JPH0545905A - Photosensitive body - Google Patents

Abstract

PURPOSE:To obtain the photosensitive body superior in sensitivity, electric charge transfer performance, initial surface potential, and dark decay resistance, and small in photofatigue due to repeated uses by using a specified diamino compound as the charge transfer material of a photosensitive layer. CONSTITUTION:The photosensitive layer formed on a conductive substrate contains the diamino compound represented by formula I in which each of Ar1-Ar4 is alkyl, aralkyl, aryl, biphenyl, or a heterocyclic group, and this compound an be embodied by a compound of formula II, thus permitting this compound to absorb light, to effectively transfer charge carriers, and therefore, to be used for not only the charge transfer material of the photosensitive body but, also the charge transfer layer of electroluminescence elements, and to be superior in photo-stability, oxidation resistance, and ozone resistance, and accordingly, to be enhanced in durability against the repeated uses of the photosensitive body.

Description

Detailed Description of the Invention

[0001]

The diamino compound of the present invention can be used as a light-sensitive material used in electrophotography and the like.
Specifically, it can be used as a charge transport material for a photoreceptor or an electroluminescence element.

[0002]

2. Description of the Related Art Various organic compounds which can be used as a light-sensitive material or a charge-transporting material are conventionally known, for example, anthracene derivative, anthraquinone derivative, imidazole derivative, carbazole derivative, hydrazone derivative, styryl derivative, etc. No. 1-142646 discloses the following general formula:

[Chemical 3] [Wherein R _{1 to} R ₆ represent those described in the above publications], and in JP-A-58-58551, the following general formula:

[Chemical 4] A compound represented by the formula [wherein R _{1 to} R ₈ represent those described in the above publication] is disclosed. However, when the above-mentioned material is applied to, for example, a photoreceptor, it is basically required to have excellent photosensitivity or charge transportability.
Furthermore, compatibility with other members, durability, weather resistance and the like are also required, and in reality, there are few materials that satisfy such characteristics.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a photoconductor or an electroluminescent device using a diamino compound different from any of the structures described above. To do.

[0004]

The present invention has the following general formula [I] on a conductive support:

[Chemical 5] There is provided a photoreceptor having a photosensitive layer containing a diamino compound represented by:

In the general formula [I], Ar ₁ , Ar ₂ , Ar ₃ and
Ar ₄ is independently an alkyl group such as a methyl group or an ethyl group, an aralkyl group such as a benzyl group,
It represents a residue of an aryl group such as a phenyl group and a tolyl group, a biphenyl group, and a heterocyclic group such as thiophene, furan and dithiophene, with a biphenyl group being particularly preferred.
These groups may have an alkyl group such as a methyl group, an alkoxy group such as a methoxy group, or a substituent such as a phenoxy group or a halogen atom. Particularly preferred Ar _{1 to} Ar ₄ are biphenyl groups having an alkyl group. R ₁ , R ₂ , R
Each ₃ independently represents a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, and a halogen atom such as Cl or Br. X is -O-, -S- or

[Chemical 6] Represents. In Chemical Formula 1, 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, and an aryl group such as a phenyl group or a tolyl group, but they do not simultaneously represent a hydrogen atom.

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

[0007]

[Chemical 7]

[0008]

[Chemical 8]

[0009]

[Chemical 9]

[0010]

[Chemical 10]

[0011]

[Chemical 11]

[0012]

[Chemical formula 12]

[0013]

[Chemical 13]

[0014]

[Chemical 14]

[0015]

[Chemical 15]

[0016]

[Chemical 16]

Among the above examples, particularly preferred compounds are [11],
These are [16], [18], [19], [25], [28], [29], [30], [36] and [37].

The diamino compound represented by the general formula [I] can be synthesized by the following method. That is, the following general formula [II]:

[0019]

[Chemical 17] [Wherein X and R _{1 to} R ₃ are the same as those in the general formula [I]] and the following general formulas [III] and [I]
V]:

[0020]

[Chemical 18] [Wherein Ar _{1 to} Ar ₄ are the same as those in the general formula [I]] by synthesizing an amino compound by Ullmann reaction in the presence of a basic compound or a transition metal compound catalyst and a solvent. You can

As the basic compound used in the present invention, alkali metal hydroxides, carbonates, hydrogen carbonates, alcoholates and the like are generally used, and quaternary ammonium compounds, aliphatic amines and aromatic compounds are used. It is also possible to use organic bases such as 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, carbonates and hydrogen carbonates of alkali metals are most preferable.

