductive 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 cross-sectional view of an electroluminescent device.

[Explanation of symbols]

 1 Base 2 Charge Transport Material 3 Charge Generation Material 4 Photosensitive Layer 5 Charge Transport Layer 6 Charge Generation Layer 7 Surface Protection 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. ⁵ Identification code Office reference number FI Technical display location G03G 5/06 312 8305-2H H05B 33/14 8815-3K

Claims (2)

[Claims] 1. The following general formula [I]: [In the formula, Ar ₁ and Ar ₂ each represent an alkyl group, an aralkyl group, an aryl group, a biphenyl group or a heterocyclic group which may have a substituent; R ₁ , R ₂ , R ₃ and R ₄ and R ₅ each represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom; X is —O—, —S— or the following formula: (In the formula, R ₆ and R ₇ each represent a hydrogen atom or an optionally substituted alkyl group or aryl group; n is 1
Represents an integer of 4 to 4]. 2. The following general formula [I]: embedded image on a conductive support. [In the formula, Ar ₁ and Ar ₂ each represent an alkyl group, an aralkyl group, an aryl group, a biphenyl group or a heterocyclic group which may have a substituent; R ₁ , R ₂ , R ₃ and R ₄ and R ₅ each represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom; X is —O—, —S— or the following formula: (In the formula, R ₆ and R ₇ each represent a hydrogen atom, which may have a substituent, or an alkyl group or an aryl group; n is 1
[Representing an integer of 4]], and a photoreceptor having a photosensitive layer containing a diamino compound represented by