Examples of the transition metal or transition metal compound used in the present invention include Cu, Fe, Co, Ni, Cr, V, Pd,
Metals such as Pt and Ag and their compounds are used.
Copper and palladium and their compounds are preferable in terms 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, cuprous acetate, cupric acetate and the like are preferable. Among them, especially CuCl, CuCl ₂ , CuBr, CuBr ₂ , CuI, Cu
O, Cu ₂ O, CuSO ₄ , Cu (OCOCH ₃ ) ₂ are preferable because they are easily available. As a 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 halide to be reacted.

The solvent used in the present invention may be a commonly used solvent, but an aprotic polar solvent such as nitrobenzene, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone is preferably used. The reaction of the present invention is generally 100 to 250 under normal pressure.
It is carried out at a temperature of ° C, but of course it may be carried out under pressure. After the reaction is completed, the solid matter precipitated in the reaction solution is removed, and then the solvent is removed to obtain the product.

The diamino compound represented by the general formula [I] can be used as a light-sensitive material for a photoconductor, especially as a charge-transporting substance. Further, it can be used for the charge transport layer of an electroluminescence device by utilizing its charge transport property. First, the case of use as a charge transport layer of a diamino compound photoreceptor represented by the general formula [I] will be described. The photoreceptor of the present invention has a photosensitive layer containing one or more diamino compounds represented by the general formula [I].
The diamino compound represented by the general formula [I] is particularly excellent in charge transportability.

Various types of photoconductors are known as the photoconductor, and the photoconductor of the present invention may be in any form. 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 resin binder are provided on a support, or a charge generation layer containing a charge generation material as a main component is provided on a support There is a so-called laminated type photoconductor in which a charge transport layer is provided thereon.

The diamino compound of the present invention acts as a charge transporting substance in the photoconductor, and can transport charge carriers generated by absorbing light extremely efficiently.
Further, the diamino compound of the present invention is excellent in light stability, is not easily oxidized because it does not have an olefin double bond in the molecule, has good ozone resistance, and has excellent durability capable of withstanding repeated use. A photoreceptor can be obtained. Further, the diamino compound of the present invention has good compatibility with the binder resin, and a photoreceptor having excellent sensitivity and repeatability can be obtained.

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 dye Organic substances such as pigments, bisbenzimidazole pigments, indathlon pigments, squalium salt pigments, azulene pigments, phthalocyanine pigments, pyrrolopyrrole pigments, selenium alloys such as selenium, selenium tellurium, selenium arsenic, and sulfides. Inorganic substances such as cadmium, cadmium selenide, zinc oxide, and amorphous silicon can be mentioned.
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 and the mechanical strength of the photosensitive layer will be weak. 0.
The range is from 01 to 2 parts by weight, preferably from 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% by weight with respect to 1 part by weight of the binder resin.
˜2 parts by weight, preferably 0.2 to 1.5 parts by weight.
If the amount is less than 0.01 parts by weight, the sensitivity will be poor, and if it is more than 2 parts by weight, the functional strength of the photosensitive layer will be weakened and the repeating characteristics will be deteriorated.

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 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. 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 5 μm.
0 μm, preferably 5 to 30 μm. The ratio of the charge transport material in the charge transport layer is 0.2 with respect to 1 part by weight of the binder resin.
To 2 parts by weight, preferably 0.3 to 1.3 parts by weight.

The photoreceptor of the present invention contains a binder resin, a plasticizer such as halogenated paraffin, polychlorinated biphenyls, dimethylnaphthalene, dibutylphthalate and O-terphenyl, chloranil, tetracyanoethylene, 2,4,7.
-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 binder such as an electrically insulating thermoplastic resin known per se or a thermosetting resin, a photocurable resin or a photoconductive resin is used. it can. The conductive support used in the photoreceptor of the present invention, copper, aluminum, silver,
A sheet or drum of iron or nickel foil or plate is used, or those metals are vacuum-deposited or electroless plated on a plastic film, or a conductive polymer, indium oxide, tin oxide. A layer of a conductive compound such as that provided on a support such as paper or a plastic film by coating or vapor deposition is also used.

1 to 5 schematically show a constitutional example of a photoreceptor using the diamino compound of the present invention. Figure 1 shows the substrate
A photoreceptor having (1) a photosensitive layer (4) in which a photocharge generating material (3) and a charge transporting material (2) are mixed with a binder, the diamino compound of the present invention being used as a charge transporting material. It is used. 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 electroluminescence device 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 the electroluminescence device. In the figure, (11) is an anode on which a charge transport layer is formed.
(12), the organic light-emitting layer (13) and the cathode (14) are sequentially laminated, and the charge transport layer has the above general formula.
It contains a diamino compound represented by [I]. Anode (1
By applying a voltage to 1) and the cathode 14, the organic light emitting layer 13 is colored.

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 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 diamino compound is 2 to the binder resin.
The thickness should be 0.0 so that the content is about 0-80% by weight.
The thickness may be about 5 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 may have a multi-layer structure in order to adjust characteristics such as emission color and emission intensity. 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). One set of transparent electrodes is a suitable lead wire such as nichrome wire, gold wire, copper wire, platinum wire for each electrode (15)
The organic luminescence element is connected to both electrodes
It emits light by applying (Vs). The organic electroluminescent element of the present invention can be applied to various display devices, display devices, and the like.

[0040]

EXAMPLES The photoconductor of the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following examples, "parts" means "parts by weight" unless otherwise specified.

Example 1 Disazo compound represented by the following general formula [A]

[Chemical 19] 0.45 parts and 0.45 part of a polyester resin (Vylon 200; manufactured by Toyobo Co., Ltd.) were dispersed together with 50 parts of cyclohexanone by a sand grinder. The obtained disazo compound dispersion was dried on aluminized mylar having a thickness of 100 μm using a film applicator to give a dry film thickness of 0.3 g.
It was coated so as to be / m ² and then dried.

70 parts of the 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 photoconductor thus obtained 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 structure as in Example 1, but the diamino compound [5], [6], [7] used in place of the diamino compound [2] used in Example 1. 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 Disazo compound represented by the following general formula [B]

[Chemical 20] 0.45 parts, polystyrene resin (molecular weight 40,000) 0.4
5 parts together with 50 parts cyclohexanone were dispersed by a sand grinder.

The dispersion of the obtained bisazo compound was applied 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 the diamino compound [10] and 70 parts of polyarylate resin (U-100; Unitika Ltd.) in 400 parts of 1,4-dioxane on the charge generation layer thus obtained was dried as a dry film. 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 [10] used in Example 5 was replaced by diamino compounds [11], [13] and [16]. 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]

[0049]

[Chemical 21] 0.45 parts, polycarbonate resin (Panlite K-13
000: manufactured by Teijin Chemicals Ltd.) 0.45 parts with dichloroethane 50
It was dispersed together with the parts by a sand grinder. 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.
On the charge generation layer thus obtained, 60 parts of diamino compound [17] and polyarylate resin (U-100;
A solution prepared by dissolving 50 parts of Unitika Co., Ltd. in 400 parts of 1,4-dioxane is applied so that the dry film thickness becomes 18 μm,
The charge transport layer was formed by drying. In this way, 2
An electrophotographic photoreceptor having a photosensitive layer composed of layers was produced.

Examples 10 to 11 Photosensitizers having the same constitution as in Example 9 except that diamino compounds [18] and [25] were used instead of the diamino compound [17] 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 formula 22] 0.45 parts and 0.45 part 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 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. On the charge generation layer thus obtained, 50 parts of a diamino compound [26] and 50 parts of a polycarbonate resin (PC-Z; manufactured by Mitsubishi Gas Chemical Co., Inc.) were added.
The solution dissolved in 400 parts of 4-dioxane has a dry film thickness of 1
It was coated so as to have a thickness of 8 μm to form a charge transport layer. 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 [28] and [29] are used instead of the diamino compound [26] used in Example 12. 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 (B
(X-1; manufactured by Sekisui Chemical Co., Ltd.) (0.45 part) was dispersed with 50 parts of dichloroethane by a sand grinder.
The obtained dispersion of phthalocyanine pigment is 100 μm thick
A film applicator was used to apply a dry film thickness of 0.3 g / m ² on the aluminized mylar of Example 1 and then dried. 50 parts of diamino compound [31] and a polycarbonate resin (P
A solution prepared by dissolving 50 parts of CZ (manufactured by Mitsubishi Gas Chemical Co., Inc.) in 400 parts of 1,4-dioxane was applied so as to have a dry film thickness of 18 μm to form a charge transport layer. In this way
An electrophotographic photosensitive member having a photosensitive layer composed of two layers was produced.

Examples 16 to 17 Photosensitizers having the same constitution as in Example 15 except that diamino compounds [36] and [37] were used instead of the diamino compound [31] used in Example 15, respectively. The body was made. The thus obtained photosensitive member was measured _{V 0, E 1/2,} DDR 1 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 in an amount of 22.5 parts of a thermosetting acrylic resin (Acridic A405; manufactured by Dainippon Ink and Chemicals) and a melamine resin (Super Beckamine J).
820; Dainippon Ink and Chemicals, Inc.) 7.5 parts, diamino compound [3
8] 15 parts were placed in a ball mill pot together with 100 parts of a mixed solvent in which methyl ethyl ketone and xylene were mixed in equal amounts, and dispersed for 48 hours to prepare a photosensitive coating liquid, which was coated on an aluminum substrate and dried. Thickness about 15μm
To form a photosensitive layer to prepare a photoreceptor. 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 The same method as in Example 18 but having the same constitution, except that the diamino compound [38] used in Example 18 was replaced by diamino compounds [42], [44] and [48]. 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 constitution as in Example 18 except that the diamino compound used in Example 18 was replaced by the following compound
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 23] 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 and the same method as in Example 18, except that the following compounds [I], [J] and [K] were used instead of the diamino compound [38] used in Example 18. A photoconductor was prepared in exactly the same manner as in Example 18 except that each was used.

[Chemical formula 24] In Comparative Examples 1 to 7, compounds [G], [H], [I]
With respect to the photosensitive coating liquid using [H] and [H], it was observed that some crystals were precipitated during the coating of the photosensitive layer. 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. Table 1 shows the measurement results of V ₀ , E _1/2 and DDR ₁ of the photoconductors obtained in Examples 1 to 21 and Comparative Examples 1 to 7.

[0058]

[Table 1]

As can be seen from Table 1, the photoconductor of the present invention has a sufficient charge holding 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.
It is also excellent in sensitivity. Furthermore, a repeated actual-photographing test was performed on the photoconductor of Example 18 at the time of positive charging with a commercially available electrophotographic copying machine (manufactured by Minolta Camera Co .; EP-350Z).
It can be seen that in the final image, the gradation is excellent, there is no change in sensitivity and a clear image is obtained, and the photoreceptor of the present invention has stable repeatability.

[0060]

The present invention provides a photoreceptor containing a diamino compound as a charge transport material in a photosensitive layer. The photoconductor to which the diamino compound of the present invention was applied as the charge transport material for the photoconductive layer was excellent in photoconductor properties such as sensitivity, charge transportability, initial surface potential, and dark decay rate, and light fatigue after repeated use was small.

[Brief description of drawings]

FIG. 1 is a schematic view of a dispersion-type photosensitive member formed by laminating a photosensitive layer on a conductive support.

FIG. 2 is a schematic diagram 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 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 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 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 element.

[Explanation of symbols]

1: conductive support, 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

Claims (1)

[Claims] 1. A compound represented by the following general formula [I] on a conductive support: [Wherein Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ are each independently an alkyl group which may have a substituent, an aralkyl group,
Represents an aryl group, a biphenyl group or a heterocyclic group; R
₁ , R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group or an alkoxy group, or a halogen atom; X is —O—, —S— or (In the formula, R ₄ and R ₅ represent a hydrogen atom, an alkyl group or an aryl group, but are not simultaneously a hydrogen atom). ] The photoreceptor which has the photosensitive layer containing the diamino compound represented by these.